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CN116120777A - Preparation method of modified silica sol for water-based ink - Google Patents

Preparation method of modified silica sol for water-based ink Download PDF

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Publication number
CN116120777A
CN116120777A CN202310002842.XA CN202310002842A CN116120777A CN 116120777 A CN116120777 A CN 116120777A CN 202310002842 A CN202310002842 A CN 202310002842A CN 116120777 A CN116120777 A CN 116120777A
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silica sol
modified silica
silane
modifier
ink
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Inventor
康立明
康利彬
车顺爱
林菁菁
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Shandong Kehan Siyuan New Material Co ltd
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Shandong Kehan Siyuan New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/106Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The invention belongs to the technical field of water-based ink, and particularly relates to a preparation method of modified silica sol for water-based ink. The method uses phenylsilane compounds with large steric hindrance structures and strong hydrophobicity as a modifier, and obtains uniform modified silica sol through polymerization after heating and hydrolysis. The obtained modified silica sol has high compatibility with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion), high concentration of the modified silica sol, high addition amount, good stability and quality meeting the requirements, and improves the hydrophobic property of the ink; the modification steps are simple, the raw materials are easy to obtain and the cost is low.

Description

Preparation method of modified silica sol for water-based ink
Technical Field
The invention belongs to the technical field of water-based ink, and particularly relates to a preparation method of modified silica sol for water-based ink.
Background
The addition of the nano inorganic filler can improve the performance of the aqueous coating without affecting the flexibility of the polymer in the emulsion. Silica nanoparticles are of particular interest due to their high surface area, low production cost and ease of surface functionalization. Hybrid silica materials combine the rigidity and high thermal stability of the inorganic component with the flexibility, ductility and processibility of the polymer matrix. When used in polymer coating formulations, silica nanoparticles can also add new functionality to the film through surface modification, protecting the film from water, temperature, friction, radiation, corrosion, and the like.
Synthetic strategies for hybrid latex typically encapsulate inorganic nanosilica particles into monomer droplets, followed by polymerization to form stable composite latex particles containing polymer and inorganic components. The method of directly doping inorganic nano silicon dioxide particles into latex polymer colloid can not destroy the stability of the latex polymer colloid, and can carry out modification regulation and control on the surfaces of the inorganic nano particles. The application of monodisperse silica in hybrid polymer coatings has not been fully explored and has great promise. Shi et al prepared an epoxy coating containing monodisperse silica that was useful as a corrosion inhibitor 8-hydroxyquinoline reservoir. Li u et al further demonstrate the preparation of mesoporous silica coatings on graphene oxide nanoplatelets and their incorporation into styrene-butadiene rubber composites to increase their thermal conductivity. Ho s sai nRi az i et al modified silicon nanoparticles with silane coupling agents containing unsaturated carbon double bonds to increase their hydrophobicity. However, in an attempt to manufacture an aqueous hydrophobic coating, although hydrophilic inorganic nanofillers may be dispersed in water, phase separation and precipitation occur due to poor interfacial compatibility between inorganic and organic components, resulting in poor mechanical stability of the ink system. There is therefore a need to develop inorganic silica sols with hydrophobically modified surfaces that modulate the amphiphilicity of the particle surface by modification to increase the affinity of the silica-polymer (by promoting van der waals forces, hydrogen bonding or ionic interactions), maximize the interfacial stability between silica and polymer matrix, to achieve good compatibility in the ink, and to improve ink performance.
Prior art studies on silane-modified colloidal silica particles usable in ink emulsions have been reported, for example, a method for preparing silane-modified colloidal silica particles usable in ink emulsions, comprising the steps of:
1. the soluble silicate is ion exchanged to produce polysilicic acid and the pH is raised to allow the anionic colloidal silica particles to grow to produce a colloidal silica sol;
2. diluting the silane compound to form a pre-mixture of silane and water, the weight ratio to silane being 1.5:1, a step of;
3. the silane and the colloidal silica particles are mixed in a weight ratio of silane in the range of 0.5 to 0.8, and the amount of silane added to the colloidal silica particles may be 1 to 2 silane molecules per nm 2 Silica particle surface area;
4. silane may be slowly added to the silica colloidal silica sol by vigorous stirring at a controlled rate at a temperature of 40 to 90 ℃;
5. after stopping the addition of silane, mixing was continued for 1 to 10 minutes.
However, the above-mentioned prior art method for preparing modified silica has the following drawbacks:
1. the modified silane groups used in the preparation have smaller steric hindrance, the modified silica sol obtained after modification has poorer hydrophobicity, and the modified silica sol has poorer compatibility with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) and is easy to generate coagulation or precipitation.
2. The hydrophobicity of the hydrophobic group of the modified silane used in the preparation is low, the hydrophobicity of the modified silica sol obtained by grafting is poor, the compatibility with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) is poor, and the coagulation or precipitation phenomenon is easy to generate.
4. The modified silane has self-polycondensation phenomenon in the modification process, and does not polymerize with silicon hydroxyl (S i-OH) on the surface of silicon dioxide to generate S i-O-S i bond, so that the prepared modified silane is not stable enough and is easy to aggregate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of modified silica sol for water-based ink. The invention takes silane compounds with large steric hindrance structure and strong hydrophobicity as modifier, and obtains uniform modified silica sol through polymerization after heating and hydrolysis. The obtained modified silica sol has higher compatibility with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion).
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the modified silica sol for the water-based ink specifically comprises the following steps:
(1) Adding silica sol into a reactor, and adding a modifier under stirring;
(2) And (3) placing the reactor in the step (1) into a homogeneous reactor, and reacting under certain conditions to obtain a uniform solution, namely the modified silica sol.
Preferably, the modifier in the step (1) is a phenylsilane compound with large steric hindrance structure and strong hydrophobicity.
Preferably, the modifier is diphenyldiethoxysilane or trimethoxy (4-methoxyphenyl) silane.
Preferably, the modifier further comprises: diphenyldiethoxysilane, trimethoxy [3- (anilinopropyl) silane, trimethoxy (4-methoxyphenyl) silane, (p-methylphenyl) trimethoxysilane, t-butyldiphenylmethoxysilane, dimethoxydi-p-tolylsilane, triethoxy (1-phenylvinyl) silane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethylphenylmethoxysilane, and the like.
Preferably, the silica sol in the step (1) is neutral (pH value is 6.5-7.5) or alkaline silica sol (pH value is 8.5-10.5), and the silica particle size is 8-50nm.
Preferably, when the modifier is diphenyldiethoxysilane, the silica sol is 40% silica sol, and the grafting density is 0.2-0.25 molecules/nm 2 . The reaction conditions in the step (2) are as follows: the reaction was carried out at 80℃for 2 hours followed by 100℃for 5 hours to give a white homogeneous solution.
