JP2003237226A - Medium for ink jet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a medium for ink jet recording which is excellent in the resistance to discoloration and in the resistance to water. <P>SOLUTION: The medium has a composition comprising polyvinyl alcohol (A) containing an acetoacetic acid ester group and a compound (B) containing an amino group which is expressed by the following general formula (1), in a support base or on the surface of the support base: R-[(CH<SB>2</SB>)<SB>n</SB>-NHR<SB>1</SB>]<SB>m</SB>(R is a residual group of a cyclic compound selected from an aromatic ring, an aliphatic ring and a hetero ring, wherefrom hydrogen is removed, R<SB>1</SB>is either hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording medium excellent in color fastness and water resistance.

[0002]

2. Description of the Related Art In recent years, an ink jet recording method for recording characters and the like by ejecting ink in the form of droplets onto the surface of a recording medium such as paper or polyethylene terephthalate enables high-speed printing and multicolor printing. It has come to be widely used because it has the advantage that it can be printed and produces less sound. The inkjet recording medium used in this recording method is
A resin coating layer is provided on a supporting base material such as paper, and specific examples of the coating layer include an ink receiving layer and an overcoat layer provided on the ink receiving layer.

It is known that these layers contain acetoacetic acid ester group-containing polyvinyl alcohol (hereinafter sometimes abbreviated as AA-PVA) for the purpose of improving the water resistance thereof. For example, JP-A-63-176173 and JP-A-2000-17723.
No. 1 and JP-A No. 2000-177232, etc.
AA PVA and a cross-linking agent are used as a support layer or recording (ink reception)
It is described to be contained in the layer. As such a cross-linking agent, a cross-linking agent such as glyoxal is specifically used in the examples.

[0004]

However, when the glyoxal of such a cross-linking agent was verified,
It was found that although the water resistance is good, discoloration due to heat history during manufacture of the ink jet recording medium or during use or aging is observed. It was also found that there is room for improving water resistance with respect to crosslinking agents such as ethylenediamine and hexamethylene. That is, while the inkjet recording medium having higher whiteness or higher transparency is desired from the market in recent years, the influence of thermal history in the printer becomes large due to the speeding up of the printing process, and the thermal history causes the recording to be performed. There is a case that the medium for use is discolored, and further, the same phenomenon may occur even when the recording medium is stored for a long period of time, and improvement is desired.

[0005]

[Means for Solving the Problems] Therefore, the present inventor has conducted diligent research in view of the above circumstances, and as a result, AA-PVA
An ink jet recording medium having a composition containing (A) and an amino group-containing compound (B) represented by the following general formula (1) in or on the surface of a supporting substrate is the above-mentioned recording medium. The inventors have completed the present invention by finding that they can solve the problems. R - [(CH _{2) n} -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R ₁ Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer. In the present invention, the amino group-containing compound represented by the general formula (1) ( B) is metaxylenediamine,
Particularly preferred is either 1,3-bisaminomethylcyclohexane or norbornanediamine.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The AA-modified PVA (A) used in the present invention is obtained by reacting polyvinyl alcohol with diketene, or by reacting polyvinyl alcohol with acetoacetic ester to transesterify the polyvinyl alcohol to form an acetoacetic acid ester group. Introduced, as such polyvinyl alcohol, generally, a saponified product or a derivative thereof obtained by saponifying a lower alcohol solution of polyvinyl acetate with a saponification catalyst such as an alkali or an acid is used. It is also possible to use a saponified product of a copolymer of a copolymerizable monomer and vinyl acetate.

Examples of such a monomer include ethylene,
Olefin such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, vinylene carbonates, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, Olefin sulfonic acids such as methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl allyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride , Polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, etc. Ether, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate and other polyoxyalkylene (meth) acrylates, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide and other polyoxyalkylene (meth) Acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxy Examples include propylene vinylamine.

The polyvinyl alcohol used as the raw material for the AA-modified PVA (A) is not particularly limited, but the saponification degree is 70 mol% or more (further 75 mol% or more, particularly 8 mol%).
0 mol% or more) is preferable, and if the saponification degree is less than 70 mol%, the water solubility is poor and it becomes difficult to prepare a coating solution, which is not preferable. The average degree of polymerization of the polyvinyl alcohol (according to JIS K6726) is not particularly limited, either, but is 100 to 5000 (further 200 to 4).
500, especially 300 to 4000) is preferable, and when the average degree of polymerization is less than 100, sufficient water resistance cannot be obtained, and conversely, when it exceeds 5000, the viscosity of the aqueous solution becomes too high, resulting in workability and paper base materials. It is not preferable because the permeability and the like are decreased.

