WO2007007547A1

WO2007007547A1 - Ink jet recording material and display material using the same

Info

Publication number: WO2007007547A1
Application number: PCT/JP2006/312817
Authority: WO
Inventors: Shigeki Nishimura
Original assignee: Mitsubishi Plastics, Inc.
Priority date: 2005-07-13
Filing date: 2006-06-27
Publication date: 2007-01-18
Also published as: JPWO2007007547A1

Abstract

This invention provides an ink jet recording material, which can simultaneously realize excellent productivity and antiblocking properties, and a display material using the same. The ink jet recording material is characterized by comprising a base material layer and, stacked on the base material layer in the following order, an optionally stacked adhesive layer and an ink receptive layer formed of a hydrophilic resin, all of the layers having been simultaneously formed by melt coextrusion molding.

Description

Inkjet recording materials and display materials using the same

TECHNICAL FIELD [0001] The present invention relates to an ink jet recording material and a display material using the same.

[0002] Inkjet recording methods are generally widely used because they enable fine recording at low cost. In recent years, higher performance inkjet printers have been developed by improving hardware such as inkjet heads and software such as raster image processors. Along with this, the development of ink jet recording materials that can record output images from printers with high image quality and can be stored for a long time is also progressing. As a result, many display materials such as signs and panels using inkjet recording materials have been found in the market.

[0003] The ink receiving layer of an ink jet recording material mainly includes a "void type" in which porous inorganic fine particles for absorbing ink are fastened with a binder of a hydrophobic resin, and a hydrophilic resin itself. There are two types of "swelling type" that absorb S ink. Of these, void-type ink-receiving layers are currently mainstream from the viewpoints of ink drying properties and water resistance.

[0004] However, a void-type inkjet recording material in which the resin of the ink receiving layer is hydrophobic has a mechanism for absorbing ink by capillary action because the pores of the porous inorganic fine particles absorb the ink. There is a limit. For this reason, the amount of ink absorbed was insufficient for commercial display materials that required high density and gradation so that they could be seen well from a distance. In order to increase the amount of ink absorbed by the void-type ink receiving layer, it may be possible to increase the thickness of the ink receiving layer. However, since the void-type ink-receiving layer is mainly formed by solution coating with an aqueous solvent, the coating amount is limited considering the high boiling point of water and poor coating properties, which is not easy.

[0005] On the other hand, those using a hydrophilic resin for the ink receiving layer are excellent in ink absorbing ability because they can absorb the ink itself. Suitable for applications that require high density and gradation.

[0006] Since display materials are used in harsh environments such as outdoors, when using an ink jet recording material as a display material, it is necessary to provide a surface protective layer for imparting scratch resistance and weather resistance. is there. As an ink jet recording material that can easily be provided with this protective layer, for example, Patent Document 1 discloses an article in which an image is back-printed (mirror print) on a heat-sensitive adhesive ink-receiving layer, and the ink-receiving layer is to be bonded. An ink jet recording material in which a base layer of the ink jet recording material is used as a surface protective layer by heat bonding to the ink jet is disclosed.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2002-67481

Disclosure of the invention

Problems to be solved by the invention

[0007] However, the ink jet recording material of Patent Document 1 is inferior in productivity because the ink receiving layer is produced by solution coating. If recording materials that are multi-layered can be produced by co-extrusion molding at once, productivity will be greatly improved.

[0008] Inkjet recording materials for display materials are often stored and transported as scrolls due to their large size, but when the inkjet recording material is placed in a scroll, the substrate layer May cause the ink receiving layer to block. In order to prevent this, if a base material layer having excellent blocking resistance is used, there has been a problem in that delamination easily occurs with the ink receiving layer.

[0009] Therefore, the present invention has an object to provide an inkjet recording material capable of achieving both excellent productivity and blocking resistance while maintaining high density and gradation, and a display material using the same. And

Means for solving the problem

[0010] Hereinafter, the present invention will be described. In order to facilitate understanding of the present invention, reference numerals in the attached drawings are appended in parentheses, but the present invention is not limited to the illustrated form.