Preferably, when the modifier is trimethoxy (4-methoxyphenyl) silane, the silica sol is 30% silica sol, and the grafting density is 1.28 molecules/nm 2 . The reaction conditions in the step (2) are as follows: the reaction was rotated at 40℃for 2 hours to give a homogeneous solution.
Advantageous effects
The invention discloses a preparation method of modified silica sol for water-based ink, which has the following beneficial effects compared with the prior art:
1. the diphenyl diethoxy silane has large steric hindrance and strong hydrophobicity, and the obtained modified silica sol has slightly high viscosity and can have better compatibility with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) with higher viscosity; the grafting group of the triphenylethoxysilane has large steric hindrance, and the obtained modified silica sol has slightly high viscosity and can be better compatible with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) with higher viscosity.
2. The phenyl groups on the surfaces of modified silica sol particles obtained by modifying diphenyl diethoxy silane are consistent with the phenyl group structures in ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion), and the modified silica sol has better compatibility according to the similar compatibility principle; the groups on the surface of the modified silica sol particles obtained by the modification of trimethoxy (4-methoxyphenyl) silane contain oxygen (O) and hydroxyl groups in the ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion), and a large number of hydroxyl groups in the silica sol can form hydrogen bonds, so that the modified silica sol has better compatibility in the ink emulsion.
3. The modified silica sol has high concentration, high addition amount, good stability and quality meeting the requirements.
4. The modification step is simple and the raw material cost is low.
Drawings
Fig. 1: photo of film forming sample of ink emulsion without silica sol;
fig. 2: photo of film forming sample of ink emulsion with 26% modified silica sol;
fig. 3: photo of film forming sample of ink emulsion with 30% modified silica sol.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
The preparation method of the modified silica sol for the water-based ink specifically comprises the following steps:
1. 25.25g (168 mmol) of 40% silica sol and 0.133g (0.489 mmol) of diphenyldiethoxysilane were added to the reactor with stirring, the grafting density being 1 molecule/4-5 nm 2
2. Putting the reactor into a homogeneous reactor, carrying out rotary reaction for 2 hours at 80 ℃, and then carrying out rotary reaction for 5 hours at 100 ℃ to obtain a white uniform solution, namely the modified silica sol.
Experimental example 1
To verify the compatibility of the modified silica sol obtained in example 1 with aqueous inks, the following experiments were now performed:
to 0.5mL of the ink emulsion (styrene-acrylic emulsion) was added 0.5mL of the modified silica sol obtained in example 1 at a time, the silica content was about 20%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
To 0.5mL of the ink emulsion (silicone-acrylic emulsion) was added 0.334mL of the modified silica sol obtained in example 1 at a time, the silica content was about 16%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
To 0.5mL of the ink emulsion (silicone-acrylic emulsion) was added 0.215mL of the modified silica sol obtained in example 1 at a time, the silica content was about 16%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
To 0.5mL of the ink emulsion (silicone-acrylic emulsion) was added 0.125mL of the modified silica sol obtained in example 1 at a time, the silica content was about 16%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
The experimental results show that the diphenyl diethoxy silane has large steric hindrance and strong hydrophobicity, and the obtained modified silica sol has slightly high viscosity and can be better compatible with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) with higher viscosity; the phenyl groups on the surfaces of the modified silica sol particles obtained by modifying the diphenyl diethoxy silane are consistent with the phenyl group structures in the ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion), and the modified silica sol has better compatibility according to the similar compatibility principle.
Example 2
The preparation method of the modified silica sol for the water-based ink specifically comprises the following steps:
1. 5.05g (25.25 mmol) of 30% silica sol and 0.1666g (0.706 mmol) of trimethoxy (4-methoxyphenyl) silane were added to the reactor with stirring and the grafting density was 1.28 molecules/nm 2
2. Putting the reactor into a homogeneous reactor, and performing rotary reaction for 2 hours at 40 ℃ to obtain a uniform solution, namely the modified silica sol.
Experimental example 2
To verify the compatibility of the modified silica sol obtained in example 2 with aqueous inks, the following experiments were now performed:
0.130mL of the modified silica sol obtained in example 2 was added to 0.5mL of an ink emulsion (styrene-acrylic emulsion) at a time, the mass ratio of the modified silica sol was 22%, the silica content was about 7.8%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
0.110mL of the modified silica sol obtained in example 2 was added to 0.5mL of an ink emulsion (silicone-acrylic emulsion) at a time, the mass ratio of the modified silica sol was 22%, the silica content was about 6.6%, and the mixture was sonicated for 10 minutes to obtain a uniform precipitate-free solution.
The experimental results show that the trimethoxy (4-methoxyphenyl) silane has large steric hindrance of the grafting group, and the obtained modified silica sol has slightly high viscosity and can be better compatible with ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion) with high viscosity. The groups on the surface of the modified silica sol particles obtained by the modification of trimethoxy (4-methoxyphenyl) silane contain oxygen (O) and hydroxyl groups in the ink emulsion (styrene-acrylic emulsion or silicone-acrylic emulsion), and a large number of hydroxyl groups in the silica sol can form hydrogen bonds, so that the modified silica sol has better compatibility in the ink emulsion.
Experimental example 3
(1) And (3) testing the compatibility of diphenyl diethoxysilane modified silica sol and ink:
to 0.5mL of the ink emulsion was added x uL of diphenyldiethoxysilane modified silica sol at a time, sonicated for 10min, and compatibility test data are shown in Table 1 below.
TABLE 1 data on compatibility of diphenyldiethoxysilane modified silica sols and inks
Figure BDA0004034692270000061
(2) Test of the compatibility of trimethoxy (4-methoxyphenyl) silane modified silica sol with ink:
to 0.5mL of the ink emulsion was added x uL of the modified silica sol at a time and sonicated for 10min, and the compatibility test data are shown in Table 2 below.
TABLE 2 data on the compatibility of trimethoxy (4-methoxyphenyl) silane modified sols with inks
Figure BDA0004034692270000062
(3) And (3) ink film forming test:
a10 um ink film was prepared on a plastic substrate using a four-sided preparer and heated at 90℃for 1-2min. And testing the surface of the film by using a dyne pen to obtain a dyne value.
The film-forming sample of the ink emulsion without silica sol is shown in fig. 1, the surface is smooth and transparent, and trace particles are separated out, and the dyne value is 30.
A film-forming sample of the ink emulsion with the addition amount of trimethoxy (4-methoxyphenyl) silane modified silica sol of 26% is shown in fig. 2, the surface is smooth and transparent, and the dyne value is 33.
A film-forming sample of the ink emulsion with 30% of trimethoxy (4-methoxyphenyl) silane modified silica sol added amount is shown in figure 3, the surface is smooth and transparent, and the dyne value is 36.
The dyne value of the ink is obviously improved after the modified silica sol is added, and the higher the numerical value is, the higher the surface energy of the film surface is, and the higher the hydrophobicity is. The higher the addition amount, the higher the dyne value, showing that after the hydrophobically modified silica is added into the ink, the hydrophobicity of the ink film is improved, and the addition amount of the modified silica sol and the hydrophobicity of the film surface are in a linear relationship within a certain range.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (7)

