JP2002052816A - Translucent recording medium for ink jet recording and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a translucent recording medium for ink jet recording capable of suppressing an adverse influence to be given to an environment to a maximum limit in the case of a waste disposal by incorporating excellent OHP suitability due to an ink jet recording and good biodegradability. SOLUTION: The translucent recording medium for ink jet recording comprises a matrix of a silicon oxide made by a decomposition polymerization of an organic silicon compound, and a saccharide material of an acetyl derivative of a cellulose or an oligosaccharide so that a translucent base of a polymer substance in which the silicon oxide and the saccharide material are made of the polymer substance made of at least one bond of a hydrogen bond, siloxane bond, urethane bond, urea bond and amide bond is surface treated by a deacetylation in such a manner that an acetyl group of the surface of the base is less than inner acetyl group of the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium,
The present invention relates to a light-transmissive recording medium suitable for inkjet recording for HP and a method for manufacturing the same.

[0002]

2. Description of the Related Art Ink jet recording is a method of recording characters and figures on the surface of a recording medium by ejecting ink as small droplets from fine nozzles. As the ink jet recording method, an electric signal is converted into a mechanical signal using an electrostrictive element, and the ink stored in the nozzle head portion is continuously or intermittently ejected, and characters or symbols are printed on the surface of the recording medium, In the method of recording a figure and the method described in JP-A-54-59936, the ink that has been subjected to the action of thermal energy causes a sudden change in volume, and the action force caused by this state change causes the ink to be ejected into the nozzle. A method of recording characters, symbols, and figures on the surface of a recording medium by ejecting ink continuously or intermittently from a recording medium has been put to practical use.

In recent years, ink-jet recording has attracted attention as a recording method capable of performing high-speed printing and color printing with little noise, and has been widely used. As a recording medium used in the ink jet recording method, a conventional paper or a recording medium in which a porous ink receiving layer is provided on a substrate called an ink jet recording paper,
Alternatively, an optically transparent recording medium for an overhead projector (OHP) has been used. In particular, when it comes to OHP recording media, these constituent materials, mainly the materials constituting the base material, include polyester resins, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, and polyvinyl chloride. Resin,
A film such as a polyimide resin is used.

On the other hand, the amount of synthetic plastic materials used in various industrial fields tends to increase year by year, and accordingly, the amount of synthetic plastic waste also increases, and the treatment thereof has become a major social problem worldwide. ing. Some of these waste plastics are collected and incinerated, while others are disposed of in landfills. In general, when synthetic plastics are incinerated, they generate a large amount of heat and may cause damage to the incinerator, and many synthetic plastics generate harmful gases when incinerated. Moreover, in the case of landfill disposal, the problem of securing a disposal site and the problem of adverse effects on the natural environment cannot be ignored.

Under these circumstances, with regard to consumables used in an ink jet recording apparatus, the problem of disposal of consumables after use has become important with the spread of the apparatus due to environmental problems and the like. Is coming. In particular, as for the recording medium for OHP, as described above, since the base material is made of synthetic plastic, sufficient consideration must be paid to disposal treatment after use. However, in the conventional OHP film for ink-jet, the above-mentioned disposal treatment is not considered, and when a large amount of waste is generated, there is a concern that it may adversely affect the environment. In consideration of this problem, JP-A-6-239014 and JP-A-9-393.
No. 79 proposes a recording medium using a biodegradable plastic sheet as a base material.

[0006] However, although the above recording medium is a recording medium which is excellent in ink jet recording and suppresses adverse effects on the environment, the recording medium for OHP is
Unlike fibrous paper, ink absorbency is poor. Therefore, there is a contrivance for heating the OHP recording medium to speed up the drying of the ink. However, since the heat resistance of the OHP recording medium is inferior, the recording medium may be deformed. It is also disclosed that an OHP recording medium is used as a base material and an ink receiving layer is provided on a surface layer. However, in the drying step of the receiving layer, if the temperature applied to the substrate is not 120 ° C or less,
Heat shrinkage of the substrate becomes a problem.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide high transparency, excellent OHP suitability, excellent heat resistance, ink absorptivity, and ink jet recording suitability such as coloring. It is still another object of the present invention to provide a light-transmitting recording medium used for ink-jet and having excellent characteristics capable of maximally suppressing the adverse effect on the environment caused by waste when disposed after use, and a method of manufacturing the same.

