JP2002187344A - Ink jet recording resin composition and material to be recorded using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording resin composition for forming an ink accepting layer, the lustrous properties, ink absorbency and image quality of which the favorable and which has an excellent storage stability such as a light resistance or the like, and a material to be recorded using the resin composition. SOLUTION: In this recording resin composition for forming an ink accepting layer on a base material, the recording resin composition at least consists of 97 to 70 wt.% of inorganic particle (a) and 3 to 60 wt.% of a binder resin (b), wherein the sum of (a) and (b) is 100 wt.% The binder resin (b) includes an emulsified ultraviolet absorbing resin (d), which is produced by obtaining a resin solution by urethanating a polyester polyol (c) including a ultraviolet absorbing group, a polyol compound (e), which is employed when necessary, and a compound (f) including an ionic group through an organic polyisocyanate (g) in an inorganic solvent and then neutralized it with a neutralizer (h), and finally dispersing the resultant resin solution in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a recording resin composition suitable for ink jet recording and a recording medium using the same.

[0002]

2. Description of the Related Art In recent years, an ink jet recording method is a method in which fine droplets of ink are caused to fly according to various operating principles and adhere to a recording medium such as paper to record images, characters, and the like. Features include high speed, low noise, easy multi-coloring, and no development or fixing process.
It is rapidly spreading in various applications. Furthermore, the image formed by the color ink jet method can obtain a print comparable to printing by the plate making method or printing by the color photographic method, and when the number of copies is small, full-color image recording is possible. It is being widely applied to fields. Recording devices have been improved with improvements in recording characteristics such as high-speed recording, higher definition, and full-color recording, but advanced characteristics are also required for recording media. Have been. Along with this, demands for not only image recording quality but also image storability (light fastness, water fastness, moisture fastness, etc.) are gradually becoming higher and stricter. In particular, improvement in light resistance is desired. Therefore, it is the present condition that completely securing these required characteristics is an essential condition of the ink jet recording material.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording resin composition for forming an ink receiving layer having good glossiness, ink absorbency and image quality, and having excellent storage stability such as light fastness. And a recording material using the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polyester polyol having an ultraviolet absorbing group can be obtained by a urethane reaction in a resin composition for ink jet recording. It has been found that a recording material having an ink receiving layer formed on a substrate using a recording resin composition containing a binder resin containing a specific ultraviolet absorbing resin can solve such a problem, and to complete the present invention. Reached.

That is, the present invention relates to a recording resin composition for forming an ink receiving layer on a substrate, wherein the recording resin composition comprises at least 97 to 40% by weight of inorganic fine particles (a) and a binder resin (b). 3) to 60% by weight (here, the total of (a) and (b) is 100% by weight), wherein the binder resin (b) is a polyester polyol (c) containing an ultraviolet absorbing group and optionally other The polyol compound (e) used in the above, and the compound (f) containing an ionic group, by the organic polyisocyanate (g),
It is characterized by containing an ultraviolet absorbing resin (d) emulsified by neutralizing the resulting resin solution with a neutralizing agent (h) and dispersing in water after a urethanization reaction in an organic solvent. And a resin composition for inkjet recording. The polyester polyol (c) having an ultraviolet absorbing group of the invention provides a resin composition for inkjet recording represented by the general formula (1).

[0006]

Embedded image(R¹And R²Is a hydrogen atom or an alkyl having 1 to 10 carbon atoms
And n and n 'are integers of 4 to 8, m and m' are 1
Mn and m'n 'Rs ¹, R
²May be the same or different. )

According to the present invention, there is provided a resin composition for inkjet recording according to the above invention, wherein the ultraviolet absorbing resin (d) is a resin obtained by removing an organic solvent after emulsification. Further, in the above invention, there is provided a resin composition for inkjet recording, wherein the compound (f) containing an ionic group is a compound containing a carboxyl group and an active hydrogen group. Compound (f) containing ionic group
Is an alkyl dialkanol amine compound. The resin composition for inkjet recording according to the invention, wherein the compound (f) having an ionic group is a macromonomer having a tertiary and / or quaternary nitrogen atom in a side chain and two or more hydroxyl groups at a terminal. provide.

In the above invention, the inorganic fine particles (a) are
Provided is a resin composition for ink jet recording, which is colloidal silica. Further, in the above invention, there is provided a resin composition for inkjet recording, wherein the binder resin (b) contains a resin (i) having a hydrolyzable silyl group. Further, the present invention provides a recording material using the resin composition for inkjet recording according to any one of the above-mentioned inventions.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The recording medium of the present invention has a configuration in which an ink receiving layer is formed on a base material. Known substrates such as paper and plastic films can be used as the substrate.