[0011] The invention described in claim 1 includes an adhesive layer (4), which is sequentially laminated on the base material layer (2) as necessary, and an ink receiving layer (3 ) And laminated An ink-jet recording material, which is a recording material and is characterized in that all layers are simultaneously produced by melt coextrusion molding, to solve the above-mentioned problems.

[0012] According to the present invention, it is possible to provide an ink jet recording material excellent in productivity and blocking resistance while maintaining high density and gradation.

[0013] The invention described in claim 2 is characterized in that, on the temporary base layer (1), a transparent base layer (2) and an ink receiving layer (3) made of a hydrophilic resin are sequentially provided. Provided is an ink jet recording material, wherein at least the base material layer (2) and the ink receiving layer (3) are simultaneously produced by melt coextrusion molding. Solve the above problems.

[0014] According to the present invention, it is possible to provide an inkjet recording material excellent in productivity and blocking resistance while maintaining high density and gradation.

[0015] The invention according to claim 3 provides the base layer (2) and the ink receiving layer (3) between the base layer (2) and the ink receiving layer (3). At the same time, the inkjet recording material according to claim 2 is provided to solve the above-mentioned problem, which has an adhesive layer (4) which is melt-coextruded.

[0016] According to the present invention, it is possible to provide an ink jet recording material having more excellent interlayer adhesion.

The invention according to claim 4 is the ink jet recording material according to claim 1 or 3, wherein the adhesive layer (4) is an acid-modified resin. To solve the above problems.

[0018] According to the present invention, an ink jet recording material excellent in adhesiveness can be obtained.

[0019] The invention described in claim 5 is the invention described in claim 1 or 3, wherein the adhesive layer (4) is a blend resin composed of two or more kinds of polymers. Ink jet recording material is provided to solve the above problems.

[0020] According to the present invention, an ink jet recording material excellent in adhesiveness can be obtained.

[0021] The invention according to claim 6 has a slight adhesive layer (5) between the temporary base material layer (1) and the base material layer (2). The ink jet recording material according to item 2 or 3 of the range is provided to solve the problem. [0022] According to the present invention, the temporary base material layer (1) is effectively prevented from peeling from the base material layer (2) before use as a display material. 2) Power to prevent scratches and dirt.

[0023] The invention according to claim 7 is the ink jet recording according to any one of claims 2 to 6, wherein all the layers are melt-coextruded at the same time. Provide materials and solve the above problems.

[0024] According to the present invention, it is possible to provide an ink jet recording material with higher productivity. The invention according to claim 8 is characterized in that the ink receiving layer (3) of the ink jet recording material is a resin represented by the following general formula (1). The display material according to any one of the items 1 is provided to solve the problem.

[0025] [Chemical 1]

A ¹ XA ¹ R ^1- (1)

[In the general formula (1), X ¹ is a residue of an organic compound having two active hydrogen groups, R ¹ is a dicarboxylic acid compound residue, and A ¹ is represented by the following general formula (2) . ]

[0026] [Chemical 2]

[In the general formula (2), Z is a hydrocarbon group having 2 or more carbon atoms, a, b, and c are each an integer of 1 or more, and a mass ratio calculated from a, b, c, {44 ( a + c) / (molecular weight of alkylene oxide having 4 or more carbon atoms) X b} is 80/20 to 94Z6. In addition, cZ (a + c) is set to 50% by mass or more in the mass ratio calculated from each repeating unit a and c. ]

[0027] According to the present invention, an ink jet recording material with higher image density can be obtained.

[0028] The invention according to claim 9 is the inkjet according to any one of claims 1 to 8, wherein the base material layer is mainly composed of polypropylene. A recording material is provided to solve the above problems. [0029] According to the present invention, an inkjet recording material excellent in cost can be obtained.

[0030] The invention according to claim 10 is characterized in that the ink receiving layer (3) contains an antioxidant, and the force 1 according to any one of claims 1-9. An inkjet recording material is provided to solve the above problems.

[0031] According to this invention, an ink-receiving layer having excellent extrusion moldability can be obtained, so that an inkjet recording material having excellent productivity can be obtained.

[0032] The invention described in claim 11 is the ink receiving layer (3) of the ink jet recording material described in any one of claims 2, 3, or 6. ) Display material produced by peeling the temporary substrate layer (1) after heat-sealing the surface to the adherend (

10) is provided to solve the above problem.