[0008]

The above object is achieved by the following invention. That is, the present invention provides a silicon oxide matrix formed by decomposition polymerization of an organosilicon compound,
A saccharide material of an acetyl derivative of cellulose or an oligosaccharide, wherein the silicon oxide and the saccharide material are composed of at least one bond of a hydrogen bond, a siloxane bond, a urethane bond, a urea bond, and an amide bond. The light-transmitting substrate which is a molecular substance is subjected to a surface treatment for deacetylation, so that the number of acetyl groups on the surface of the light-transmitting substrate is smaller than the number of acetyl groups inside the substrate. It is a light transmitting recording medium. Also,
The present invention comprises a silicon oxide matrix formed by decomposition polymerization of an organosilicon compound, and a saccharide material of an acetyl derivative of cellulose or an oligosaccharide, and the silicon oxide and the saccharide material form a hydrogen bond or a siloxane bond. , A urethane bond, a urea bond, a polymer substance comprising at least one bond of an amide bond, the light-transmitting substrate is subjected to a deacetylation surface treatment, acetyl on the surface of the light-transmitting substrate A method for producing a light-transmissive recording medium for inkjet recording, comprising a step of reducing the number of groups to be smaller than the acetyl groups in the base material.

It is preferable that the surface treatment for deacetylation is at least one of an alkali solution treatment and an enzymatic treatment.

That is, due to the above-mentioned material constitution, the recording medium of the present invention has not only high transparency and excellent OHP suitability but also good ink jet suitability and excellent heat resistance. Heating for drying the ink becomes possible.

Further, the recording medium of the present invention is discarded because all or most of the base material is a saccharide material having biodegradability and a silicon oxide which is a component of soil. At this time, it is possible to minimize the adverse effect on the environment.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The recording medium of the present invention is characterized by comprising a polymer substance which is a reaction product of a saccharide material (acetyl derivative of cellulose or oligosaccharide) and a silicon oxide from an organosilicon compound. That is, the polymer substance constituting the recording medium of the present invention has not only heat resistance but also high transparency.

Particularly, as a recording medium for OHP, 10
%, It is preferable to use a substrate made of a material having a haze (turbidity) of not more than 0.1%. Note that the haze degree is one of the indexes of translucency, and is represented by the following equation (1).

[0014]

(Equation 1)

Preferred examples of such a synthetic polymer of a silicon oxide-saccharide material include cellulose, cellulose, and the like.
Oligosaccharides and their derivatives. Oligosaccharides are
It means from disaccharide to about decasaccharide, and is classified into homo-oligosaccharide composed of a single saccharide and hetero-oligosaccharide composed of two or more monosaccharides. Particularly preferred is cellobiose. And cellulose-based oligosaccharides such as cellotriose, cellotetraose and cellopentaose; starch-based oligosaccharides such as maltose, maltotriose, maltotetraose and maltopentaose; and sucrose heteroheterosaccharides. Examples of the derivatives include acetylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc., acetylated products of each oligosaccharide (eg, acetylcellobiose), esterified products (eg, cellobiose adipate), and etherified products (eg, hydroxyethylmaltose). It is.

In particular, a light-transmissive recording medium using an acetyl derivative of cellulose or oligosaccharide is preferred because of its ease of synthesis. The organic silicon compound is a compound represented by the following chemical formula (2).

[0017]

Embedded image

(Wherein R ′ represents a lower alkyl group having about 1 to 4 carbon atoms which may have a substituent or an aryl group which may have a substituent. C 1-4
R ′ and R ″ may be different depending on n. N is an integer of 0 to 2. Specifically, trimethoxysilane, triethoxysilane, triethoxysilane, Propoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane , Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminobutyltrimethoxysilane, aminobutyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiphenyl Ethoxysilane and the like.

In the present invention, the weight ratio of silicon oxide is 50% with respect to the total amount (silicon oxide-saccharide material) in order to impart flexibility to the light transmitting recording medium.
The following is preferred.

The bonds between the above-mentioned cellulose, oligosaccharides and derivatives thereof and the silicon oxide formed by the decomposition polymerization of the above-mentioned organosilicon compound are hydrogen bonds (-OH ... O <),
Siloxane bond (-O-Si), urethane bond (-NH
-CO-O-), urea bond (-NH-CO-NH)
-) And an amide bond (-NH.CO-).