Next, the ink-jet recording resin composition used for forming the ink receiving layer will be described. Examples of the inorganic fine particles (a) include alumina, silica, calcium carbonate, aluminum hydroxide, and calcium silicate. Preferred is silica, and particularly preferred is colloidal silica. Specifically, it is an aqueous dispersion type silica sol or organosilica sol. For the gloss and transparency of the ink receiving layer, those having a small particle size are preferred.
For example, the range is preferably 3 to 300 nm, more preferably 5 to 50 nm. The shape of the inorganic particles may be spherical, flat, columnar, or rosary.

Examples of the binder resin (b) that can be used include natural polymers or derivatives thereof (starch, sodium alginate, gelatin, casein, etc.), cellulose derivatives (methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc.), Vinyl alcohol-based polymers (polyvinyl alcohol, modified polyvinyl alcohol such as ethylene-vinyl alcohol copolymer carboxyl group-modified), ethylene-based polymers (ethylene-vinyl acetate copolymer, ethylene-maleic anhydride copolymer, etc.), Vinyl acetate-based polymers (polyvinyl acetate, vinyl acetate- (meth) acrylate copolymer, etc.), polyalkylene oxides (polyethylene oxide, ethylene oxide-propylene oxide) Such as de block copolymers), styrene polymers (styrene - butadiene copolymer, styrene - maleic anhydride copolymer, styrene -
(Meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester copolymer, etc.), acrylic polymer [(meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid Copolymer, a (meth) acrylate-nitrogen-containing compound (such as dimethylaminoethyl (meth) acrylate)], a polyurethane polymer, a polyester polymer, and a vinyl chloride copolymer. These can be used alone or in combination of two or more. Any resin can be used without limitation as long as the resin satisfies the function as a binder.

[0012] The binder resin (b) is preferably used in the form of an emulsion of the resin in that the ink absorption of the ink receiving layer can be improved. Any resin that can form an emulsion and satisfies the function as a binder can be used without limitation. Examples of such resins include acrylic polymers, styrene copolymers, polyurethane polymers, vinyl chloride polymers, polyvinyl acetate,
Examples thereof include an ethylene-vinyl acetate copolymer and the like, and one kind or a combination of two or more kinds can be used.

The weight average molecular weight of the binder resin (b) is not particularly limited, but is preferably 1,000 or more. The preferred average particle diameter of the emulsion formed by the binder resin (b) is 20 to 200 n.
m, more preferably 30 to 100 nm. If the particle size is larger than 200 nm, the transparency and the gloss are reduced.
If it is smaller than 20 nm, the ink absorbing property of the ink receiving layer is reduced. Among the above-mentioned binder resins (b), a polyurethane-based polymer is mentioned as a preferred resin because a functional group-containing component such as an ultraviolet absorbing group described later can be introduced relatively easily and the binder suitability is good.

The ultraviolet absorbing resin (d) contained in the binder resin (b) will be described. As the polyester polyol (c) having an ultraviolet absorbing group used for improving the light resistance (durability to ultraviolet light) of the binder resin, an ultraviolet absorber containing the compound represented by the formula (1) as an active ingredient is used. Good to do. Equation (1)
The UV-absorbing compound represented by the formula (1) can be used without any particular limitation as long as the values of m and m 'are within the above ranges.

As a method for producing the compound having an ultraviolet absorbing group represented by the formula (1), a lactone represented by the following formula (3) is ring-opening addition-polymerized with an alcohol represented by the following formula (2). Is what you get.

[0016]

Embedded image (R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 4 to 8.)

The alcohol represented by the above formula (2) is
Bis [3- (2H-benzotriazol-2-yl)-
4-hydroxy-benzeneethanol] methane.
As the alcohol, a synthetic product or a commercially available product can be used. The lactones represented by the formula (3) include ε-caprolactone, trimethyl-ε-caprolactone, monomethyl-ε-caprolactone, γ-butyrolactone, δ
-Valerolactone and the like.

The catalyst used for ring-opening addition polymerization of the lactone represented by the formula (3) to the alcohol represented by the formula (2) includes, for example, tetraethyl titanate, tetrabutyl titanate and tetrapropyl titanate. Organotitanium compounds, stannous octoate, dibutyltin oxide, dibutyltin dilaurate, organic tin compounds such as mono-n-butyltin fatty acid salts, stannous chloride, stannous bromide, stannous iodide, etc. Stannous halide, etc.

The amount of the catalyst used is 0.1
It is 10000 ppm, preferably 1-5000 ppm. If the amount of the catalyst used is less than 0.1 ppm, the ring-opening reaction of lactones is remarkably slow, which is not economical. Conversely 1000
When the content is 0 ppm or more, the ring opening reaction time is shortened, but the physical properties such as durability and water resistance of the synthetic resin using the obtained compound are deteriorated, and neither is preferable. Reaction temperature is 90 ~
240 ° C, preferably 100 to 220 ° C. When the reaction temperature is lower than 90 ° C., the ring-opening reaction of lactones is extremely slow, which is not economical. On the other hand, when the temperature is 240 ° C. or higher, a depolymerization reaction of the ring-opening addition-polymerized polylactone occurs, and neither is preferable. During the reaction, synthesis in an atmosphere of an inert gas such as nitrogen gas gives a good result on the hue and the like of the product. Thus, the polyester polyol (c) having an ultraviolet absorbing group of the present invention (hereinafter sometimes abbreviated as component (c)) is synthesized.

