WO2024091239A1

WO2024091239A1 - Additive particle treated with isocyanate for toner composition

Info

Publication number: WO2024091239A1
Application number: PCT/US2022/048031
Authority: WO
Inventors: Seungsik Woo; Jinmo HONG
Original assignee: Hewlett-Packard Development Company, L.P.
Priority date: 2022-10-27
Filing date: 2022-10-27
Publication date: 2024-05-02

Abstract

A toner composition of at least one toner particle may include at least one toner particle including a binder resin, a colorant, a releasing agent and an additive disposed on a surface of the at least one toner particle. The additive includes silica particles treated with an alkyl isocyanate to hydrophobize the silica particles.

Description

ADDITIVE PARTICLE TREATED WITH ISOCYANATE FOR TONER

COMPOSITION

BACKGROUND

[0001] An image forming apparatus forms an image on a recording medium, for example, in an electrophotographic manner. An image forming apparatus using the electrophotographic method may supply printing material in form of a toner composition of toner particles (may be referred to as toner) to an electrostatic latent image formed on a photoconductor to form a visible toner image on the photoconductor, may transfer the toner image to the recording medium via an intermediate transfer medium or directly to a recording medium, and then may fix the transferred toner image on the recording medium.

[0002] A development system of an image forming apparatus may include a cartridge that stores toner and capable of being detachably coupled to the image forming apparatus. The cartridge may include an assembly of members including a photoconductor, a developing roller (DR), and a supplying roller (SR) for forming the visible toner image on the photoconductor. The cartridge may be detachably coupled to a main body of the image forming apparatus and be a consumable item that is replaced when service life of the cartridge is over.

BRIEF DESCRIPTION OF THE DRAWINGS

[0003] FIG. 1 is a schematic diagram illustrating a structure of an image forming apparatus with a cartridge storing toner, according to an example;

[0004] FIG. 2 is an enlarged sectional view diagram of the cartridge shown in FIG. 1 according to an example;

[0005] Fig. 3 is a perspective view of a cartridge with toner, according to an example;

[0006] Fig. 4 is an illustration of a toner particle with a silica based surface additive including isocyanate, according to an example;

[0007] Fig. 5 is a structure diagram illustrating reaction of isocyanate with silanol groups on silica in a surface additive of a toner particle, according to an example;

[0008] Figs. 6A and 6B are illustrations of reaction between silanol groups on silica and alkyl isocyanate, according to examples;

[0009] Fig. 7 is a structure diagram of a toner surface treated silica using isocyanate with various alkyl chains, according to examples;

[0010] Fig. 8 is a Table 1 of experimental data for toner, according to an example according to an example;

[0011] Fig. 9 are scanning electron microscope (SEM) images of toner, according to an example;

[0012] Fig. 10 is a Table 2 of experimental data for toner, according to an example; and

[0013] Fig. 11 is a graph of toner composition detection results by a Fourier- transform Infrared (FT-IR) specstroscopy, according to an example.

DETAILED DESCRIPTION

[0014] Nano silica used as an external surface toner particle additive may be highly likely to accumulate in the human body when inhaled due to size of nano silica, and in case of Hexamethyldisilazane (HMDS) used in HMDS treated silica in form of an external additive on toner particles, HMDS may be classified as a regulated substance, because in case of biocidal activity of synthetic amorphous silica-HMDS (SAS-HMDS), according to European Union (EU) risk assessment committee (RAC), the SAS-HDMS behavioral mode (adsorbent or abrasive) may cause functional damage or destruction of lipid-wax layer cuticle, which, for example, may cause an animal to lose water after chronic exposure. Therefore, HMDS can affect both aquatic and terrestrial life after chronic exposure and has been reclassified as SAS-HMDS (CAS: STOT RE2) at the 18th ATP, May 2021 , and the content of standards may be as follows.

*lf it is between 1 % and 10% all countries will require information from the Safety Data Sheets (SDS) and may require a label warning

**Above 10% will require both SDS and label warning

- HMDS: Hexamethyldisilazane

- CLP : Classification, Labelling and Packaging

- ATP : Adaptation to Technical and Scientific Progress

- STOT-RE : Specific Target Organ toxicity - Repeated Exposure [0015] Therefore, use of HDMS may become limited or restricted subject to a hazard notification.

[0016] Other types of treatment agents of silica for toner that may be available include dimethyl-dicholorsilane (DiMeDi), Octyl silane (OTES), Cyclic silazane (+) (amino silane), and PDMS (silicone oil).

