JPH04263980A - Image protection member - Google Patents

Abstract

PURPOSE:To provide a highly water-proof and a color generating image protection member for protecting an image formed in an ink jet mode on a porous material on which data is recorded, using a laminate. CONSTITUTION:An image protection member consists of a layer based on a polyester copolymer resin composed of an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit and an aliphatic polyol unit and containing 5 to 30wt.% of ester aromatic carboxylate provided on a non-porous support.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an image protection member for imparting gloss to prints formed by printing or various recording methods, or for protecting prints from water, light, etc. be. Specifically, the present invention relates to an image protection member suitable for protecting printed matter formed by an inkjet recording method.

0002

[Prior art] The inkjet recording method produces less noise.
It has become rapidly popular in recent years because it has the advantage of being easy to form multicolor and large images, and has low running costs. Recording materials used for inkjet recording include plain paper, coated paper, and ink-receiving materials made of organic or inorganic fine particles and binder resin on plastic film with a porous surface layer or non-porous hydrophobic plastic film. Examples include those coated with layers.

[0003] Furthermore, since a water-based recording liquid is mainly used for inkjet recording from the viewpoint of safety and printing characteristics, it is preferable that a hydrophilic substance is used for the recording material as well. On the other hand, printed matter after recording is required to have high water resistance and light resistance.
2-59076, JP-A-62-60683, JP-A-62
-202794, JP-A-62-273889, JP-A-6
2-273890, JP-A No. 62-280085, and JP-A No. 62-280086, methods of laminating a printed matter with a plastic film have been proposed.

However, in such conventional laminating methods, the color development is insufficient, and if the size of the laminated film and the printed matter are the same, or if necessary parts are cut after lamination, it is difficult to seal the edges. It has been difficult to prevent problems such as smearing of printed characters due to water infiltration from the printed parts. Also, JP-A-62-1
No. 61583, JP-A No. 62-280086, etc., disclose laminating acrylic resin, paraffin wax, etc. on an image, but these are not sufficient for practical use.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image protection member particularly excellent in water resistance and color development for protecting an image formed by an inkjet method on a porous recording material by laminating it. It is in.

[0006]

[Means for Solving the Problems] The present invention can solve the above-mentioned problems in the conventional method by laminating an image with a translucent non-porous support coated with a specific compound on the lamination surface. It is based on new findings, and its gist is that it is a member used to protect images recorded on a porous recording material by an inkjet recording method, and the member is a translucent material. The main component is a polyester resin, 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, and 5 to 30% by weight of aromatic carboxyl. An image protection member comprising a layer containing an acid ester.

The present invention will be explained in detail below. The image protection member of the present invention has a layer containing a polyester resin as a main component and an aromatic carboxylic acid ester on a light-transmitting non-porous support. That is, this polyester resin is a copolymer composed of aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and aliphatic polyol units. The units constituting this polyester resin are saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, and glutaconic acid. Units derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and units derived from aromatic dicarboxylic acids such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, and glycerin. These units are derived from aliphatic polyols, and each unit may contain one type or two or more types. In addition, this polyester resin can be produced by reacting aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic polyols forming each of these units in the presence of an acid or alkali catalyst to form a copolymer. A polyester resin having each unit is manufactured by the following steps.

Such polyester resin has a molecular weight of 5,000 to 25,000, and has a low melting point (softening temperature) due to ease of thermocompression bonding (low thermocompression temperature) and compatibility with the coating layer of the recording material. point); 50 to 130°C, glass transition point; -
It is suitable that the material exhibits physical properties at 30°C to 40°C, and
Its viscosity when melted is 700 to 3,000 poise (
200°C) is preferred. In order for the polyester resin used in the present invention to exhibit the above-mentioned performance, the molar percentage ratio of aliphatic dicarboxylic acid units to aromatic dicarboxylic acid units is 8. :2
It is preferable that the ratio is ~2:8.

The above-mentioned polyester resin can be produced by a method such as copolymerization by reacting an aliphatic dicarboxylic acid with an aromatic dicarboxylic acid and a polyol, as described above. Product name Byron 300, 500, GX590, GX1 from Toyobo Co., Ltd.
30, GXS11 or those sold under the trade names of Polyester LP033, -044, and -035 by Nippon Gosei Kagaku Kogyo Co., Ltd., which are easily available on the market, can be used.