1. The preparation method of the modified silica sol for the water-based ink is characterized by comprising the following steps of:
(1) Adding silica sol into a reactor, and adding a modifier under stirring;
(2) Placing the reactor in the step (1) into a homogeneous reactor, and reacting under certain conditions to obtain a uniform solution, namely the modified silica sol;
the modifier is a silane compound with a large steric hindrance structure and strong hydrophobicity.
2. The method for preparing a modified silica sol for aqueous ink according to claim 1, wherein the modifier is a phenylsilane compound.
3. The method for preparing a modified silica sol for aqueous ink according to claim 2, wherein the modifier phenylsilane compound comprises: one or more of diphenyldiethoxysilane, trimethoxy [3- (anilinopropyl) silane, trimethoxy (4-methoxyphenyl) silane, (p-methylphenyl) trimethoxysilane, t-butyldiphenylmethoxysilane, dimethoxydi-p-tolylsilane, triethoxy (1-phenylvinyl) silane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethylphenylmethoxysilane.
4. The method for producing a modified silica sol for aqueous ink according to claim 1, wherein the silica sol in step (1) is neutral (pH value of 6.5 to 7.5) or alkaline silica sol (pH of 8.5 to 10.5), and the silica particle diameter is 8 to 50nm.
5. The method for preparing a modified silica sol for water-based ink according to claim 2, wherein the modifier is a phenylsilane compound, the silica sol is 30-40% silica sol, and the grafting density is 0.2-1.8 molecules/nm 2
6. The method for preparing modified silica sol for water-based ink according to claim 2, wherein the modifier is phenylsilane compound, the silica sol is 30-40% silica sol, and the addition amount of the modifier is 0.5% -5%.
7. The method for producing a modified silica sol for aqueous ink according to claim 5, wherein the reaction conditions in step (2) are: the reaction was carried out at 40-90℃for 2 hours and then at 5 hours to give a white homogeneous solution.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6025455A (en) * 1997-05-26 2000-02-15 Nissan Chemicals Industries, Ltd. Process of producing hydrophobic organosilica sol
US20040077768A1 (en) * 2002-10-14 2004-04-22 Akzo Nobel N.V.. Colloidal silica composition
JP2005022915A (en) * 2003-07-01 2005-01-27 Mitsubishi Rayon Co Ltd Surface-modified spherical silica, method of manufacturing the same and resin composition for sealing
JP2006022314A (en) * 2004-06-07 2006-01-26 Fuso Chemical Co Ltd Film-forming composition and method for forming film
JP2007246656A (en) * 2006-03-15 2007-09-27 Kao Corp Ink set for ink-jet recording
CN102027074A (en) * 2008-04-18 2011-04-20 纳米树脂股份公司 Surface modified silicon dioxide particles
CN102190936A (en) * 2011-04-08 2011-09-21 华南理工大学 Swelling-preventing polyacrylate dispersion/SiO2 hybrid aqueous wood coating
CN102286233A (en) * 2011-09-10 2011-12-21 中国十七冶集团有限公司 Nano-modified elastic coating with high stain resistance and preparation method thereof
CN103415575A (en) * 2011-03-14 2013-11-27 阿克佐诺贝尔化学国际公司 Modified silica particles
CN113574128A (en) * 2019-03-14 2021-10-29 诺力昂化学品国际有限公司 Pigment dispersion comprising silane-modified colloidal silica particles and water-soluble thickening polymer
JP2022155890A (en) * 2021-03-31 2022-10-14 日本化薬株式会社 Ink, ink medium set, and method for improving scratch resistance

