JP3003168B2 - Image protection member and image protection method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is intended to impart gloss to printed matter formed by printing or various recording methods, or to protect the printed matter from water, light, etc. And an image protection member. More specifically, the present invention relates to an image protection member suitable for protecting a print formed by an inkjet recording method.

(Prior Art) The ink jet recording system has advantages such as low noise, easy multi-color and large image formation, and low running cost, and has been rapidly spread in recent years.

Non-recording materials used for inkjet recording include:
In addition to plain paper and coated paper, there may be mentioned those obtained by coating an ink receiving layer comprising organic or inorganic fine particles and a binder resin on a plastic film having a porous surface layer or a non-porous hydrophobic plastic film.

Further, as a recording liquid for ink jet recording, a water-based recording liquid is mainly used from the viewpoint of safety and printing characteristics, and therefore, a hydrophilic substance is preferably used for the recording material. On the other hand, for printed matter after recording, high water resistance and light resistance are required, in order to satisfy these requirements,
For example, JP 62-56184, JP 62-59076, JP 62
-60683, JP-A-62-202794, JP-A-62-273889, JP-A-62-273890, JP-A-280085 and JP-A-62-280086. Laminating methods have been proposed.

However, in such a conventional lamination method, the color developability is insufficient, and when the size of the printed film is the same as that of the laminated film or when the necessary portion is cut after lamination, it is difficult to seal at the end, and water from the end is difficult. It has been difficult to prevent problems such as blurring of the printed image due to infiltration.

JP-A-62-161583, JP-A-62-280086 and the like describe lamination of acrylic resin, paraffin wax, etc. on an image, but this was not practically sufficient. .

(Problems to be Solved by the Invention) The present invention provides an image protection member which is particularly excellent in water resistance and color development for protecting printed matter formed by an ink jet method by lamination, and an image protection method using the same. Is to do.

(Means for Solving the Problems) The present invention can solve the problems in the conventional method as described above by laminating a light-transmitting non-porous support having a specific compound applied on a bonding surface to an image. The gist is a member used to protect an image recorded on a porous recording material by an ink jet recording method, and the member is transparent. An image comprising a layer having a polyester resin as a main component, which is a copolymer composed of an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit and an aliphatic polyol unit, on a non-porous support. The protective member is laminated on the image recorded on the porous support by the protective member and the inkjet recording method so that the layer containing the polyester resin as a main component is in contact with the protective member, and is thermocompression-bonded. Lies in the image protection method.

 Hereinafter, the present invention will be described in detail.

The image protection member of the present invention comprises a light-transmitting non-porous support provided with a layer mainly composed of a polyester resin.

That is, the polyester resin is a copolymer composed of an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit and an aliphatic polyol unit.

Each unit constituting the polyester resin is a saturated or unsaturated aliphatic aliphatic such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, and glutaconic acid. Units derived from dicarboxylic acids, terephthalic acid, units derived from aromatic dicarboxylic acids such as isophthalic acid and ethylene glycol, propylene glycol, butylene glycol,
A unit derived from an aliphatic polyol such as hexylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, and glycerin, and each unit is one or two.
It may contain more than one species. Further, specifically, the polyester-based resin is obtained by reacting an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid and an aliphatic polyol forming these units in the presence of an acid or an alkali catalyst to form a copolymer. Thus, a polyester resin having each unit is produced.

Such a polyester resin has a molecular weight of 5,000 to 25,
The melting point (softening point) is 50 from the point of simplicity of thermocompression bonding (low thermocompression temperature) and conformity with the coating layer of the recording material;
~ 130 ° C, glass transition point; those exhibiting physical properties of -30 ° C to 40 ° C are suitable, and the viscosity at melting is 700 to 3,000.
Poise (200 ° C.) is preferred.

The polyester-based resin used in the present invention has a molar ratio of 8 to 8 of the aliphatic and aromatic dicarboxylic acid units in the aliphatic and aromatic dicarboxylic acid units. : 2 to 2: 8.

As described above, the polyester-based resin as described above can be produced by a method of reacting an aliphatic dicarboxylic acid with an aromatic dicarboxylic acid and a polyol to copolymerize the resin. Products readily available from the market, such as those sold under the trade names Byron 300, 500, GX590, GX130, GXS11 from Nippon Synthetic Chemical Industry Co., Ltd. under the trade name Polyester LP033, −044, −035 Can be used.