Here, “peeling the temporary base material layer” means that the temporary base material layer itself is peeled off, and if the layer configuration includes a fine adhesive layer, the fine adhesive layer is peeled off together with the temporary base material layer. .

[0033] According to the present invention, it is possible to obtain a display material that is excellent in productivity and cost and has reduced contamination and scratches on the surface layer before use.

The invention's effect

[0034] The ink jet recording material of the present invention is excellent in productivity because it is laminated by coextrusion molding, and blocking of the base material layer and the ink receiving layer during storage and transportation can be prevented. Furthermore, recording materials with a temporary base material layer can prevent the base material layer surface from being soiled and scratched before use as a display material, and if you want to make the base material layer thinner, Since the recording material can be stiff depending on the thickness of the temporary base material layer, an ink jet recording material having excellent handleability can be obtained.

Brief Description of Drawings

FIG. 1 is a cross-sectional view of an ink jet recording material of the present invention.

FIG. 2 is a schematic view of a process for producing the display material of the present invention using the ink jet recording material (F) of FIG.

Explanation of symbols

[0036] 1 Temporary substrate layer

2 Base material layer 3 Ink receiving layer

4 Adhesive layer

5 Slightly adhesive layer

6 Adhesive material

10 Display material

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described based on embodiments shown in the drawings.

FIG. 1 is a cross-sectional view of the ink jet recording material of the present invention. The ink jet recording material according to the first aspect of the present invention has a structure in which an ink receiving layer 3 is laminated on a base material layer 2 as shown in FIG. 1 (A). In order to enhance the interlayer adhesion between the base material layer 2 and the ink receiving layer 3, a structure (B) in which an adhesive layer 4 is provided between the base material layer 2 and the ink receiving layer 3 may be employed. The ink jet recording material of the second aspect of the present invention has a structure in which the base material layer 2 and the ink receiving layer 3 are laminated on at least the temporary base material layer 1 as shown in (C). The ink jet recording material of the second aspect may have a structure (D) in which an adhesive layer 4 is provided between the base material layer 2 and the ink receiving layer 3 as in the first aspect. In addition, the ink jet recording material of the second aspect has the temporary base material layer 1 peeled off before being used as a display material, for example, when the adhesive force between the temporary base material layer 1 and the base material layer 2 is too weak. In order to prevent this, the structure (E) having the slight adhesion layer 5 between the temporary base material layer 1 and the base material layer 2 may be used. Further, the ink jet recording material of the second aspect may have a structure (F) provided with the adhesive layer 4 and the slightly adhesive layer 5.

FIG. 2 is a schematic view of a process for producing the display material of the present invention using the ink jet recording material (F) of FIG. First, an image is mirror-printed with an ink jet printer on the three ink receiving layers of the ink jet recording material (F) (F-1). Subsequently, the adherend layer 6 is laminated on the surface of the ink receiving layer 3 and thermally fused (F-2). Thereafter, the laminated portion of the temporary base material layer 1 and the slightly adhesive layer 5 is peeled off at the boundary surface between the slightly adhesive layer 5 and the substrate layer 2 (F-3). In the case of recording materials that do not have the slightly adhesive layer 5 as shown in Fig. 1 (C) and (D), the temporary base material layer 1 is peeled off at the interface between the temporary base material layer 1 and the base material layer 2. Is done. In the display material 10 bonded to the adherend 6, the base material layer 2 is the outermost layer and serves as a protective layer for the ink receiving layer 3. (F—4). Thus, the base material layer 2 protected by the temporary base material layer 1 becomes a surface layer only after the adhesion to the adherend 6. Accordingly, it is possible to prevent blocking due to contact between the base material layer 2 and the ink receiving layer 3 when the ink jet recording material is applied or overlapped before the display material 10 is formed. Further, it is possible to prevent the base material layer 2 from being stained or scratched during storage or transportation of the ink jet recording material.

[0039] Each layer and manufacturing method of the ink jet recording material of the present invention will be described below.