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6025455A (en) * 1997-05-26 2000-02-15 Nissan Chemicals Industries, Ltd. Process of producing hydrophobic organosilica sol
US20040077768A1 (en) * 2002-10-14 2004-04-22 Akzo Nobel N.V.. Colloidal silica composition
JP2005022915A (en) * 2003-07-01 2005-01-27 Mitsubishi Rayon Co Ltd Surface-modified spherical silica, method of manufacturing the same and resin composition for sealing
JP2006022314A (en) * 2004-06-07 2006-01-26 Fuso Chemical Co Ltd Film-forming composition and method for forming film
JP2007246656A (en) * 2006-03-15 2007-09-27 Kao Corp Ink set for ink-jet recording
CN102027074A (en) * 2008-04-18 2011-04-20 纳米树脂股份公司 Surface modified silicon dioxide particles
CN103415575A (en) * 2011-03-14 2013-11-27 阿克佐诺贝尔化学国际公司 Modified silica particles
CN102190936A (en) * 2011-04-08 2011-09-21 华南理工大学 Swelling-preventing polyacrylate dispersion/SiO2 hybrid aqueous wood coating
CN102286233A (en) * 2011-09-10 2011-12-21 中国十七冶集团有限公司 Nano-modified elastic coating with high stain resistance and preparation method thereof
CN113574128A (en) * 2019-03-14 2021-10-29 诺力昂化学品国际有限公司 Pigment dispersion comprising silane-modified colloidal silica particles and water-soluble thickening polymer
JP2022155890A (en) * 2021-03-31 2022-10-14 日本化薬株式会社 Ink, ink medium set, and method for improving scratch resistance

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