[0017] An example of an image forming apparatus and a developing system, such as a system involving a cartridge with toner according to examples to develop an image will be described with reference to the accompanying drawings. Elements having substantially the same configurations are denoted by the same reference numerals in the specification and the accompanying drawings, and thus, a repeated description thereof is omitted.

[0018] Referring to FIGS. 1 and 2, an electrophotographic image forming apparatus 1 may be an image forming apparatus such as an electrophotographic image forming apparatus in which an electrostatic latent image formed on an external surface of a photosensitive drum 15 is developed into a visible image by supplying a developing agent, for example, toner, to the electrostatic latent image. The visible image may then transferred to a recording medium, for example, printing paper P and may then be fused to obtain a desired printed image. In the image forming apparatus 1 , the printing paper P may be moved from a lower portion to an upper portion thereof along a C-shaped path indicated in Fig. 1 by directional arrows. The image forming apparatus 1 may include a developing system in form of a developing cartridge 10, a transferring roller 25, a fixing unit 30, a laser scanning unit (LSU) 70, and a pick-up unit 50 including a pickup roller, which picks up the printing paper P from a paper feeding cassette 51 receiving sheets of paper P.

[0019] The LSU 70 scans light (L) that corresponds to image information to be printed onto the photosensitive drum 15 according to a computer signal to form the electrostatic latent image on the external surface of the photosensitive drum 15.

[0020] The developing cartridge 10 may be detachably coupled in a frame 2 of the image forming apparatus 1. The developing cartridge 10 may include a developing housing 11 to store toner 100 according to an example.

[0021] According to an example, the developing housing 11 may include a developing roller (DR) 16, and a supplying roller 18. The developing cartridge 10 may also include an agitator 21 , and a toner layer regulating unit 18. In addition, a toner storing portion 12 to store a developer as printing material, for example, toner 100 according to an example is provided in the developing housing 11 of the developing cartridge 10. For example, the developing cartridge 10 may be replaced when the toner 100 contained in the toner storing portion 12 is fully consumed.

[0022] The toner 100 according to an example contained in the toner storing portion 12 may be transferred on an external surface of the developing roller 16, which supplies the toner 100 to the photosensitive drum 15. The developing roller 16, which may be coated with toner 100, and which may be in a solid powder form (may be referred to as toner particles), develops the electrostatic latent image into a toner image by supplying the toner 100 to the electrostatic latent image formed on the photosensitive drum 15. A developing bias voltage may be applied to the developing roller 16 to supply the toner 100 to the photosensitive drum 15. The supplying roller 18 may supply the toner 100 in the toner storing portion 12 to the developing roller 116 while rotating in a determined direction. The agitator 21 may agitate the toner 100 in the toner storing portion 12 at a determined speed to prevent caking of the toner 100 and moves the toner in the toner storing portion 12 closer to the supplying roller 18. [0023] The photosensitive drum 15 rotates in a predetermined direction and is installed such that a portion of the external surface thereof is exposed. The photosensitive drum 15 is charged to a predetermined potential by a charging roller 13, which is described below. As described above, the electrostatic latent image that corresponds to an image to be printed may be formed on the external surface of the photosensitive drum 15 according to the light emitted by the LSU 70. An exposed portion of the external surface of the photosensitive drum 15 faces the transferring roller 25.

[0024] A charge bias voltage may be applied to the charging roller 13. The charging roller 13 then may charge the photosensitive drum 15 to a determined potential.

[0025] Referring to FIG. 1 , the transferring roller 25 may be installed to face a circumference of the photosensitive drum 15 and applies a transfer bias voltage having a polarity opposite to the toner image developed on the photosensitive drum 15 such that the toner image can be transferred to the paper P. The toner image may be transferred to the paper P by the electrostatic force exerted between the photosensitive drum 15 and the transferring roller 25.

[0026] The fixing unit 30 may include a heating roller 31 and a pressing roller 33 installed to face the heating roller 31 . The fixing unit 30 fixes the toner image to the paper P by applying heat and pressure to the toner image. The heating roller 31 , which may be a heat source for fixing the toner image, may be installed to face the pressing roller 33 along the axial direction. The pressing roller 33, which is installed to face the heating roller 31 , fixes the toner image to the paper P by applying a high pressure to the paper P. A paper discharging roller 35 discharges the paper P to which the toner image has been fixed out of the image forming apparatus 1 . The paper P that is discharged out of the image forming apparatus 1 is laid on a printed paper cassette 3.