Other polyol compounds (e) (hereinafter sometimes abbreviated as compound (e)) according to the present invention include polyester polyols, polyether polyols, polycarbonate polyols, poly (meth) acryl polyols, Examples thereof include polyalkyl polyols and polyalkylene polyols. The compounds containing these polyol components are used alone or in combination of two or more. Compound (e) is a component (c) 1
0 to 200 parts by weight with respect to 00 parts by weight, and further 0 to 10 parts by weight
It is preferable to add 0 parts by weight.

As the compound (f) containing an ionic group according to the present invention (hereinafter sometimes abbreviated as compound (f)), a compound containing a carboxyl group and an active hydrogen group [dimethylolpropionic acid] Dimethylolbutanoic acid, a reaction product of a polyamine with an acid anhydride, a lactone adduct using dimethylolpropionic acid or dimethylolbutanoic acid as an initiator], an alkylalkanolamine compound [N-methyldiethanolamine, N-ethyldiethanolamine , N-phenyldiethanolamine, N
A lactone adduct using ethyl diethanolamine as an initiator], a macromonomer having a tertiary and / or quaternary nitrogen atom in a side chain and two or more hydroxyl groups at a terminal [dimethylaminoethyl methacrylate is 3-mercapto-
Macromonomer obtained by radical polymerization in an organic solvent such as methyl ethyl ketone in the presence of 1,2-propanediol. The compound (f) is preferably added in an amount of 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the component (c).

The organic polyisocyanate (g) according to the present invention includes 2,4-toluene diisocyanate,
2,6-toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyldimethylmethane diisocyanate, dibenzyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, Aromatic diisocyanates such as tetramethylxylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-
Aliphatic diisocyanate such as diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate And alicyclic diisocyanates such as hydrogenated trimethylxylylene diisocyanate. These organic polyisocyanates are used alone or in combination of two or more. Furthermore, these adduct modified products, carbodiimide modified products, allophanate modified products, buret modified products, uretdione modified products,
Modified products such as uretoimine modified product and isocyanurate modified product can also be used. These polyisocyanates are preferably hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate in consideration of light resistance. The organic polyisocyanate (g) is composed of the component (c) 10
3 to 200 parts by weight, more preferably 5 to 100 parts by weight per 0 parts by weight
It is preferable to add parts by weight.

The neutralizing agent (h) of the present invention includes ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanol. Amine, diethylethanolamine,
Morpholine, N-methylmorpholine, 2-amino-2-ethyl-
Organic amines such as 1-propanol, alkali metals such as lithium, potassium and sodium, sodium hydroxide,
Examples include inorganic alkalis such as potassium hydroxide,
In order to improve the weather resistance and water resistance after drying, those having high volatility which easily dissociates by heating are preferable, and ammonia, trimethylamine and triethylamine are preferable. Also, hydrochloric acid, sulfuric acid, inorganic acids such as nitric acid, formic acid, acetic acid, propionic acid, organic acids such as butyric acid, methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride,
Examples include quaternizing agents such as p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromhydrin, epichlorohydrin, and brombutane.
These neutralizing agents may be used alone or in combination of two or more. The neutralizing agent (h) is preferably added in an amount of 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the component (c).

The polyurethane resin, which is one type of the ultraviolet absorbing resin (d) obtained by reacting the polyester polyol (c) having an ultraviolet absorbing group in the present invention, is emulsified, but has a water dispersing ability. The compound (f) containing an ionic group as a hydrophilic group is introduced into the molecule, but if necessary, an anionic polar group such as a carboxylate, a sulfonate, a phosphate or a phosphonate is used. A nonionic polar group such as a group, a cationic polar group other than a quaternary ammonium salt, or an ether group may be introduced.

The blending ratio of the ultraviolet absorbing resin (d) blended in the binder resin (b) of the present invention is not particularly limited and can be appropriately selected from a wide range, but is preferably 0.1 to 100. % By weight, more preferably 0.3 to 9
It is 5% by weight, most preferably 0.5-90% by weight.

The polyurethane resin, which is one kind of the ultraviolet absorbing resin (d) obtained by reacting the polyester polyol (c) having an ultraviolet absorbing group, comprises a polyester polyol (c) having an ultraviolet absorbing group and another polyol. It can be obtained by subjecting compound (e) and compound (f) containing an ionic group to urethanization reaction with an organic polyisocyanate (g) in an organic solvent. Emulsification can be obtained by neutralizing the obtained resin solution with a neutralizing agent (h) and then dispersing it in water. Further, after the emulsion is formed, the organic solvent may be removed. A known method can be used for the method of emulsification.