[0010] Further, the aromatic carboxylic acid esters added in the present invention are solid at room temperature and have a melting point (softening point).
is preferably in the range of 50 to 140°C, and
Examples include those having good compatibility with the polyester resin used, and the amount added is in the range of 5 to 30% by weight, more preferably 10 to 20% by weight. Specifically, the aromatic carboxylic acid esters used in the present invention include phthalic acid esters such as dimethyl isophthalate, diphenyl isophthalate, diethyl terephthalate, dimethyl terephthalate, diphenyl phthalate, dicyclohexyl phthalate, phenyl benzoate, naphthyl benzoate, etc. Examples include benzoic acid esters. In addition, when the above-mentioned aromatic carboxylic acid ester is mixed with the polyester resin, the viscosity at the time of melting is 50 to 100 poise (
100°C) is preferred.

[0011] As the light-transmitting non-porous support, films of aromatic polyester, acrylic polymer, polyvinylidene fluoride, polycarbonate, polyimide, polyvinyl chloride, etc. can be used, and the thickness thereof is 3.
0 to 100 μm is suitable. Although these films can be used alone, they can also be used together in a bonded form. A layer containing the polyester resin as a main component is formed on these films by coating, and the appropriate thickness (dry) of the layer is 5 to 40 μm.

[0012] As the coating method, conventional coating means such as a bar coater, die coater, gravure coater, knife coater, reverse roll coater, hot melt coater, etc. can be used. Among the above coating methods, when coating by a method other than the method using a hot melt coater, the polyester resin and aromatic carboxylic acid ester are mixed with a suitable solvent, such as a ketone such as methyl ethyl ketone, or an ester such as ethyl acetate. alcohols such as isopropyl alcohol, toluene,
It can be applied by dissolving or dispersing it in an aromatic solvent such as xylene or chlorobenzene in an amount of 10 to 30% by weight. In addition, a crosslinking agent may be added to the polyester resin layer to improve blocking resistance, and antioxidants,
It is also possible to add ultraviolet absorbers, other resins, etc. as necessary.

In the present invention, the recording material to be recorded by the inkjet method is not particularly limited and may be selected from commonly used recording materials, specifically bond paper, electrophotographic paper, high-quality paper, and zeolite. In addition to coated paper coated with polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyoxazoline, polyvinylamine, polyethyleneimine, etc., the surface of a non-porous plastic film made of plastics such as polyester, polyvinyl chloride, polystyrene, etc. , hydrophilic resins such as hydroxypropyl cellulose, ethyl cellulose, polyamide epoxy, polyester urethane, and polyether urethane, and organic materials such as colloidal silica, Aerosil, alumina fine powder, zirconia fine powder, urea-formalin resin fine particles, benzoguanamine resin fine particles, etc. Alternatively, a coating layer formed by applying a coating liquid made of inorganic fine particles using a conventional coating method such as a bar coater may be used.

[0014] Further, as a specific example of the above-mentioned recording material,
A film containing an ionomer type (polyester type, polyether type) aqueous urethane resin having a carboxyl group and organic and/or inorganic fine particles is formed on a non-porous support described in EP-A-339,604. These can be preferably used. Since the recording material provided with these coating layers is hydrophilic and porous, it is not only possible to print with water-based ink using an inkjet method, but also to be compatible with the polyester resin of the image protection member of the present invention. It is characterized by good conformability, and the melted material of the polyester resin in the thermocompression bonding process easily permeates into the coating layer on the recording material.

The printed matter protected by the present invention is an image recorded on the above-mentioned porous recording material by an inkjet method. In this case, a conventionally known inkjet method is used for recording by the inkjet method, such as a method in which ink is ejected from a nozzle using a piezoelectric element or the like, or a method in which ink is ejected from a nozzle using air bubbles generated by heating. .

The recording liquid used to form 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. A dye or a pigment is used as the coloring agent. As the dye, azo type, phthalocyanine type, quinophthalone type, etc. can be used, but in particular, Direct Yellow-86,
-142 Acid Red-35, -37 D
direct Blue-86,-199 Dire
ct Black-154, Food Black
-2 etc. are preferable. On the other hand, as a pigment, azo type, phthalocyanine type, quinacridone type, and carbon black can be used, but in particular, Pigment Yellow
ow-74,-154 Pigment Red-
5,-122 PigmentBlue-15 is preferred.