To obtain AA-PVA (A), a method of reacting polyvinyl alcohol with diketene as described above,
Examples include a method of transesterifying polyvinyl alcohol and acetoacetate ester, a method of copolymerizing vinyl acetate and vinyl acetoacetate, and the like. However, since the production process is simple and high-quality AA-PVA can be obtained. Preferably, it is produced by a method of reacting polyvinyl alcohol (powder) with diketene. As a method of reacting polyvinyl alcohol and diketene, polyvinyl alcohol and gaseous or liquid diketene may be directly reacted, or after organic acid is adsorbed and absorbed in polyvinyl alcohol in advance, it is liquid or under an inert gas atmosphere. A method of spraying and reacting gaseous diketene, or spraying and reacting polyvinyl alcohol with a mixture of an organic acid and liquid diketene is used.

As a reaction apparatus for carrying out the above reaction, an apparatus capable of heating and equipped with a stirrer is sufficient. For example, a kneader, a Henschel mixer, a ribbon blender, other various blenders, and a stirring / drying device can be used.

The content of acetoacetic acid ester group in the thus obtained AA-PVA (A) is 0.1 to 40 mol%.
(Further, 0.3 to 30 mol%, particularly 0.5 to 20 mol%) is preferable, and if the content is less than 0.1 mol%, sufficient water resistance cannot be obtained, and conversely 40 mol% If it exceeds the range, the water solubility in the coating solution is lowered and the storage stability of the obtained coating solution is lowered, which is not preferable.

The amino group-containing compound (B) used in the present invention is represented by the following general formula, wherein R is a cyclic compound selected from an aromatic ring, an aliphatic ring and a heterocycle. residue obtained by removing a hydrogen, R ₁ is hydrogen, with either an alkyl radical, n is 0 or a positive integer, m is intended to represent a positive integer, respectively. R - [(CH _{2) n} -NHR _{1] m} ··· (1) according alkylamino group-containing compound as (B) is meta-xylene diamine, norbornane diamine, 1,3
Bisaminomethylcyclohexane, bisaminopropylpiperazine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenylmethane, 3,3 ′, 5 5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,
4-phenylenediamine, 3-methyl-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2 -Methyl-4,
6-diethyl-1,3-phenylenediamine, 2,4-
Diethyl-6-methyl-1,3-phenylenediamine,
Examples thereof include 2,4,6-trimethyl-1,3-phenylenediamine and 2-chloro-1,4-phenylenediamine, but water-soluble or water-dispersible ones are preferable, and among them, metaxylenediamine, 1 It is particularly preferable to use any of 3,3-bisaminomethylcyclohexane and norbornanediamine.

The ink jet recording medium of the present invention has a composition containing the above-mentioned AA-PVA (A) and the amino group-containing compound (B) in or on the surface of the supporting substrate. AA-ized P in such a composition
The content ratio of VA (A) and the amino group-containing compound (B) is not particularly limited, but the content ratio (A / B) of the AA-modified PVA (A) and the amino group-containing compound (B) is 100/0.
1-100 / 30 (further 100 / 0.3-100 /
25, particularly 100 / 0.5 to 100/20) (weight ratio), and the content ratio is 100 / 0.5.
When it exceeds 0.1, the water resistance tends to decrease, and when it is less than 100/30, the discoloration resistance tends to decrease, which is not preferable.

In the present invention, an ink fixing agent (cationic compound), an inorganic filler (synthetic silica, colloidal silica, alumina, etc.), a defoaming agent are added to such a composition as long as the object of the present invention is not impaired. Known additives such as agents, release agents, surfactants (silicon-based, fluorine-based, polyethylene glycol-based, etc.), preservatives, insect repellents, rust preventives, thickeners, etc. can also be added. Other paper-processing agents, for example, other conventionally known water-soluble resins such as polyvinyl alcohol, starch and carboxymethyl cellulose, and water-soluble inorganic compounds such as water-dispersible resins such as acrylic latex and SBR latex may be mixed. it can. It is also useful to add an acid (organic acid, inorganic acid), a metal compound (alum, aluminum sulfate, etc.), a β-diketone compound (acetylacetone, methyl acetoacetate, etc.) in order to suppress thickening due to the crosslinking agent. Is.

The ink jet recording medium of the present invention comprises the above composition in the supporting base material or on the surface of the supporting base material. A method for producing such recording medium will be described. First, examples of the supporting substrate include polyester, polyamide, polystyrene, polyvinyl chloride, polymethylmethacrylate, cellulose acetate, polycarbonate, polyimide, cellophane, celluloid, and other resin films, sheets, high-quality paper, medium-quality paper, ( Examples include papers such as (semi) glassine paper, glossy paper, (resin) coated paper, and synthetic paper, and further include films, sheets, etc. of cloth, metal, wood, etc., but not limited to these. It is not something that will be done.