The molecular weight of the thus-obtained silicon oxide-saccharide polymer material is preferably about several thousand to several hundred thousand, more preferably about 10,000 to 100,000. I do.

The base material of the recording medium of the present invention has a thickness of:
It is optional according to the specifications of the ink jet recording apparatus to be used, and is not particularly limited.
Those having a thickness of about 300 μm are preferably used.

Next, in the present invention, the surface of the substrate of the present invention can be treated to further improve the print quality. This is because acetylated cellulose or oligosaccharide cellulose is used as a saccharide material having a silicon oxide matrix and at least one bond of a hydrogen bond, a siloxane bond, a urethane bond, a urea bond, and an amide bond. It has the advantage that the compatibility with the reaction solvent becomes better and the reaction can be easily performed.On the other hand, when the aqueous ink for ink is mainly used,
It is better to modify the surface of the light-transmitting substrate to be more hydrophilic,
This is because better printing quality can be obtained.

In order to increase the hydrophilicity of the surface of the light-transmitting substrate, it is effective to reduce the number of acetyl groups bonded to cellulose or oligosaccharide (deacetylation treatment).

The deacetylation treatment includes a treatment performed by immersion in an alkaline solution (alkali solution treatment), a treatment performed by immersion in an enzyme solution (enzymatic treatment), or a combination of both.

For the alkali solution treatment, a known alkali solution can be used. Aqueous solutions of sodium, potassium, calcium, barium, etc. and ammonium hydroxide, and aqueous solutions of salts of weak acids with strong alkalis such as sodium acetate, potassium acetate, sodium carbonate, sodium borate, potassium borate, sodium methoxide, sodium Metal alkoxides such as sodium, potassium and calcium such as ethoxide and potassium methoxide;

The pH of the solution to be used may be on the alkali side, but is preferably 7.5 or more and 12 or less. If it is a strong alkali, the surface may be roughened.

For the enzymatic treatment, an enzyme such as esterase or lipase which can selectively cleave the ester bond between the acetyl group and the sugar can be used. The biodegradability of the light-permeable recording medium treated with an alkali solution or / and enzymatic treatment in the present invention is improved by the deacetylation treatment during disposal treatment after use as an inkjet recording medium.

Also, the physical properties of the recording medium for ink jet,
For example, in order to improve beading resistance, blocking resistance, etc., various additives, dispersants, lubricants, PH adjusters, fluorescent paints, preservatives, etc., do not reduce the performance of the recording medium in the present invention. It can be used in a range.

In the present invention, the effect of improving the printing quality mainly when an aqueous inkjet ink is used is recognized by subjecting the surface of the light-transmitting substrate to deacetylation treatment. By the effect of improving hydrophilicity by such a deacetylation treatment, it is possible to improve the surface of the light-transmitting substrate, for example, to improve the coating properties of the surface. Therefore, an ink receiving layer with further improved adhesion can be provided. The ink receiving layer is an ink absorbing layer for improving printing quality by means different from the present invention, and a known material can be used.

In the case of providing an ink receiving layer, in the present invention, since the light-transmitting substrate has heat resistance, the temperature of 120 ° C.
The above heating does not cause thermal deformation such as thermal shrinkage of the substrate. Therefore, the time for the drying step and the like can be reduced.

[0032]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

Example 1, Reference Example 1 10 g of acetylcellulose having a degree of acetylation of 40% was added to T
Dissolved in 40 g of HF (tetrahydrofuran), added 8.44 g of tetramethoxysilane and 2.5 g of 0.1 N hydrochloric acid, and stirred at room temperature for 2 hours to obtain acetyl cellulose-silicon oxide having a siloxane bond. As a result of measuring the molecular weight, the average molecular weight was about 30,000.

This reaction product was cast to 80 μm
The following characteristics were evaluated for a thick film. In FIG.
Indicates infrared total reflection absorption spectrum data. This result
Fruit, 1740cm ^-1There is a peak indicating an acetyl group near
You.