In the image protection method of the present invention, the recording liquid used may be dye-based or pigment-based, but from the viewpoint of the light resistance of the image itself to be protected, pigment-based recording liquids are generally suitable. is also suitable for protecting recorded images using pigment-based recording liquids. The content of the above dyes or pigments is as follows:
The amount may be in the range of 0.5 to 10 wt%, preferably 1 to 7 wt%, based on the total weight of the recording liquid. Moreover, when using a pigment as a coloring agent, it is preferable to use a dispersant.

Anionic, nonionic and cationic dispersants can be used, but anionic and nonionic ones are preferred from the viewpoint of safety. Examples of anionic dispersants include styrene-maleic acid copolymer, diisobutylene-maleic acid copolymer, poly(meth)acrylic acid, (meth)acrylic acid ester-(meth)acrylic acid copolymer, and condensed naphthalene. Examples include salts of sulfonic acid and the like. Examples of nonionic dispersants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene-polyoxypropylene copolymers, etc. It will be done. The amount of these dispersants used is 10 to 1
00% by weight.

Furthermore, examples of hydrophilic organic solvents include 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, It preferably contains ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. The content of the hydrophilic organic solvent is 0 to 50% by weight based on the total weight of the recording liquid.
The range of

The recording liquid used in the present invention may contain other various additives as required. Specific examples of such recording liquid include known recording liquids described in JP-A-47-12,105, JP-A-55-29,546, JP-A-56-147,863, etc. Can be used. After an image is recorded on a porous recording material using an inkjet method using such a recording liquid, the above-mentioned protective member of the present invention is thermally pressed onto the recording surface and laminated to protect the image. be done.

[0021] In the present invention, the thermocompression bonding temperature is 80°C.
It is carried out at about 150°C, preferably 90 to 130°C, and the pressing pressure is about 1 to 10 kg/cm2, preferably 2 to 6 kg/cm2. The thermocompression bonding method may be any means as long as the temperature and compression conditions can be selected, but specifically, an iron, a laminator, etc. may be used.

[0022]

[Action] By adding aromatic carboxylic acid esters to polyester resin according to the present invention, the melting point (softening point) of the polyester resin is lowered, and the melt viscosity is also significantly lowered, which has been difficult until now. It is believed that the hot melt agent can easily penetrate even into porous recording materials, making it possible to protect the desired image.

[0023]

[Examples] The present invention will be explained in more detail below using Examples, but the following Examples are not intended to limit the present invention in any way. Example 1 A polyvinyl chloride film with a thickness of 200 μm was used as the support, and an ionomer type polyester urethane resin (trade name: HydranHW-) was used as the ink absorption layer.
310 Dainippon Ink & Chemicals Co., Ltd.) 50 parts by weight (resin solid content 30%), acrylic resin (product name Vo
ncoat V (manufactured by Dainippon Ink & Chemicals Co., Ltd.)2.
5 parts by weight (resin solid content 30%), Demol EP (polycarboxylate type surfactant, Kao Corporation) 0.1 part by weight, Fluorad FC-170C (fluorinated nonionic surfactant manufactured by 3M Co., Ltd.) ) 0.1 parts by weight, and 12 parts by weight of urea formaldehyde resin (particle size 0.1 to 3 μm)
) was coated with a bar coater method until the dry film thickness was 2.
Coat it on the film so that it has a thickness of 0 μm and heat it at 80°C.
, and dried for 10 minutes to obtain a recording material.

[0024] An inkjet printer IO ejects ink onto the obtained recording material using a piezo vibrator.
Inkjet recording was performed using -730 (manufactured by Sharp Corporation) to obtain a recorded image. Vinylidene fluoride film (trade name: Kureha KFC AT-50) with a thickness of 50 μm
(manufactured by Y Kureha Chemical Industry Co., Ltd.), the composition of dicarboxylic acid units is terephthalic acid: isophthalic acid: adipic acid = 29:31
:40, and the composition of diol units is ethylene glycol:neopentyl glycol=45:55 (trade name: Vylon 50AS, manufactured by Toyobo Co., Ltd., molecular weight 20,000-25,000, softening point 11)
4℃, glass transition point 4℃, melt viscosity (200℃) 700
P) 40 parts by weight, dimethyl isophthalate (trade name DM
I, manufactured by Daihachi Kagaku Kogyo Co., Ltd.), 20 parts by weight of methyl ethyl ketone and 80 parts by weight of chlorobenzene was coated with a bar coater method to give a dry film thickness of 20 μm.
This was dried at 80° C. for 5 minutes to produce a laminate film. This laminate film was thermocompression bonded onto the above-mentioned recorded image under lamination conditions such as a surface temperature of 120° C. and a press pressure of 5 kg/cm 2 . The recorded images had good light resistance, water resistance, and color development.