[0027] Fig. 3 is a perspective view illustrating a developing cartridge according to an example. According to an example, a developing cartridge 10 is to contain a developer, such as toner 100 according to an example, and may include a developing roller 16 carrying the developer, and a supplying roller 18 to form a nip with the developing roller 16 to supply the developer in form of toner 100 according to an example to the developing roller 16.

[0028] As an example, the developing cartridge 10 is a non-magnetic one- component developing system to develop the electrophotographic image in the electrophotographic image forming apparatus 1. The electrophotographic image forming apparatus forms an electrostatic latent image on a photosensitive layer formed on an external surface of the photosensitive drum 15 as a photoconductor, for example, an organic photo conductor (OPC). The photosensitive layer of the photosensitive drum 15 may be charged to form a visible toner image when a developer as printing material, toner 100 according to an example is applied by a developing cartridge 10 to the electrostatic latent image on the photosensitive layer. The photosensitive drum 15 transfers and fixes the visible toner image to a recording medium, for example, paper, thereby printing the image.

[0029] Referring to Fig. 3, the developing cartridge 10 may be a non-magnetic one-component or magnetic two component developing system that includes the photoconductor drum 15, the developing roller 16 and the supplying roller 18 to supply a developer, for example, toner 100, contained in the cartridge 10, to the developing roller 16 to cause the developing roller 16 develop the electrostatic latent image in cooperation with the photoconductor drum 15. [0030] An example may be a method to effectively control the flowability and charging performance of toner used in an electrophotographic system through external additive composition control, which may satisfy flowability and charging characteristics while satisfying high image quality and high durability that may at least be equivalent to toner containing HMDS-treated silica.

[0031] To impart excellent flowability, an external additive may be treated on the surface of toner particles of a toner composition. As the external additive, various types of surface treated silica powder may be used. The toner 100 according to an example may obtain properties equivalent to those of HMDS by hydrophobizing the hydrophilic silica surface using various isocyanate compounds. According to the examples, a toner with excellent flowability and charging performance by securing a surface treatment agent that can replace HMDS may be provided.

[0032] The shape and surface control technology of particles of toners may become increasingly important to cope with the trend of full color, high speed, and high quality of printers, as well as small (light), low cost, and eco-friendly trends. High durability may achieve long life, high flowability may respond to high speed, and high charging stability and uniformity may satisfy high image quality. In general, in the composition of the toner particle, the control of the binder resin and wax, the manufacturing process change may improve durability. In addition, charging property and flowability may be improved by controlling the external additives, which are located on the outermost side of the toner particles.

[0033] Therefore, to impart excellent flowability, an external additive may be treated on the surface of toner particles. As the external additive, various types of surface treated silica powder may be used. In an example, properties equivalent to those of HMDS to replace HMDS may be obtained by hydrophobizing a hydrophilic silica surface of toner particles 100 using various isocyanate compounds.

[0034] Fig. 4 is an illustration of a toner particle with a silica based surface additive including isocyanate, according to an example. In an example, a toner composition including toner particles 100 may include at least one toner particle 102, among the toner particles 100, including a binder resin, a colorant, and a releasing agent. An additive may be disposed on a surface of the at least one toner particle 102 in form of an additive surface 104, the additive surface 104 including hydrophobic silica particles 110 by treating silica particles with an isocyanate 120. In the examples, Fig. 4 illustrates different shapes and/or sizes A, B and C of silica treated with different alkyl isocyanates, resulting from controlling different shapes and/or sizes in producing silica core particles in turn resulting in the different shapes and/or sizes of toner 100.

[0035] Fig. 5 is a structure diagram illustrating reaction of isocyanate with silanol groups on silica in a surface additive of a toner particle, according to an example. In an example, Fig. 5 illustrates reaction of a silica based additive surface 104 for a toner particle 102 when treated with an isocyanate 120.