Next, it was immersed in a methanol solution of sodium methoxide (pH 9.0) for 3 hours to perform a deacetylation treatment. FIG. 2 shows the infrared total reflection absorption spectrum data. It was found that the peak of the acetyl group near 1740 cm ^-1 was reduced, indicating that the deacetylation treatment was performed. The transparency of this film was 94% on average in the visible light range, and the haze was 0.5%. Thermal properties are
There is no change up to around 300 ° C., indicating that the heat resistance is good.

Next, recording was performed on the above-mentioned film-shaped recording medium using an ink jet printer BJC-600J (manufactured by Canon Inc.), and the obtained recorded matter was evaluated for OHP suitability by ink jet recording and biodegradability. Was evaluated by the following method. (1) OHP Suitability by Inkjet Recording Using the inkjet printer described above, an arbitrary full-color image is recorded on the recording medium obtained above and a commercially available OHP film for color inkjet (Canon: CF-102) as a comparison. Then, each image was projected with a reflection type OHP and observed visually. As a result, when the image was equivalent to the commercially available product, it was evaluated as 、, when other images were obtained, as ◎, and when the image was inferior to the commercially available product, as ×. (2) Biodegradability A recording medium in the form of a film is embedded in compost soil,
After months, observe whether biodegradation has progressed.
And

The results are shown in Table 1. The recorded image as OHP was the same as a commercial product in the film before the surface treatment (Reference Example 1), and the film after the surface treatment (Example 1) was
More images were obtained. It was found that it was also biodegradable.

Example 2 A film synthesized in the same manner as in Example 1 was treated with an enzyme solution (p-type) using an esterase enzyme (Boehringer Mannheim).
H8.6) was taken out after immersion for 2 days.
High performance liquid chromatography (column; Shodex)
When the acetic acid eluted in SH1011) was detected, and the film was measured for the infrared total reflection absorption spectrum, acetic acid was detected from the immersion liquid, and the acetyl group peak near 1740 cm ^-1 was detected from the film. Is about 20
% Had decreased.

This film-like recording medium was evaluated for OHP suitability and biodegradability in the same manner as in Example 1. The result is
It is shown in Table 1. OHP suitability was improved and biodegradability was good.

Examples 3 to 7, Reference Example 2 10 g of cellulose was acetylated, then dissolved in 120 ml of tetrahydrofuran (THF), and added to a solution of 9 g of 3-isocyanatopropyltriethoxysilane in THF. Further, a solution prepared by dissolving a few drops of di-n-butyltin dilaurate in THF was added as a catalyst.
The mixture was reacted by stirring for 2 hours.

Next, the urethane-bonded cellulose-silanized product is dissolved in THF, 0.005N hydrochloric acid is added thereto, and the mixture is stirred, and further reacted with a solution of tetramethoxysilane dissolved in 0.01N hydrochloric acid to obtain an average molecular weight. About 25,000 high molecular substances were obtained. The urethane-bound cellulose-silicon oxide obtained in this manner is subjected to a roll coating method,
The film was 90 μm thick.

The film was immersed in various aqueous solutions of sodium hydroxide (pH 8, 9, 10, 11, 12).
Deacetylation treatment was performed. The resulting film has a transmittance of 91 to 93% in a visible light region and a haze of 0.5 to 1.0.
%, And the thermal characteristics did not change up to around 300 ° C.
The OHP suitability and semi-decomposability were good as shown in Table 1, and the image quality was particularly improved by the deacetylation treatment.

Example 8, Reference Example 3 6 g of sodium acetate was added to 80 ml of acetic anhydride, and 10 g of maltopentaose was gradually added thereto, followed by heating under reflux. The reaction was poured into ice water and extracted with ethyl acetate. After the organic layer was dried over magnesium sulfate, ethyl acetate was distilled off to obtain 12 g of acetylated maltopentaose crystallized using propanol.

6.7 g of acetylated maltopentaose was dissolved in 50 ml of dimethylformamide, and 0.46 g of hydrazine acetate was added, followed by reaction at 60 ° C. Ethyl acetate and water were added to the reaction mixture, and the organic layer was extracted.
The organic layer was dried over magnesium sulfate, and ethyl acetate was distilled off to obtain a reaction product.