Examples of the organic solvent include alcohols (eg, ethanol, isopropanol, n-butanol, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), and aliphatic hydrocarbons (eg, pentane, hexane, etc.). Heptane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), esters (e.g., ethyl acetate, n-butyl acetate, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g.,
Diethyl ether, dioxane, tetrahydrofuran, etc.). These organic solvents
You may use individually or in combination of 2 or more types.

The binder resin (b) of the present invention may further contain, if necessary, at least known additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, a processing stabilizer, an antioxidant, and a compatibilizer. One type can be blended. Examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 5-chloro-2-
Examples include benzotriazoles such as (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole and benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone. . Further, there may be mentioned those obtained by adding a group having a polymerizable double bond such as a vinyl group to the above-mentioned ultraviolet absorber, and polymerizing this to obtain a high molecular weight. Examples of the antioxidant include 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 3,5-di-ter
Hindered phenol-based antioxidants such as t-butyl-4-hydroxybenzylphosphonate-diethyl ester; organic sulfur-based antioxidants such as dilauryl 3,3'-dithiodipropionate; and phosphorus-based oxidation such as trialkylphenyl phosphate. And the like.
Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and nickel salt light stabilizers such as nickel dibutyldithiocarbamate. it can.
As the processing stabilizer, for example, Tris (2,4-di-te
and phosphorus-based processing stabilizers such as (rt-butylphenyl) phosphate. Examples of the antioxidant include 1,1-bis (4-hydroxyphenyl) cyclohexene, N, N′-diphenyl-p-phenylenediamine and the like. Although the amount of these additives is not particularly limited, it is usually 0.1% based on the binder resin.
It is preferable to use about 01 to 20% by weight.

As the resin (i) having a hydrolyzable silyl group contained in the binder resin (b), an alkoxysilane group-modified polyvinyl alcohol (for example, Kuraray R polymer), a hydrolyzable silyl group-containing polymerizable An acrylic copolymer obtained by copolymerizing an unsaturated monomer is exemplified. Examples of the hydrolyzable silyl group-containing polymerizable unsaturated monomer include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tributoxy silane, vinyl methoxy dimethyl silane, vinyl ethoxy dimethyl silane, vinyl isobutoxy dimethyl silane, vinyl dimethoxy methyl Silane, vinyldiethoxymethylsilane, vinyltris (β-methoxyethoxy) silane, vinyldiphenylethoxysilane, vinyltriphenoxysilane, γ-
(Vinylphenylaminopropyl) trimethoxysilane, γ- (vinylbenzylaminopropyl) trimethoxysilane, γ- (vinylphenylaminopropyl) triethoxysilane, γ- (vinylbenzylaminopropyl) triethoxysilane, divinyldimethoxysilane,
Divinyldiethoxysilane, divinyldi (β-methoxyethoxy) silane, vinyldiacetoxymethylsilane,
Vinyltriacetoxysilane, vinylbis (dimethylamino) methylsilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltrichlorosilane,
Vinylmethylphenylchlorosilane, allyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, allyldiacetoxymethylsilane, allyltriacetoxysilane, allylbis (dimethylamino) methylsilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyltrichlorosilane, Methacrylphenyldichlorosilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltri Ethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyltri Such as (beta-methoxyethoxy) silane can be exemplified.

The inorganic fine particles (a) thus obtained
And the binder resin (b) and the ultraviolet absorbing resin (d) are mixed to prepare a recording resin composition. The mixing method is
Known methods such as a homomixer, a Kedi mill, an azihomomixer, an ultrasonic mixer, and a toothed disk mixer can be used. The mixing ratio is preferably 97 to 40% by weight of the inorganic fine particles (a) and the binder resin (b).
3 to 60% by weight, more preferably 95 to 60% by weight of the inorganic fine particles (a), 5 to 40% by weight of the binder resin (b), and most preferably 90 to 30% by weight of the inorganic fine particles (a).
% By weight and 10 to 70% by weight of the binder resin (b). If the amount of the inorganic fine particles (a) exceeds 97% by weight, the film-forming property tends to decrease. If the amount is less than 40% by weight, the quick-drying property and the ink absorbency decrease.

The coating liquid used for forming the ink receiving layer includes known ink fixing agents, cross-linking agents, anti-blocking agents, film-forming auxiliaries, etc., such as ink jet recording properties, storage stability of recorded images, and improvement of coating liquid properties. May be further added as necessary. The recording resin composition used for forming the ink receiving layer of the present invention is applied to a known substrate such as paper or a plastic film by using a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a gravure coater, or silk. A known coating method such as a screen coater method or a die coat method, or a known coater, is applied, and an ink receiving layer is formed on at least one surface of the substrate to obtain a recording material. The thickness of the ink receiving layer is, for example, 1 to 50μ, further 3 to 30μ,
Particularly, 5 to 20 μm is preferable.