The translucent non-porous support includes aromatic polyesters, acrylic polymers, polyvinylidene fluoride,
Polycarbonate, polyimide, polyvinyl chloride and other films can be used, the thickness of which is 30 to 100 μm
Is appropriate. These films can be used alone, but can also be used together in a laminated form.
A layer containing the polyester-based resin as a main component is formed on these films by coating, and the thickness (dry) of the layer is suitably 5 to 40 μm.

Coating method is bar coater, die coater, gravure coater, knife coater, reverse roll coater,
Conventional coating means such as a hot melt coater can be used. Among the above-mentioned coating methods, when applying by a method other than the method using a hot melt coater, the polyester-based resin is mixed with a suitable solvent, for example, ketones such as methyl ethyl ketone, esters such as ethyl acetate, and isopropyl alcohol. It can be applied by dissolving or dispersing 10 to 30% by weight in a solvent such as an alcohol such as an alcohol or an aromatic such as toluene, xylene or chlorobenzene. In addition, a crosslinking agent may be added to the polyester-based resin layer to improve blocking resistance, and an antioxidant, an ultraviolet absorber, other resins, and the like may be added as necessary.

 Meanwhile, the image protection method of the present invention will be described.

That is, the present invention relates to a method for protecting an image recorded on a recording material by an inkjet recording method,
On a porous recording material on which an image is recorded, on a light-transmitting non-porous support, an image protection member having a layer containing the polyester resin as a main component, the polyester resin as a main component And a thermocompression bonding method.

The recording material to be recorded by the ink jet method in the present invention is not particularly limited, and is selected from commonly used recording materials. Specifically, bond paper, electrophotographic paper, and high quality paper are coated with zeolite or the like. Polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyoxazoline, polyvinylamine, polyethyleneimine, hydroxypropyl on the surface of non-porous plastic film formed from plastic such as polyester, polyvinyl chloride, polystyrene etc. Hydrophilic resin such as cellulose, ethylcellulose, polyamide epoxy, polyester urethane, polyether urethane and colloidal silica, aerosil, alumina fine powder, zirconia fine powder, urea-formalin resin fine particle benzog Coating the organic or an inorganic particulate coating liquid fine particles of Namin resin by conventional method of applying such a bar coater which is provided a coating layer is used.

Further, as a specific example of the recording material, EP-A-33
9,604, a non-porous support having an ionomer type (polyester type, polyether type) aqueous urethane resin having a carboxyl group and a film containing organic and / or inorganic fine particles formed thereon, which is preferably used. Can be done. Since the recording material provided with these coating layers is hydrophilic and porous, it can be printed with the aqueous ink of the ink jet system, as well as with the polyester resin of the image protection member of the present invention. It is well-adapted and has a feature that the melt in the thermocompression bonding step of the polyester resin easily penetrates the coating layer on the recording material.

The printed matter protected by the present invention is an image recorded on the above-described porous recording material by an inkjet method.

In this case, the recording by the ink jet method is performed by a conventionally known ink jet method, for example, a method of ejecting ink from a nozzle by a piezoelectric element or the like, or a method of ejecting ink from a nozzle using bubbles generated by heating. .

The recording liquid used for forming a print protected by the image protection member of the present invention contains a colorant, water, a hydrophilic organic solvent and, if necessary, a dispersant. Dyes or pigments are used as colorants. As the dye, azo type, phthalocyanine type, quinophthalone type and the like can be used, and in particular, Direct Yellow-86, -142 Acid Red-35, -37 D
irect Blue−86, −199 Direct Black−154, Food Bl
ack-2 and the like are preferable. On the other hand, as the pigment, azo-based, phthalocyanine-based, quinacridone-based and other carbon blacks can be used, particularly Pigment Yellow-74,
-154 Pigment Red-5 and -122 Pigment Blue-15 are preferred.

In the image protection method of the present invention, the recording liquid to be used may be a dye or a pigment, but from the viewpoint of the light resistance of the protected image itself, a pigment is generally suitable, and the protective member of the present invention is preferably a pigment. It is also suitable for protecting a recorded image with a recording liquid.

The content of the above dye or pigment is in the range of 0.5 to 10% by weight, preferably in the range of 1 to 7% by weight based on the total weight of the recording liquid.