[0040] <Temporary base material layer and slightly adhesive layer>

The temporary base material layer 1 serves to prevent blocking of the base material layer 2 and the ink receiving layer 3, and serves as a protective layer for the base material layer 2 before use. In addition, the provision of the temporary base material layer 1 can give stiffness to the ink jet recording material. Thereby, even when it is desired to make the base material layer 2 thin, an ink jet recording material excellent in handling properties such as printing and carrying can be obtained. From these roles, the temporary base material layer 1 is preferably a material that does not adhere to the ink receiving layer 3 or the base material layer 2 due to heat and is firm. Specifically, biaxially stretched polyester, polypropylene, polyethylene, ethylene vinyl acetate copolymer, olefinic acid-modified product, ethylene ethyl acrylate, fluorine resin, etc. that have been subjected to release treatment such as silicon treatment Is given as an example.

[0041] When the temporary base material layer 1 is laminated on the base material layer 2, the slight adhesion layer 5 may be interposed. Temporary base material layer

This is particularly effective when the adhesive strength between 1 and the base material layer 2 is too strong or too weak. The slight adhesion layer 5 is a resin having a weak adhesive strength that can be easily peeled off from the base material layer 2 with the base material layer 2, for example, an ethylene vinyl acetate copolymer, Examples include those mainly composed of urethane resin and acrylic resin. Also, grades of olefinic acid-modified products having high adhesiveness at room temperature, ethylene ethyl acrylate, and the like can be used. Furthermore, an amorphous resin having a low modulus of elasticity, such as amorphous polypropylene, can be used, and a crystalline resin such as homopolypropylene can be blended to adjust the adhesiveness.

[0042] As a resin that is particularly preferable as the temporary base material layer 1, in the case where the slightly adhesive layer 5 is not laminated, an ethylene acetate butyl copolymer or olefinic acid-modified is used from the viewpoint of adhesive strength with the base material layer 2. Things are preferred. In addition, when laminating the slightly adhesive layer 5, polypropylene or polyethylene Len is preferable in terms of blocking resistance. Further, as the slightly adhesive layer 5, a point strength ethylene glycol acetate copolymer is preferable.

[0043] <Base material layer>

The base material layer 2 of the ink jet recording material of the present invention is preferably transparent so that the image of the ink receiving layer 3 can be visually recognized through the base material layer 2. In that case, it is necessary that the image of the ink receiving layer 3 is transparent through the base material layer 2 that is completely transparent.

[0044] Examples of the resin preferably used as the base material layer 2 include an acrylic resin and a polyester resin.

In addition, those generally used as a base material layer of an ink jet recording material such as a salt vinyl resin can be used. Polyesters with excellent processability and acrylic resins with excellent weather resistance are particularly preferred. From the viewpoint of cost, polyolefin resins such as polypropylene and polyethylene are particularly preferred. Polypropylene or polyethylene may be used alone to form the base material layer, or the base material layer may be formed from a mixture of these resins. The resin constituting the base material layer may be mainly composed of the above resin. The term “mainly” as used herein refers to a case where it is 70% by mass or more when the entire base material layer is 100% by mass.

In addition, additives such as an ultraviolet absorber, an antioxidant, and an antiblocking agent can be added to the base material layer 2. Among them, it is preferable to add an ultraviolet absorber in consideration of light resistance when used as a display material. Preferred ultraviolet absorbers include benzotriazole, benzophenone, hindered amine, zinc oxide, cerium oxide and the like. A preferable amount of the additive is 0.0 :! to 2 mass% with respect to the base material layer 2.

[0046] <Ink receiving layer>

Examples of the hydrophilic resin used in the ink receiving layer 3 include polybulal alcohol, polybutylpyrrolidone, carboxymethylcellulose, polyalkylene oxide, or a mixture thereof. Among these, polyethylene oxide is suitable as a hydrophilic resin that can be formed into a film by a dry method such as an extrusion method having excellent ink absorbability and excellent productivity. In the present invention, a resin composed of a repeating unit represented by the following general formula (1) is used as a resin that can independently realize two functions of ink absorption and hot melt adhesion. It is preferable to use a lenoxide-based hydrophilic resin as the resin for the ink receiving layer 3.