[0036] Figs. 6A and 6B are illustrations of reaction between silanol groups on silica and alkyl isocyanate, according to examples. Fig. 6A illustrates reaction between silanol groups on silica and alkyl isocyanate. Fig. 6B illustrates examples of isocyanate treatment agents with various alkyl chains 140. In an example, the hydrophilic silica particles treated with isocyanate 120 resulting in hydrophobic silica particles 110 are further treated with an alkyl chain 140. [0037] Fig. 7 is a structure diagram of a toner surface treated silica using isocyanate with various alkyl chains, according to examples. In examples, toner surface-treated silica hydrophobized by using silyl isocyanate was further treated with various alkyl chains 140a-1 , 140a-2, 140a-3 to test flowability and charging performance of the toner 100. In examples, Fig. 7 illustrates number of carbon atoms in form of alkly chains (may be referred to as alkyl groups) on the silyl isocyanate, and Fig. 8 (discussed below) is experimental data of how well the silyl isocyanates treated with various alkyl chains may perform regarding hydrophobicity, flowability, tribo-charge, and high-temperature high- humidity (HH)/low-temperature low-humidity (LL) conditions. Referring to examples in Fig. 7, silyl isocyanate 140a-1 , 140a-2 are 140a-3 may be representative of silyl isocyanate 140 in Fig. 6B, and other alkyl isocyanates 140b, 140c and 140d. Referring to the examples in Fig. 7, a) may be the alkyl chain Trimethyl with silyl Isocyanate, b) may be the alkyl chain (Dimethyl)butyl with silyl Isocyanate, c) may be the alkyl chain (Dimethyl)octyl with silyl Isocyanate. Referring to Fig. 7, other alkyl chains may be alkoxy, phenyl, phenoxy, phenyl alkyl, phenyl alkoxy, or cycloalkyl. Referring to the examples in Fig. 6B, other examples of alkyl chains to treat an isocyanate may be Tert-Butyl isocyanate 140b, Trimethyl phenyl isocyanate 140c, or Perfluoro-tert-Butyl isocyanate 140d. [0038] Figs. 6A and 7 illustrate examples of different alkly icocyanates that may be applied to different sizes and/or shapes of silica core particles by controlling manufacturing condition of the silica core particles, that may result in the possible different sizes and/or shapes of hydrophobic silica particles 110 (A, B, and C) as shown in Fig. 4.

[0039] Fig. 8 is a Table 1 of experimental data for toner, according to an example. Table 1 along with the toner performance graphs for cohesion and Tribo-charge vs. treatment type & size of silica, is experimental data for toner surface-treated silica hydrophobized by using silyl isocyanate with various alkyl chains and flowability and charging performance of the toner according to the type of alkyl group were tested using this treated silica. Fig. 8 is experimental data of how well the isocyanates treated with various alkyl chains may perform regarding hydrophobicity, flowability, tribo-charge, and high-temperature high- humidity (HH)/low-temperature low-humidity (LL) conditions.

[0040] Referring to Table 1 , Examples (Ex) 1-1 to 5-1 for silica size of 12 nanometer (nm), illustrate that as the number of carbon atoms in an alkly chain decrease, toner performance metrics of flowability (cohesion) and Tribo-charge - -micro coulomb/g (-pC/g) improve from bad/low to good/high, respectively, with good/high hydrophobicity indications, and HH/LL ratio improves from low to high with good hydrophobicity indication, collectively resulting in very high hydrophobicity. Ex 1-2 to 5-2 for silica size of 40nm, illustrate that as the number of carbon atoms in an alkly chain decrease, toner performance metrics of flowability (cohesion) and Tribo-charge (-pC/g) improve from bad/low to good/high, respectively, with normal hydrophobicity indications, and HH/LL ratio improves from low to high with good hydrophobicity indication, collectively resulting in high hydrophobicity. Ex 1-3 to 5-3 for silica size of 110nm, illustrate that as the number of carbon atoms in an alkly chain decrease, toner performance metrics of flowability (cohesion) and Tribo-charge (-pC/g) improve from bad/low to good/high, respectively, with normal hydrophobicity indications, and HH/LL ratio improves from low to high with normal hydrophobicity indication, collectively resulting in medium hydrophobicity. The experimental data may suggest that alkyl treatment type on an isocyanate with a size of silica can control hydrophobicity in the surface additive for a toner particle 100. In an example, a size of a silica particle among the silica particles as hydrophobized may be from about 10nm to about 150nm.

[0041] Fig. 9 are scanning electron microscope (SEM) images of toner, according to an example. In Fig. 9, images of hydrophobic treated silica sizes of 12nm, 40nm and 110nm illustrate toner surface dispersion level of external surface additives of toner, according to the examples. Fig. 9 may suggest that as silica size increases, the dispersion state increases, impacting hydrophobicity from good to normal as indicated in Fig. 8 experimental data.