[0032]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. still,
Unless otherwise specified, parts by weight and% by weight are converted to solid contents. The recording materials obtained in Examples and Comparative Examples were evaluated as follows. (Lightfastness 1) Yellow: Y, Magenta: M, Cyan: C, Black: B
Was printed on a recording material and stored for one month in an indoor environment through a south-facing window glass, and the color density before and after storage was measured with a Macbeth color densitometer. The average color density retention of CMYB was 85% or more, ○, 70 to 85%: Δ, and less than 70%: X. (Lightfastness 2) Yellow: Y, Magenta: M, Cyan: C, Black: B
Is printed on the recording material, the temperature of the xenon weather meter black panel is 65 ° C, and the humidity in the bath is 5
0% RH, irradiation energy at 340 nm: 0.3
Exposure was performed at 5 W / m ² at 90 kJ / m ² . Next, the color density before and after the exposure was measured with a Macbeth color densitometer. The average color density retention of CMYB is 85% or more ○, 70 to 85%: Δ,
Less than 70%: x

(Ink Drying Property) After printing solid images of cyan, magenta, yellow, black and mixed colors of red, green and blue using the following printer, after 30 seconds, PPC copy paper was printed on the printed portion. And load (500 g / cm ² ) 10
After a lapse of 2 seconds, the PPC paper was peeled off, and the degree of transfer of the ink to the copy paper was visually determined based on the following criteria. ：: No transfer of ink to copy paper was observed at all. Δ: Slight transfer of ink was observed. ×: Marked transfer of ink. (Print Quality) An ISO standard image was printed using the following printer, and visually judged based on the following criteria. ：: No poor image quality such as bleeding or unevenness is observed. Δ: Slightly poor image quality such as blurring or unevenness is observed. X: Image quality defects such as bleeding and unevenness are remarkable, and a clear image cannot be obtained. (Glossiness) The glossiness (85 °) was measured using a glossmeter. ：: 60 or more. Δ: 40 or more. X: 40 or less.

(Synthesis Example 1 of Polyester Polyol (c) Having Ultraviolet Absorbing Group) 1,1-Bis- [3- (2H) was placed in a glass flask equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer. -Benzotriazol-2-yl) -4
-Hydroxy-benzeneethanol] methane (trade name “MBEP”, manufactured by Otsuka Chemical Co., Ltd.), 129.3 g, ε-
170.3 g of caprolactone and 50 ppm of mono-n-butyltin fatty acid salt (trade name “SCAT-24”, manufactured by Sankyoki Gosei Co., Ltd.) were added. The reaction temperature was maintained at 150 ° C., and after 6 hours, the concentration of ε-caprolactone in the reaction solution was measured by gas chromatography and found to be 0.43%, so the reaction was terminated. This reaction product has an acid value (mgKOH /
g) 1.8, viscosity 2645 CP / 60 ° C., number average molecular weight (MN) 1391, weight average molecular weight (M
W) Compound (1) in liquid form at room temperature with 1688 and MW / MN 1.213 was obtained. Further, as a result of dissolving 10 mg of compound (1) in 50 ml of chloroform and measuring an ultraviolet-visible absorption spectrum using a quartz cell having an optical path length of 1 mm,
As shown in JP-A-10-265557, it was found that the compound (1) showed a sufficiently large absorption in the ultraviolet region.

(Synthesis Example 2 of Polyester Polyol (c) Having an Ultraviolet Absorbing Group) Using the same apparatus as in Synthesis Example 1, 1,1-bis- [3- (2H-benzotriazol-2-yl)- 4-hydroxy-benzeneethanol]
Methane (trade name “MBEP”, manufactured by Otsuka Chemical Co., Ltd.) 9
3.7 g, ε-caprolactone 206.3 g, mono-n
-50 ppm of butyltin fatty acid salt (trade name "SCAT-24", manufactured by Sankyoki Gosei Co., Ltd.) was added. Reaction temperature 1
After 6 hours while maintaining the temperature at 50 ° C., the concentration of ε-caprolactone in the reaction solution was measured by gas chromatography and found to be 0.55%. Thus, the reaction was terminated. The reaction has an acid number (m
gKOH / g) 2.5, viscosity 987CP / 60 ° C, GP
From C analysis, MN2017, MW2465, MW / MN
Compound (2) as a solid at room temperature of 1.222 was obtained. Also, 10 mg of compound (2) was dissolved in 50 ml of chloroform, and the ultraviolet-visible absorption spectrum was measured using a quartz cell having an optical path length of 1 mm.
As shown in Japanese Patent Publication No. 7, compound (2) was found to exhibit a sufficiently large absorption in the ultraviolet region.