When applying such a composition to a supporting substrate, the composition is applied to the surface of the supporting substrate so that the composition permeates the surface of the supporting substrate or the supporting substrate, and the composition is applied to the supporting substrate. The composition can be present, and in such coating, a size press coat, a roll coater method,
Any known method such as an air-coater method, a blade coater method, or a gate roll coater method is adopted. When the composition is applied, the solid content is 1 to 70% by weight (further, 2
-60% by weight, especially 5 to 50% by weight) is preferable, and when the solid content is less than 1% by weight, the adhesion amount is small, the printing density and the strength of the surface paper are low and the practicability is poor. On the contrary, if it exceeds 70% by weight, the viscosity of the coating solution becomes high, which makes coating difficult and causes coating unevenness, which is not preferable. The coating amount of the composition coated on the supporting substrate is 0.1 to 40 g / m ^{2 in} terms of solid content,
Particularly preferably, the amount is about 0.5 to 20 g / m ² . It is also possible to separately apply the coating liquids containing the AA-PVA (A) and the amino group-containing compound (B).

The thus obtained ink jet recording medium of the present invention is excellent in discoloration resistance and water resistance since the above-mentioned specific composition is present on the surface or in the substrate.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

Example 1 400% 10% aqueous solution consisting of 40 parts of AA-PVA (A) and 2 parts of metaxylenediamine (B) having a saponification degree of 99 mol%, an average degree of polymerization of 1200, and an acetoacetic acid ester group of 5 mol%. Amorphous synthetic silica (“Silysia 446” manufactured by Fuji Silysia Chemical Ltd., shape: spherical, particle diameter: 4.5
40 μm) and 10 parts of a cationized resin (“Sumiraz resin 100” manufactured by Sumitomo Chemical Co., Ltd.) as an ink fixing agent, and mixed and stirred to obtain a coating liquid, and the coating liquid has a basis weight of 1
After bar coating so as to 10 g / m ² of resin solids in fine paper 200 g / m ^2, dried for 2 minutes at at 105 ℃ cylindrical rotary dryer, an inkjet recording medium of the present invention Obtained.

The following evaluations were carried out on the obtained ink jet recording medium. (Discoloration resistance) The obtained ink jet recording medium is
After being left for 12 hours in a 50 ° C, 50% RH atmosphere, the YI (yellow index) value was measured by a reflection method using a color difference meter (“SZ-Σ90” manufactured by Nippon Denshoku Industries Co., Ltd.).

(Water resistance) An ink jet printer (Epson's "PM
-770 "), after leaving for 5 minutes in an atmosphere of 20 ° C and 65% RH, water droplets are dripped on the printed surface, and the state of the printed portion when rubbed with a finger is visually observed. It was evaluated as. ○: No peeling of the printed surface is observed △: Some peeling is observed on the printed surface, but the print is readable ×: The printed surface is peeled from the substrate

Example 2 Inkjet was carried out in the same manner as in Example 1 except that as the AA-modified PVA (A), an AA-modified PVA having a saponification degree of 95 mol%, an average degree of polymerization of 1700, and an acetoacetic ester group of 3 mol% was used. A recording medium was obtained and evaluated in the same manner.

Example 3 An ink jet recording medium was obtained in the same manner as in Example 1 except that norbornanediamine (B) was used instead of metaxylenediamine (B), and the same evaluation was performed.

Example 4 An ink jet recording medium was obtained in the same manner as in Example 1 except that the mixing amount of meta-xylenediamine (B) was changed to 1.5 parts, and the same evaluation was performed.

Example 5 An ink jet recording medium was obtained in the same manner as in Example 1 except that the mixing amount of norbornanediamine (B) was changed to 5 parts, and the same evaluation was performed.

Example 6 An ink jet recording medium was obtained in the same manner as in Example 1 except that 3 parts of 1,3-bisaminomethylcyclohexane (B) was used instead of the metaxylenediamine (B), and the same. Was evaluated.

Comparative Example 1 An ink jet recording medium was obtained in the same manner as in Example 1 except that glyoxal was used instead of metaxylenediamine (B), and the same evaluation was performed.

Comparative Example 2 An ink jet recording medium was obtained in the same manner as in Example 1 except that hexamethylenediamine was used instead of metaxylenediamine (B), and the same evaluation was performed.