[0047] [Chemical 3]

In general formula (1), X ¹ is a residue of an organic compound having two active hydrogen groups. Examples of X ¹ include ethylene glycol, propylene glycol, bisphenol A, aniline propylene glycol, polytetramethylene glycol, and the like. R ¹ is a dicarboxylic acid compound residue. Examples of R ¹ include dicarboxylic acids, dicarboxylic acid anhydrides, and lower alkyl esters of dicarboxylic acids, which are desirable for cyclic dicarboxylic acid compounds or linear dicarboxylic acid compounds.

[0049] Examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, malonic acid, succinic acid, sebacic acid, maleic acid, fumaric acid, adipic acid, and itaconic acid. Examples of the dicarboxylic acid anhydride include anhydrides of the above various dicarboxylic acids. Examples of the lower alkyl ester of the dicarboxylic acid include methinoreestenole, dimethinoreestenole, ethinoreestenole, jetinoreesterol, propinoester, and dipropyl ester of the various dicarboxylic acids. Particularly preferred are linear dicarboxylic acids having 12 to 36 carbon atoms and lower alkyl esters thereof. Specific examples include 1,10-decamethylene dicarboxylic acid, 1,14-tetradecamethylene dicarboxylic acid, 1,18-otadecamethylene dicarboxylic acid, 1,32-dotriacontane methylene dicarboxylic acid, and the like.

[0050] Examples of the lower alkyl ester include methyl esters, ethyl esters, propyl esters, and dipropyl esters of these dicarboxylic acids. These alone

Or two or more can be used in combination. Among these, from the viewpoint of easy reaction, it is preferable to use the dicarboxylic acid anhydride and the lower alkyl ester of dicarboxylic acid. These can be used alone or in combination of two or more.

[0051] A ¹ is represented by the following general formula (2).

[0052] [Chemical 4]

[0053] In the general formula (2), Z is a hydrocarbon group having 2 or more carbon atoms. Preferred examples of Z include alkyl groups such as an ethyl group and a propyl group. a, b, and c are each an integer of 1 or more, and the mass ratio calculated from a, b, and c is (44 (a + c) / (molecular weight of alkylene oxide having 4 or more carbon atoms) X b} is between 80/20 and 94/6. Even if it is smaller than 80/20, it can be used as the hydrophilic resin, but in this case, there are problems such as poor hydrophilicity, poor water absorbability and printability. On the other hand, even if it exceeds 94 Z6, it can be used as the hydrophilic resin, but in this case, there is a problem that it is inferior in terms of ink bleeding resistance and the like. By setting the ratio of a, b, and c within the above-mentioned range, hydrophilicity can be maintained and water can be insolubilized. Also, in the mass ratio calculated from each repeating unit a, c. 7 (& + ji) is set to be 50% by mass or more.

[0054] A powerful hydrophilic resin is obtained by polymerizing ethylene glycol with ethylene oxide, followed by addition polymerization of alkylene oxide, and further by addition polymerization of ethylene oxide to dialkylene compound. Can be made to react.

[0055] Various additives may be added to the ink receiving layer 3 as necessary. For example, porous inorganic fine particles such as silica and alumina can be contained in order to increase the ink absorbability. In addition, it is possible to add a cationic resin such as polyallylamine hydrochloride or polyalkylaminoacrylate for the purpose of improving the ink bleeding characteristics and fixability. Furthermore, additives other than these may be added to the ink receiving layer 2. For example, antioxidants such as tocopherol butylhydroxylazole, silane coupling agents and the like can be mentioned. In particular, it is preferable to add an antioxidant because co-extrusion with the base material layer 2 and the adhesive layer 4 can be stably performed, and an ink jet recording material having excellent productivity can be obtained.

[0056] <Adhesive layer>

The adhesive strength between the resin used for the ink receiving layer 3 and the resin used for the base layer 2 is weak. In some cases, an adhesive layer 4 can be provided between them in order to improve the adhesion between them. Examples of the resin used as the adhesive layer 4 include ethylene-butyl acetate copolymer, polyamide, polyester, rosin, pinene polymers and mixtures and derivatives thereof, copolymers, and modified products. In order to further increase the adhesive strength, it is also preferable to use a resin having a silane coupling function or an acid-modified product. Furthermore, by using a resin blended with a resin having an affinity for the resin used in the ink receiving layer 3 and the base layer 2 for the adhesive layer 4, the base layer 2—the adhesive layer 4 and the one ink receiving layer 3 This is more preferable because the interlayer adhesion of the laminated portion can be further increased.