Example 2 A polyethylene terephthalate film with a thickness of 100 μm was used as a support, and as an ink absorbing layer, 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) were used.
) was coated and dried on a film using a bar coater method to a dry film thickness of 15 μm to prepare a recording material, and a recorded image was formed on this in the same manner as in Example 1. Polyester film with a thickness of 150 μm (
The product name is Lumirror W #150 (manufactured by Toray Industries, Inc.), and the composition of dicarboxylic acid units is terephthalic acid: sebacic acid = 69:31.
A polyester resin whose diol unit composition is ethylene glycol:neopentyl glycol = 46:54 (trade name Polyester LP033, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.; molecular weight 16,000, flow start temperature 84 ° C.
, glass transition point 15℃, melt viscosity (190℃) 150P
) 28 parts by weight, dimethyl terephthalate (trade name DMT
A composition consisting of 2 parts by weight (manufactured by Mitsubishi Kasei Corporation) and 70 parts by weight of toluene was coated with a bar coater method to give a dry film thickness of 1.
It was applied to a thickness of 5 μm and dried at 90° C. for 10 minutes to produce a laminate film. This laminate film was thermocompression bonded onto the recorded image at a surface temperature of 105° C. and a press pressure of 4 kg/cm 2 . Lightfastness of recorded images,
Water resistance and color development were good.

Example 3 Aliphatic polyester resin (trade name) in Example 1
Byron 50AS (manufactured by Toyobo Co., Ltd.), the dicarboxylic acid unit composition is terephthalic acid: isophthalic acid:
Sebacic acid = 35:35:30, and the composition of diol units is ethylene glycol: neopentyl glycol =
It is 30:70. Polyester resin (trade name Polyester LP044, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., molecular weight 7)
,000, flow start temperature 56℃, glass transition point 20℃,
Example 1 except that the melt viscosity (150°C) was 300P) and the dry film thickness on the laminate film was 30 μm.
An image protection member was created in the same manner as above.

On the other hand, as an image to be protected, each recording liquid prepared in the following composition and method was used on the same recording material as that prepared in Example 1, and the same inkjet printer IO-730 as in Example 1 was used. (manufactured by Sharp) were charged with these and the protective member was thermocompression bonded to the image recorded in the same manner as in Example 1. As a result, the water resistance, light resistance, and color development of the image were good. (Preparation method of recording liquid) Composition Glycerin

20 parts pigment*

Part 3
Polyster S-2-1020

2 parts (styrene-maleic acid dispersant, product name, manufactured by NOF Corporation) Water

Residue
amount

A total of 100 parts of each of the above components was placed in a container and ground together with 130 ml of glass beads having an average diameter of 0.5 mm using a sand grinder (manufactured by Igarashi Kikai Seizo Co., Ltd.) for 20 hours. After pressure filtration using a Teflon filter with a pore size of 3 μm, deaeration treatment was performed using a vacuum pump and an ultrasonic washer to prepare a recording liquid.

0028 *Face fee Recording liquids were prepared using the following pigments a to d individually.

a Black Carbon Black #45 (manufactured by Mitsubishi Kasei Corporation) b Cyan Pigment Blue-1
5 (manufactured by Dainichiseika Kagyo Co., Ltd.) c Magenta Pigment Red-122
(manufactured by Dainippon Ink and Chemicals Co., Ltd.) d Yellow Pigment Yellow-
74 (manufactured by Dainichiseika Kagyo Co., Ltd.)

[0030]

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. It has excellent color stability, light resistance, and color development, and is suitable for use in indoor and outdoor displays, automobile displays, etc.

Claims (1)

[Claims] 1. A member used to protect an image recorded on a porous recording material by an inkjet recording method, the member comprising an aliphatic film on a transparent non-porous support. The main component is a polyester resin, which is a copolymer composed of dicarboxylic acid units, aromatic dicarboxylic acid units, and aliphatic polyol units, and 5 to 30% by weight.
An image protection member comprising a layer containing an aromatic carboxylic acid ester.