5 g of this reaction product was dissolved in 50 ml of dry dimethyl sulfoxide (DMSO), and 30 ml of acetic anhydride was added dropwise and stirred. Thereafter, ethyl acetate and water were added, and the organic layer was extracted. After washing the organic layer, it was dried over magnesium sulfate, and ethyl acetate was distilled off. Next, the obtained viscous substance was dissolved in 20 ml of toluene and dropped into petroleum ether to obtain a crystal of acetylated maltopentanolactone.

Next, 3.3 g of the crystallized product was dissolved in 50 ml of dry toluene, and a solution of 0.5 g of aminobutyltriethoxysilane dissolved in 50 ml of dry toluene was dropped and stirred to react. The toluene was distilled off to obtain a urethane-bonded acetylated maltopentaose reactant.

This urethane-linked oligosaccharide is dissolved in THF, 0.005N hydrochloric acid is added thereto, and the mixture is stirred and reacted with a solution of tetramethoxysilane dissolved in 0.01N hydrochloric acid to obtain a polymer having an average molecular weight of about 12,000. Was. The urethane-linked oligosaccharide-silicon oxide obtained in this way was
m thick film.

The obtained film was immersed in an enzyme solution (pH 9.2) using a lipase enzyme (manufactured by Wako Pure Chemical Industries, Ltd.) for 3 days, and the decrease in acetyl groups was measured by infrared total reflection absorption spectrum. 30% of the original. The properties of the film after this treatment were 92% transmittance and 1% haze in the visible light range, and the thermal properties did not change up to around 250 ° C.

The OHP characteristics of this film recording medium are as follows:
The film after surface treatment is better than the film before treatment.
The image quality was good. The results are shown in Table 1 together with the evaluation of biodegradability.

Comparative Example 1 Using a copolymer film of polyhydrobutyrate and valerate (Biopol, manufactured by Zeneca), the OHP suitability and the biodegradability by ink-jet recording were evaluated in the same manner as in the example. Although it had biodegradability, it was found that it was inferior in OHP suitability.

[0051]

[Table 1]

[0052]

As described above, the light-transmissive recording medium for ink-jet recording according to the present invention is obtained by a deacetylation treatment by an alkali solution treatment and / or an enzymatic treatment.
Since it is excellent in OHP suitability by ink jet recording and has good biodegradability, it is possible to minimize adverse effects on the environment when disposed.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of infrared total reflection absorption spectrum data of a light-transmitting recording medium before deacetylation treatment of the present invention.

FIG. 2 is a view showing an example of infrared total reflection absorption spectrum data of a light-transmitting recording medium after a deacetylation treatment of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA04 EA19 FB02 FC06 2H086 BA17 4F073 AA01 AA14 BA03 BA33 BB01 EA41 4J031 AA02 AA59 AB06 AC07 AC08 AC13 AD01 AE17 AF28 CC05

Claims (4)

[Claims] 1. A matrix comprising a silicon oxide matrix formed by decomposition polymerization of an organosilicon compound and a saccharide material of an acetyl derivative of cellulose or oligosaccharide, wherein said silicon oxide and said saccharide material form a hydrogen bond, The light-transmitting base material, which is a polymer substance comprising at least one of a bond, a urethane bond, a urea bond, and an amide bond, is subjected to a deacetylation surface treatment to form an acetyl group on the surface of the light-transmitting base material. A light-transmissive recording medium for ink-jet recording, wherein the number of groups is smaller than the number of acetyl groups inside the substrate. 2. The light-transmissive recording medium for ink jet recording according to claim 1, wherein the surface treatment for deacetylation is at least one of an alkali solution treatment and an enzymatic treatment. 3. A matrix comprising a silicon oxide matrix formed by decomposition polymerization of an organosilicon compound and a saccharide material of an acetyl derivative of cellulose or oligosaccharide, wherein said silicon oxide and said saccharide material form a hydrogen bond, siloxane. Bond, urethane bond, urea bond, the light-transmitting substrate, which is a polymer substance comprising at least one of amide bonds, is subjected to a deacetylation surface treatment, and the surface of the light-transmitting substrate is A method for producing a light-transmitting recording medium for inkjet recording, comprising a step of reducing the number of acetyl groups to be smaller than the acetyl groups inside the substrate. 4. The method according to claim 3, wherein the surface treatment for deacetylation is at least one of an alkali solution treatment and an enzymatic treatment.