[0057] <Adhesive material>

The adherend 6 to which the ink jet recording material of the present invention is bonded is not particularly limited as long as the ink receiving layer 3 is a material that can be heat-sealed. Examples of these include vinyl chloride, acrylic, polyester, polycarbonate, and ABS. The heat-sealing temperature is a force depending on the resin used for the ink receiving layer 3 and is usually 60 ° C to 150 ° C.

[0058] <Method for producing inkjet recording material>

The ink jet recording material of the present invention is produced by coextrusion melt molding at least the layers other than the temporary base material layer 1 and the slightly adhesive layer 5 at the same time. For example, the resin composition of each layer of the base material layer 2 and the ink receiving layer 3 is blended or formed into pellets as necessary, and charged into each hopper of a two-layer T-die extruder with a T-die shared connection. To do. Next, it can be co-extruded from a two-layer T-die and directly extruded and laminated on a film that becomes the temporary base layer 1 coated with a resin that becomes the slightly adhesive layer 5. It can also be produced by laminating all layers by coextrusion melt molding. For example, a three-layer T die extruder in which the resin composition of each layer of the temporary base layer 1, the base layer 2 and the ink receiving layer 3 is blended or pelletized as necessary, and T dies are covalently connected. Each of the hoppers is co-extruded from a three-layer T-die, and cooled and solidified by a cooling roll, water or air cooling, etc., and a three-layer laminate ink jet recording material can be formed. Alternatively, in the case of laminating the slightly adhesive layer 5 and the adhesive layer 4, it can be produced in the same manner by using a T-die extrusion apparatus equipped with a T-die capable of co-extruding a required number of layers. By producing in this way, a simple and high-quality recording material can be produced. Example

[0059] Examples are shown below, but the present invention is not limited thereto.

(Example 1)

After addition polymerization of ethylene oxide to ethylene glycol, addition polymerization of butylene oxide was performed. Further, methyl otadecane 1,18 dicarboxylate was added to polyalkylene oxide obtained by addition polymerization of ethylene oxide, and transesterification was performed to obtain Resin A having a weight average molecular weight of 150,000. An ink receiving layer was prepared by adding 1 part by mass of Tocophenol (UVI NUL2000AO manufactured by BASF) as a heat stabilizer. Further, HPR VR105 manufactured by Mitsui Dupont Polychemical Co., Ltd. was used as the adhesive layer, and polypropylene resin (Novatech PP EA7A) manufactured by Nippon Polychem Co., Ltd. was used as the base material layer, and melt molding was performed using a T-type multi-hold die. At the same time as molding, ink jet recording is performed by laminating a biaxially stretched polypropylene film as a temporary base layer with a coating of an ethylene-acetic acid butyl copolymer (manufactured by Nijunika Co., Ltd.) as a slightly adhesive layer. Obtained material. The thickness of each layer was 30 μm for the ink receiving layer, 5 μm for the adhesive layer, 15 μm for the base material layer, 2 μm for the slightly adhesive layer, and 70 × m for the temporary base material layer.

[0060] (Example 2)

Using the same resin as in Example 1 as the ink receiving layer, the adhesive layer, and the base material layer, an ethylene-butyl acetate copolymer made by Nippon Tunica Co., Ltd. is laminated as a temporary base material layer on the outside of the base material layer. It was melt-molded with a T-type multi-hold die. The thickness of each layer was 30 μm for the ink receiving layer, 5 μm for the adhesive layer, 30 μm for the base material layer, and 70 μm for the temporary base material layer.

[Example 3]

In Example 1, the layer and configuration of the temporary base material layer were set to Example 3.

[Example 4]

Using the same resin as in Example 1 as the ink receiving layer, adhesive layer, and base material layer, the outer layer of the base material layer is a polypropylene FY6H made by Nippon Polypro Co., Ltd., and Tuff Selenium T3712 made by Sumitomo Chemical Co., Ltd. was blended 1: 1. Further, melt molding was performed with a T-type multi-hold die so that FY6H was laminated on the outer side as a temporary base material layer. The thickness of each layer is the ink receiving layer 30 / im. The adhesion layer was 5 μm, the base material layer was 30 μm, and the temporary base material layer was 70 μm.