(Ultraviolet absorbing resin-1) 250 parts by weight of acetone and 262.2 parts by weight of isophorone diisocyanate (IPDI) are placed in a glass flask equipped with a cooling tube, a nitrogen introducing tube, a dropping funnel, a thermometer and a stirrer. While stirring under a nitrogen atmosphere, 689.77 parts by weight of the ultraviolet absorbing compound obtained in Synthesis Example 1 is further added dropwise. The temperature of the flask was raised to 65 ° C., the reaction was carried out for 2 hours, and 48.02 parts by weight of dimethylolbutanoic acid (DMBA) was charged.
0.30 parts by weight of dibutyltin dilaurate was charged and 1
The reaction was continued for 0 hours. NC at the end of prepolymer reaction
The O concentration was 0.452 mmol / g (theoretical NCO concentration was 0.44 mmol / g).
g), the number average molecular weight by gel permeation chromatography (GPC) is 4400, and the weight average molecular weight is 810
It was 0. Next, dimethylaminoethanol 28.6
6 parts by weight to neutralize the carboxylic acid content,
An acetone solution of the prepolymer was dropped into parts by weight to form an emulsion. Then, acetone as a solvent was removed under reduced pressure to obtain a desired aqueous ultraviolet absorbing resin. The nonvolatile content of this water-based UV-absorbing resin is 40%, and the average particle size by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics) is 9%.
It was 5 nm.

(Ultraviolet absorbing resin-2) 250 parts by weight of acetone and 53.8 parts by weight of isophorone diisocyanate (IPDI) were placed in a glass flask equipped with a cooling tube, a nitrogen introducing tube, a dropping funnel, a thermometer and a stirrer. , Under nitrogen atmosphere,
While stirring, 178.7 parts by weight of the ultraviolet absorbing compound obtained in Synthesis Example 1 is further added dropwise. The temperature of the flask was raised to 65 ° C., the reaction was carried out for 2 hours, 17.5 parts by weight of N-methyldiethanolamine was charged, and 0.30 part by weight of dibutyltin dilaurate was further charged, and the reaction was continued for 10 hours. The NCO concentration at the end of the prepolymer reaction was 0.452 mmol / g (theoretical NCO concentration 0.44 mmol / g)
The number average molecular weight by gel permeation chromatography (GPC) was 4,400, and the weight average molecular weight was 8,100. Next, 8.84 parts by weight of acetic acid was added to neutralize the amine component, and an acetone solution of the prepolymer was dropped into 600 parts by weight of water to form an emulsion. Then, acetone as a solvent was removed under reduced pressure to obtain a desired aqueous ultraviolet absorbing resin. The nonvolatile content of this water-based ultraviolet absorbing resin is 4
At 0%, the average particle size measured by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics Co., Ltd.) was 93 nm.

(Ultraviolet absorbing resin-3) Synthesis was carried out in the same manner as for ultraviolet absorbing resin-1, except that the ultraviolet absorbing compound used was changed to the compound obtained in Synthesis Example 2, and the desired aqueous ultraviolet absorbing resin was obtained. A water-soluble resin was obtained. The nonvolatile content of this aqueous ultraviolet absorbing resin was 40%, and the average particle size measured by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics) was 82 nm.

(UV absorbing resin-4) 225 parts by weight of methyl ethyl ketone, 262 parts by weight of dimethylaminoethyl methacrylate, 1-mercapto 13 parts by weight of 2,3-propanediol, azobismethylbutyronitrile (ABN-E) 1.5 by Wako Pure Chemical Industries, Ltd.
A part by weight was charged and polymerization was carried out at 80 ° C for 6 hours to obtain a macromonomer. The nonvolatile content of the obtained macromonomer is 5
3.2%, hydroxyl value (KOHmg / g) 25.8, amine value (KO
Hmg / g) was 181. Next, acetone 139.8
Parts by weight, dibutyltin dilaurate 0.30 parts by weight, isophorone diisocyanate (IPDI) 20.7 parts by weight,
While stirring under a nitrogen atmosphere, 129.2 parts by weight of the ultraviolet absorbing compound obtained in Synthesis Example 1 and 21.0 parts by weight of the macromonomer are further added dropwise. 75 ° C flask temperature
And the reaction was continued for 6 hours. The number average molecular weight of the urethane solution at the end of the reaction was 4000 by gel permeation chromatography (GPC), and the weight average molecular weight was 100.
00. Next, 9.73 parts by weight of acetic acid was added to 217.4 parts by weight of the urethane solution to quaternize the tertiary amine part, and the mixture was dropped into 507 parts by weight of water to form an emulsion. Thereafter, the solvent, methyl ethyl ketone, was removed under reduced pressure to obtain a desired ultraviolet absorbing resin emulsion.
The non-volatile concentration of this ultraviolet absorbing resin emulsion is 3
At 5%, the average particle size measured by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics Co., Ltd.) was 90 nm.