When a pigment is used as the colorant, a dispersant is preferably used.

As the dispersant, anionic, nonionic and cationic dispersants are used, and from the viewpoint of safety, anionic and nonionic dispersants are preferable. Examples of the anionic dispersant include styrene-maleic acid copolymer, diisobutylene-maleic acid copolymer, poly (meth) acrylic acid (meth) acrylate- (meth) acrylic acid copolymer and condensed naphthalene sulfone And salts of acids and the like.

As nonionic dispersants, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters,
Examples thereof include polyoxyethylene alkylamines and polyoxyethylene-polyoxypropylene copolymers.

The amount of these dispersants used is 10 to 100% by weight based on the pigment.
Range.

Further, as the hydrophilic organic solvent, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 400), glycerin, N-methyl-pyrrolidone, N
-Ethyl-pyrrolidone, N-vinyl-pyrrolidone, 1,3
-Dimethyl-imidazolidinone, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like, and the content of the hydrophilic organic solvent is preferably 0 to 50% based on the total weight of the recording liquid. % By weight.

The recording liquid used in the present invention may contain other various additives as necessary.

As such a recording liquid, specifically, JP-A-47-121.1
Known recording liquids described in JP-A No. 05-29,546 and JP-A-56-147863 can be used.

Then, after an image is recorded on a porous recording material by an ink jet method using such a recording liquid, the protective member of the present invention is thermocompression-bonded on the recording surface, and the image is protected by lamination. Is done.

In the present invention, the temperature of the thermocompression bonding is performed at about 80 to 150 ° C., preferably from 90 to 130 ° C., as the pressing pressure conducted at about ^{1~10kg / cm 2, 2~6kg / cm} 2 Is preferred.

As the method of thermocompression bonding, any means can be used as long as the temperature and the conditions of compression bonding can be selected, but specifically, an iron, a laminator or the like may be used.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the present invention in any way.

Example 1 A polyvinyl chloride film having a thickness of 200 μm was used as a support, and 50 parts by weight of an ionomer type polyester-based urethane resin (trade name, Hydran HW-310, manufactured by Dainippon Ink and Chemicals, Inc.) as an ink absorbing layer ( Resin solid 30
%), Acrylic resin (trade name: Voncoat V, manufactured by Dainippon Ink and Chemicals, Inc.) 2.5 parts by weight (resin solid content: 30%), Demol EP (polycarboxylate type surfactant, Kao Corporation)
A composition comprising 0.1 parts by weight of Fluorad FC-170C (manufactured by Fluoro-Nonionic surfactant 3M) and 12 parts by weight of urea-formaldehyde resin (particle size: 0.1 to 3 μm) was prepared by a bar coater method. The dried film was applied on a film so as to have a thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a recording material.

The recording material thus obtained was subjected to ink jet recording using an ink jet printer IO-730 (manufactured by Sharp Corporation) for discharging ink by a piezo vibrator to obtain a recorded image.

The composition of dicarboxylic acid units in a vinylidene fluoride film (Kureha KFC AT-50Y Kureha Chemical Industry Co., Ltd.) having a thickness of 50 μm is terephthalic acid: isophthalic acid: adipic acid = 29: 31: 40, and diol units Polyester resin whose composition is ethylene glycol: neopentyl glycol = 45: 55 (trade name, Byron 50AS, Toyobo Co., Ltd.)
, Molecular weight 20,000-25,000, softening point 114 ° C, glass transition point 4 ° C, melt viscosity (200 ° C) 700P) 50 parts by weight, vinylidene chloride resin (trade name: ARON CX-S, manufactured by Toa Gosei Chemical Industry Co., Ltd.) 2 Parts by weight, 20 parts by weight of methyl ethyl ketone and 80 parts by weight of chlorobenzene were applied by a bar coater method so that the dry film thickness became 20 μm.
The laminate was dried at 5 ° C. for 5 minutes to form a laminate film. This laminate film was thermocompression-bonded on the above recorded image at a surface temperature of 120 ° C. and a press pressure of 5 kg / cm ² as lamination conditions. The recorded image had good light fastness, water fastness, and color developability.