Table 1 shows the evaluation results of the examples and comparative examples.

[0030]

[0031]

The ink jet recording medium of the present invention comprises:
Excellent discoloration resistance and water resistance.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 2, 2002 (2002.12.
2)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

[0005]

[Means for Solving the Problems] Therefore, the present inventor has conducted diligent research in view of the above circumstances, and as a result, AA-PVA
An ink jet recording medium having a composition containing (A) and an amino group-containing compound (B) represented by the following general formula (1) in or on the surface of a supporting substrate is the above-mentioned recording medium. The inventors have completed the present invention by finding that they can solve the problems. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, _{R 1} Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer. In the present invention, the amino group-containing compound represented by the general formula (1) ( B) is Metakishi Li diamine, and particularly preferably one of 1,3-bis-aminomethyl cyclohexane or norbornane diamine.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

The amino group-containing compound (B) used in the present invention is represented by the following general formula, wherein R is a cyclic compound selected from an aromatic ring, an aliphatic ring and a heterocycle. residue obtained by removing a hydrogen, R ₁ is hydrogen, with either an alkyl radical, n is 0 or a positive integer, m is intended to represent a positive integer, respectively. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) according alkylamino group-containing compound as (B) is Metakishi re diamine, norbornane diamine, 1,3
-Bisaminomethylcyclohexane, bisaminopropylpiperazine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 3,3 ', 5 , 5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,
4-phenylenediamine, 3-methyl-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2 -Methyl-4,
6-diethyl-1,3-phenylenediamine, 2,4-
Diethyl-6-methyl-1,3-phenylenediamine,
2,4,6-trimethyl-1,3-phenylenediamine, 2-chloro-1,4 can be cited phenylenediamines, etc., but is preferably a water-soluble or water-dispersible, among others Metakishi Li diamine, It is particularly preferable to use either 1,3-bisaminomethylcyclohexane or norbornanediamine.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

[0019] Example 1 saponification degree of 99 mol%, average polymerization degree of 1200, 10% aqueous solution of AA-PVA (A) 40 parts of Metakishi Li diamine (B) 2 parts of 5 mole% containing acetoacetate groups In 400 parts, amorphous synthetic silica (“Silysia 446” manufactured by Fuji Silysia Chemical Ltd., shape: spherical, particle diameter: 4.
5 μm) 40 parts and 10 parts of a cationized resin (“SUMIREZ Resin 100” manufactured by Sumitomo Chemical Co., Ltd.) as an ink fixing agent, and mixed and stirred to obtain a coating liquid, and the coating liquid has a basis weight of 100 g / after bar coating so as to 10 g / m ² of resin solids in fine paper of m ^2, dried for 2 minutes at at 105 ℃ cylindrical rotary drier, to obtain an ink jet recording medium of the present invention .

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023] In Example 3 Example 1, instead of the Metakishi Li diamine (B), except for using the norbornane diamine (B) to obtain an ink jet recording medium in the same manner were evaluated in the same manner.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

[0024] In Example 4 Example 1, except for changing the mixing amount of Metakishi Li diamine (B) to 1.5 parts to obtain a ink jet recording medium in the same manner were evaluated in the same manner.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

[0026] In Example 6 Example 1, instead of the Metakishi Li diamine (B), 1,3-bis-aminomethyl cyclohexane (B)
An ink jet recording medium was similarly obtained except that 3 parts of was used, and the same evaluation was performed.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027] In Comparative Example 1 Example 1, instead of the Metakishi Li diamine (B), except for using the glyoxal is to obtain an ink jet recording medium in the same manner were evaluated in the same manner.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

[0028] In Comparative Example 2 Example 1, instead of the Metakishi Li diamine (B), except for using hexamethylenediamine is to obtain an ink jet recording medium in the same manner were evaluated in the same manner.

Claims (3)

[Claims] 1. A composition comprising a polyvinyl alcohol (A) containing an acetoacetic ester group and an amino group-containing compound (B) represented by the following general formula (1) in a supporting substrate or on the surface of a supporting substrate. An ink jet recording medium comprising: R - [(CH _{2) n} -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R ₁ Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer.) 2. The amino group-containing compound (B) represented by the general formula (1) is any one of metaxylene diamine, 1,3-bisaminomethylcyclohexane and norbornanediamine. 1. The inkjet recording medium according to 1. 3. The content ratio (A / B) of the acetoacetic acid ester group-containing polyvinyl alcohol (A) and the amino group-containing compound (B) represented by the general formula (1) is 100/0.
The inkjet recording medium according to claim 1 or 2, wherein the ratio is 1 to 100/30 (weight ratio).