[0063] (Example 5)

Resin A for the ink receiving layer, PET resin for the base layer I (PETG676 3 manufactured by Eastman Chemical Co., Ltd.), modified polyolefin resin (Admer SF731 manufactured by Mitsui Chemicals Co., Ltd.) for the base material section I, and polypropylene resin for the base material section II (Japan) Polypro FY6H) was used. These ink receiving layer, base material layer I, base material layer II, and base material layer ΠΙ were melt-molded using a T-type multi-holding die so that they were laminated in this order. The thicknesses at that time were 30 μm, 50 μm, 20 μm, and 50 μm, respectively.

[0064] (Example 6)

Resin A for the ink-receiving layer, PET resin for the base material layer (PETG6763 manufactured by Eastman Chemical Co., Ltd.), polypropylene resin (FY6H made by Nippon Polypro Co., Ltd.) on the outside of the base material layer The blended slightly adhesive layer was melt-molded with a T-type multi-hold hold so that a polypropylene resin (FY6H manufactured by Nippon Polypro Co., Ltd.) was placed on the outside as a temporary base layer. The thickness of each layer was 30 μm, 50 μm, 5 μm, and 50 μm, respectively.

[0065] One effective material for constituting the substrate is polyethylene terephthalate resin from the viewpoint of improving image visibility due to high transparency and adhesion to the ink receiving layer. On the other hand, the ink-jet recording material of the present invention is scraped off so that the innermost ink-receiving layer and the outermost layer are in contact with each other when the ink-jet recording material is scraped into a roll after production. Therefore, when the ink receiving layer and the outermost layer are in a roll form, they may adhere to each other due to heat or the like to cause blocking, which may hinder actual operation. For this reason, as a temporary base material layer, a material layer that is difficult to adhere to the ink receiving layer can be disposed to prevent blocking.

[0066] In Example 5, PET resin is used as a resin having high adhesiveness to the ink receiving layer and high transparency. In order to prevent the blocking, a resin having no adhesiveness to the ink receiving layer (polypropylene) is used. ) Are laminated via an adhesive resin. In addition, a resin having no adhesion to the ink receiving layer can be provided as a temporary base material. In Example 6, polypropylene is provided as a temporary base material via an adhesive layer so that it can be peeled off in an actual process. It is a thing. [0067] (Comparative Example 1)

Evaluation was performed using a commercially available void-type inkjet media with an adhesive on the back.

[0068] <Sample evaluation>

The evaluation tests described below were carried out on each of the display materials of Examples 1 to 6 and Comparative Example 1 prepared as described above.

Each sample was printed using “Design Jet 5500” manufactured by Hewlett-Packard Co., and the sensory evaluation was visually performed on the print quality of the printed sample. Those that could read 5 point characters correctly were recorded as “◯”, and those that could not read 5 point characters were recorded as “X”.

Lamination strength>

For Examples 1 to 6, the ink receiving layer surface of each sample surface was laminated at a temperature of 100 ° C. on a plastic plate made of polyvinyl chloride and vinyl (thickness 3 mm) with a thermal laminator (Ramimonki, manufactured by Rummy Corporation). A display sump nore was prepared, and the laminate strength of the ink receiving layer and the plastic plate was measured. For Comparative Example 1, the adhesive side was bonded to a plastic plate made of polyvinyl chloride (thickness 3 mm). Those that could not be easily peeled by hand were recorded as “◯”, and those that could be easily peeled by hand were recorded as “X”.

Water running test>

After 5 minutes of running tap water on the surface of the printed Sampnore, “5” indicates that the 5-point character can be read accurately, and “X” indicates that the 5-point character cannot be read accurately.

Fastness test>

“レ” indicates that the image has no problem, “◯” indicates that the image has no scratch on the surface, but “X” indicates that there is no problem with the image, and “X” indicates that there is a problem with the image.