(Ultraviolet absorbing resin-5) The synthesis was carried out in the same manner as the ultraviolet absorbing resin-4, except that the ultraviolet absorbing compound used was changed to the compound obtained in Synthesis Example 2. A resin emulsion was obtained. The non-volatile content of this ultraviolet absorbing resin emulsion was 35%, and the average particle size measured by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics) was 82 nm.

As (binder resin-1), an anionic water-based polyurethane emulsion NeoRez R-960 (manufactured by Avicia Co., Ltd.) was used. As (binder resin-2), cationic water-based polyurethane emulsion F-8559D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
It was used. (Binder resin-3) 219 parts by weight of IPA (isopropyl alcohol) was placed in a 2 liter reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer, and 1.23 parts by weight of AIBN was stirred. Was added and dissolved, and the mixture was heated to 80 ° C. As copolymerization components, 4.93 parts by weight of 3-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.), 49.3 parts by weight of diethylaminoethyl methacrylate, MMA9
6.16 parts by weight, BA (butyl acrylate) 96.2
4 parts by weight were mixed and dropped into the reaction vessel over about 4 hours using a dropping funnel. After the completion of the dropping, AI is added as an additional catalyst.
BN (0.25 parts by weight) was dissolved in IPA (25 parts by weight) and added dropwise to the reaction vessel, and the reaction was maintained for 2 hours. After completion of the polymerization, 16 parts by weight of acetic acid was added to the reaction vessel while stirring was continued, and 705 parts by weight of water was dropped into the reaction vessel over about 2 hours to form an emulsion. After emulsification, IPA was evaporated using a rotary evaporator to obtain a cationic acrylic copolymer f-3. The solid content of this resin composition was 40% by weight. (Binder resin-4)
A 30% aqueous solution of polyvinyl alcohol PVA-405 (manufactured by Kuraray Co., Ltd.) was used.

Example 1 100 parts of a binder resin (b) were mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 1 of the composition was obtained. Inorganic fine particles (a)
As spherical colloidal silica (manufactured by Nissan Chemical Industries, Ltd., S
T-20, solid content 20%, particle size 15 nm).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 1) and 90 parts of (binder resin-1) was used.

(Example 2) A recording resin was prepared by mixing 100 parts of a binder resin (b) with 400 parts of inorganic fine particles (a) and adding ion-exchanged water so that the solid content of the coating solution became 20%. A coating solution 2 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 2) and 90 parts of (binder resin-2) was used.

Example 3 100 parts of a binder resin (b) were mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 3 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 2) and 90 parts of (binder resin-3) was used.

Example 4 A recording resin was prepared by mixing 100 parts of a binder resin (b) with 400 parts of inorganic fine particles (a) and adding ion-exchanged water so that the solid content of the coating solution was 20%. A coating solution 4 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Made, Snowtex AK, solid content 19%, particle size 15n
m) was used. 10 parts of (ultraviolet absorbing resin-3) and (binder resin-2) as the binder resin (b)
Was used in a proportion of 90 parts.

Example 5 100 parts of a binder resin (b) was mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 5 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 4) and 90 parts of (binder resin-2) was used.

Example 6 100 parts of a binder resin (b) were mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating liquid 6 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 5) and 90 parts of (binder resin-2) was used.

Example 7 100 parts of a binder resin (b) were mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 7 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (ultraviolet absorbing resin-
A mixture of 10 parts of 5) and 90 parts of (binder resin-3) was used.

(Comparative Example 1) A recording resin was prepared by mixing 100 parts of a binder resin (b) with 400 parts of inorganic fine particles (a) and adding ion-exchanged water so that the solid content of the coating solution was 20%. A coating liquid 8 of the composition was obtained. Inorganic fine particles (a)
As spherical colloidal silica (manufactured by Nissan Chemical Industries, Ltd., S
T-20, solid content 20%). (Binder resin-1) was used as the binder resin (b).

Comparative Example 2 100 parts of a binder resin (b) were mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 9 of the composition was obtained. Inorganic fine particles (a)
As cationic colloidal silica (Nissan Chemical Co., Ltd.)
Manufactured by Snowtex AK, solid content 19%).
As the binder resin (b), (binder resin-2)
It was used.

Comparative Example 3 100 parts of binder resin (b) was mixed with 400 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 10 of the composition was obtained. As the inorganic fine particles (a), cationic colloidal silica (Snowtex AK, manufactured by Nissan Chemical Co., Ltd., solid content 19%) was used. (Binder resin-4) was used as the binder resin (b).

(Comparative Example 4) 400 parts of a binder resin (b) was mixed with 100 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating liquid 11 of the composition was obtained. As the inorganic fine particles (a), cationic colloidal silica (Snowtex AK, manufactured by Nissan Chemical Co., Ltd., solid content 19%) was used. As a binder resin, (ultraviolet absorbing resin-
A mixture of 40 parts of 2) and 360 parts of (binder resin-2) was used.