Example 2 A 100 μm-thick polyethylene terephthalate film was used as a support, and an ink-absorbing layer was composed of 50 parts by weight of a polyvinylpyrrolidone aqueous solution (resin solid content: 30%) and 20 parts by weight of colloidal silica (particle size: 10 to 100 nm). The composition was applied on a film by a bar coater method so as to have a dry film thickness of 15 μm and dried to prepare a recording material, and a recorded image was formed in the same manner as in Example 1. Thickness, 150μ
m polyester film (trade name Lumirror W # 150 manufactured by Toray Industries, Inc.), the composition of the dicarboxylic acid unit is terephthalic acid: sebacic acid = 69: 31, and the composition of the diol unit is ethylene glycol: neopentyl glycol = 46: 54
Polyester resin (trade name: Polyester LP033, manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; molecular weight 16,000, flow start temperature)
84 ℃, glass transition point 15 ℃, melt viscosity (190 ℃) 150P) 30
A composition consisting of 70 parts by weight of toluene and 70 parts by weight of toluene was applied by a bar coater method so as to have a dry film thickness of 15 μm, and dried at 90 ° C. for 10 minutes to form a laminate film. The laminated film was placed on the above recorded image at the surface temperature.
Thermocompression bonding was performed at 105 ° C. and a press pressure of 4 kg / cm ² . The light resistance, water resistance, and color development of the recorded image were good.

Example 3 Instead of the aliphatic polyester resin (trade name: Byron 50AS manufactured by Toyobo Co., Ltd.) in Example 1, the composition of the dicarboxylic acid unit was terephthalic acid: isophthalic acid: sebacic acid = 35: 35: 30, The composition of the diol unit is ethylene glycol: neopentyl glycol = 30: 70. Polyester resin (trade name: Polyester LP044), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., molecular weight 7,000, flow start temperature 56 ° C,
Glass transition point 20 ℃, melt viscosity (150 ℃) 300P)
An image protection member was prepared in the same manner as in Example 1 except that the dry film thickness on the laminate film was 30 μm.

On the other hand, as an image to be protected, the same ink jet printer IO-730 (manufactured by Sharp) as in Example 1 was used, using each recording liquid prepared by the following composition and method on the same recording material as that prepared in Example 1. ), And the recorded image was subjected to thermocompression bonding of the protective member in the same manner as in Example 1. As a result, the image was excellent in water resistance, light resistance, and coloring.

(Method of preparing the recording liquid) composition Glycerin 20 parts Pigment ^* 3 Polystar S-2-1020 (styrene - maleic acid dispersant trade name manufactured by NOF Corporation) 2 parts water remainder Total 100 parts of the above Each component was placed in a container, and crushed for 20 hours using a sand grinder (manufactured by Igarashi Machine Manufacturing Co., Ltd.) together with 130 ml of glass beads having an average diameter of 0.5 mm. 3μ pore size
After filtration under pressure using a Teflon filter described above, the recording liquid was prepared by de-treatment using a vacuum pump and an ultrasonic cleaner.

^* Pigment A recording liquid was prepared using each of the following pigments a to d.

a Black carbon black # 45 (manufactured by Mitsubishi Kasei Corporation) b Cyan Pigment blue-15 (manufactured by Dainichi Seika Kogyo Co., Ltd.) c Magenta Pigment Red-122 (manufactured by Dainippon Ink & Chemicals, Inc.) d Yellow Pigment Yellow-74 (manufactured by Dainichi Seika Kogyo Co., Ltd.) (Effects of the Invention) The present invention relates to a novel image protection member having a layer containing a specific resin as a main component. The image protected by performing the image protection method is excellent in water resistance, light resistance, and coloring, and is suitable for use in indoor and outdoor displays and displays for automobiles and the like.

Claims (2)

(57) [Claims] 1. A member used to protect an image recorded on a porous recording material by an ink jet recording method, wherein the member is made of an aliphatic dicarboxylic acid on a light-transmitting non-porous support. An image protection member comprising a layer mainly composed of a polyester resin which is a copolymer composed of an acid unit, an aromatic dicarboxylic acid unit and an aliphatic polyol unit. 2. A method for protecting an image recorded on a recording material by an ink jet recording method, wherein the image protection member according to claim 1 is provided on a porous recording material on which an image is recorded. An image protection method comprising: laminating a layer containing a polyester resin as a main component provided on a porous support so that the layers are in contact with each other; and thermocompression bonding.