Final product image clarity>

The visual quality of the printed image was visually evaluated when the outermost layer was peeled after the composite and the final product was obtained. “◎” for clear items, “Yes” for good items, not clear The thing was named "X".

Final product curl

The curl of the final product after combining was measured. Those with 3 mm or less lift from the edge were marked with “◎”, those with a height of more than 3 mm but less than 5 mm were marked with “◯”, and those with a height of more than 5 mm were marked with “X”. These results are summarized in Table 1.

[table 1]

[0070] As is apparent from Table 1, the examples satisfying the requirements stipulated in the present invention:! To 6 display materials were excellent in print quality and had a laminate strength that had no practical problem. In addition, the running water test, fastness test, final product image clarity, and final product curl evaluation results were also good. In addition, the display materials of Example 5 and Example 6 have the advantage that the PETG layer is introduced, so that linear expansion during heating such as laminating is suppressed and curling is suppressed. confirmed. In particular, in the display material of Example 6, since PETG was the outermost layer as the final product, the advantage of clearer images with better transparency than polypropylene resin was recognized. On the other hand, the normal inkjet media having a void-type ink-receiving layer in Comparative Example 1 has many unevenness and streaks in the image and inferior print quality, and the result is that the image is disturbed in the running water test and fastness test. It was. In addition, although the display materials of Examples 3 and 5 having a configuration without a temporary base layer showed slightly inferior results in the fastness test in comparison with the display materials of other examples, the print quality and the laminate The strength and running water tests showed excellent results.

[0071] While the present invention has been described above in relation to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. The invention can be changed as appropriate without departing from the spirit or concept of the invention which can be read from the scope of the claims and the entire specification, and ink jet recording materials accompanying such changes are also within the technical scope of the present invention. Must be understood as encompassed by I must.

Claims

The scope of the claims

[1] An inkjet recording material in which an adhesive layer and an ink-receiving layer made of a hydrophilic resin are sequentially laminated on a base material layer as necessary. An ink jet recording material produced by extrusion molding.

[2] An ink jet recording material in which a base material layer and an ink receiving layer made of a hydrophilic resin are sequentially laminated on a temporary base material layer, wherein at least the base material layer and the ink receiving layer are An ink jet recording material produced by melt coextrusion molding at the same time.

[3] The adhesive film according to claim 2, further comprising an adhesive layer melt-coextruded at the same time as the base material layer and the ink receiving layer between the base material layer and the ink receiving layer. The ink jet recording material according to Item.

[4] The claim 1 or 2, wherein the adhesive layer is an acid-modified resin.

Item 4. The ink jet recording material according to item 3.

[5] The inkjet recording material according to item 1 or 3, wherein the adhesive layer is a blend resin composed of two or more kinds of polymers.

[6] The ink jet recording material according to claim 2 or 3, wherein a slight adhesion layer is provided between the temporary base material layer and the base material layer.

[7] All the layers are melt coextruded at the same time.

7. The ink jet recording material according to any one of items 6.

8. The ink jet recording material according to any one of claims 1 to 7, wherein the ink receiving layer is a resin represented by the following general formula (1).

[Chemical 1]

[In the general formula (1), X ¹ is a residue of an organic compound having two active hydrogen groups, R ¹ is a dicarboxylic acid compound residue, and A ¹ is represented by the following general formula (2) . ] [Chemical 2]

(2) [In the general formula (2), Z is a hydrocarbon group having 2 or more carbon atoms, a, b, and c are each an integer of 1 or more, and a mass ratio calculated from a, b, c, {44 ( a + c) Z (molecular weight of alkylene oxide having 4 or more carbon atoms) X b} is 80/20 to 94Z6. In addition, cZ (a + c) is set to 50% by mass or more in the mass ratio calculated from each repeating unit a and c. ]

[9] The base material layer according to claim 1, wherein the base material layer is mainly composed of polypropylene.

9. The inkjet recording material according to any one of items 1 to 8.

10. The ink jet recording material according to any one of claims 1 to 9, wherein the ink receiving layer contains an antioxidant.

[11] The force of any one of claims 2, 3, or 6 after heat-sealing the ink-receiving layer surface of the ink-jet recording material according to claim 1 to an adherend, and then the temporary base material layer Display material made by peeling off