(Comparative Example 5) 400 parts of binder resin (b) was blended with 100 parts of inorganic fine particles (a), and ion-exchanged water was added so that the solid content of the coating solution became 20%. A coating solution 12 of the composition was obtained. As the inorganic fine particles (a), cationic colloidal silica (Snowtex AK, manufactured by Nissan Chemical Co., Ltd., solid content 19%) was used. As the binder resin (b), a resin obtained by mixing 40 parts of (ultraviolet absorbing resin-4) and 360 parts of (binder resin-2) was used.

A coating solution of the recording resin composition obtained in each of Examples and Comparative Examples was applied so as to have a dry coating amount of 45 μm, and an ink receiving layer having a thickness of 190 μm was made of a base material: art paper (N
K white tong loss 180.0). Epson printer (Epson PM)
800C). Table 1 shows the evaluation results of the recording materials.

[0055]

[Table 1]

As is evident from the examples, the storage material prepared from the recording resin composition of the present invention has good glossiness, ink absorbency and image quality, and has excellent light fastness, so that it can be stored stably. The present invention can provide a recording resin composition having excellent properties and a recording material using the same. Further, in Examples 3 and 7 using the binder resin 3 which is a resin having a hydrolyzable silyl group, it can be seen that there is almost no powder dropping phenomenon when cutting the recording material, so that the effect of improving the coating film strength is high.

[0057]

According to the present invention, there is provided a recording resin composition for forming an ink receiving layer having good glossiness, ink absorbency and image quality, and having excellent storage stability such as light resistance. The used recording material can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 75/06 C08L 101/10 101/10 C09D 5/02 C09D 5/02 5/32 5/32 175 / 04 175/04 B41J 3/04 101Y F-term (reference) 2C056 EA05 FC06 2H086 BA15 BA33 BA34 4J002 AB021 AB041 AB051 AD011 AD021 BB061 BB101 BB221 BC041 BD031 BE021 BF021 BG041 BG051 BG071B03 001 001 GH00 GS00 HA07 4J034 BA05 BA08 CA02 CA04 CA13 CA14 CA17 CA22 CB03 CB04 CB08 CC02 CC12 CC62 CD01 DA01 DA05 DB03 DB07 DB08 DF01 DF02 DF11 DF12 DF17 DF32 DG00 DP02 DP18 HA01 HA07 HB06 HB08 HCB12 HC13 HCB HC HC HC HC HC HC67 HC71 HC73 JA02 JA14 JA30 LA16 LA36 QB17 QC05 RA07 RA16 4J038 DG111 DG181 DG271 DG281 DG291 DL151 GA08 HA156 HA446 KA0 8 KA20 LA02 MA08 MA10 NA01 NA03 PC08 PC10

Claims (9)

[Claims] 1. A recording resin composition for forming an ink receiving layer on a substrate, wherein the recording resin composition comprises at least 97 to 40% by weight of inorganic fine particles (a) and 3 to 40% by weight of a binder resin (b). 60% by weight (here, the total of (a) and (b) is 100% by weight), and the binder resin (b)
Is a polyester polyol (c) containing an ultraviolet absorbing group, another polyol compound (e) optionally used, and a compound (f) containing an ionic group, are reacted with an organic polyisocyanate (g) in an organic solvent. Wherein the resulting resin solution is neutralized with a neutralizing agent (h) and then dispersed in water to form an emulsion, thereby containing an ultraviolet absorbing resin (d). Recording resin composition. 2. Polyester poly containing an ultraviolet absorbing group
The all (c) is represented by the general formula (1).
Ink-jet recording resin composition. Embedded image(R¹And R²Is a hydrogen atom or an alkyl having 1 to 10 carbon atoms
And n and n 'are integers of 4 to 8, m and m' are 1
Mn and m'n 'Rs ¹, R
²May be the same or different. ) 3. The resin composition for ink jet recording according to claim 1, wherein the ultraviolet absorbing resin (d) is a resin obtained by removing an organic solvent after emulsification. 4. The resin composition for ink jet recording according to claim 1, wherein the compound (f) containing an ionic group is a compound containing a carboxyl group and an active hydrogen group. 5. The resin composition for ink jet recording according to claim 1, wherein the compound (f) containing an ionic group is an alkyl dialkanolamine compound. 6. The compound (f) containing an ionic group is a macromonomer having a tertiary and / or quaternary nitrogen atom in a side chain and two or more hydroxyl groups at a terminal.
The resin composition for inkjet recording according to any one of the above. 7. The resin composition for ink jet recording according to claim 1, wherein the inorganic fine particles (a) are colloidal silica. 8. The resin composition for ink jet recording according to claim 1, wherein the binder resin (b) contains a resin (i) having a hydrolyzable silyl group. 9. A recording material using the resin composition for ink jet recording according to claim 1.