[0042] Fig. 10 is a Table 2 of experimental data for toner, according to an example. Table 2 illustrates toner flowability (cohesiveness) and charging property when measure by use of instruments (devices), for example, HOSOKAWA powder test (PT-5) and EPPING charge-to-mass meter. In Fig.

10, for Ex 1-1 to Ex 1-3 in Table 1 , measured cohesions of toner according to the examples with corresponding indications of flowability (cohesion) from excellent, good, acceptable to bad are illustrated, and measured charging properties at HH/LL of toner according to the examples with corresponding indications of HH/LL charge-to-mass (Q/M) ratios from excellent, good, acceptable to bad are illustrated.

[0043] Fig. 11 is a graph of toner composition detection results by a Fourier- transform Infrared (FT-IR) specstroscopy, according to an example. By using an FT-IR spectrometer 200, isocyanate treatment on silica may be detected based on detection of formation of urethane type bonds the silica surface, where in the graph of Fig. 11 , the horizontal axis may represent ‘wavenumber’ and the vertical axis may represent ‘absorbance.’

[0044] In an example, an additive of a toner particle in toner composition, may include silica powder formed from hydrophilic silica particles treated with an isocyanate to hydrophobize the hydrophilic silica particles, the hydrophobic silica powder applied to an external surface of the toner particle. In an example, the additive may be applied to other types of particles to be applied as an externa surface additive to toner 100, such as inorganic oxide particles.

[0045] In an example, an external surface additive of a toner particle in toner composition may include an additive particle treated with an isocyanate to hydrophobize the additive particles, the hydrophobic additive particles to be applied in form of an external surface to the toner particle. The hydrophobic isocyanate particles may be further treated with various types of alkyl groups. The additive particles may be any one of silica particles forming a silica powder, inorganic oxide particles, or organic-inorganic composite materials. In examples, combination of external additives treated according to the described examples of treatments may be provided.

[0046] In an example, a method of producing a toner composition for an electrophotography system may include treating an external additive for a surface of toner of the toner composition using silyl isocyanate with an alkyl chain according to the examples, and applying the surface-treated external additive to the toner. In an example, silica surface treatment using isocyanate to be applied as an external additive to toner may include dispersing naked silica (Fumed I sol-gel (one of silica manufacturing process)) in solvent (solid content 10~20% weight (wt)), in an example, silyl isocyanate may generally be used in an amount of equal mol or more relative to the silica, a stirring in room temperature, heating and treating at the boiling point of solvent (Check NCO peak has disappeared using FT-IR), cooling, filtering and drying to get the surface treated silica. Though a use amount of the silyl isocyanate may not be particularly limited, to obtain a hydrophobic effect, a use amount may be, for example, from 10% by mass to 100% by mass, or in an example, from 10% by mass to 80% by mass, relative to a particular shape and/or size silica particle. Other available methods to produce the surface additive according to the examples may be used. Example effects may be high hydrophobicity and excellent toner flowability, high environmental tribo-charge Ratio (HH/LL), and toner charging characteristics may be controlled by introducing various functional alkyl groups. In an example, in a toner composition including silica treated with an isocyanate, the isocyanate is a silyl Isocyanate and treated with an alkyl chain from any one of Trimethyl producing Trimethyl silyl Isocyanate, (Dimethyl)butyl producing (Dimethyl)butyl silyl Isocyanate, or (Dimethyl)octyl producing (Dimethyl)octyl silyl Isocyanate. In an example, in a toner composition including silica treated with an isocyanate, the isocyanate, the isocyanate is treated with an alkly chain from any one of Tert-Butyl producing Tert-Butyl isocyanate, Trimethyl phenyl producing Trimethyl phenyl isocyanate, or Perfluoro-tert-Butyl producing Perfluoro-tert-Butyl isocyanate.

[0047] According to the examples, silica surface may be modified by using an isocyanate treatment agent with excellent reactivity, and can control the physical properties required for toner properties by using various types of isocyanate compounds. In an example, to realize the same level of performance as the excellent flowability and charging performance of HMDS-treated silica, the required toner properties can be realized by simultaneously treating isocyanate compounds with various branched alkyl groups. In addition, various sizes of silica (10-150nm) can be surface-modified to optimize toner storage and environmental characteristics. It is a mechanism of forming a urethane bond on the silica surface, and may be detected by an analysis method using instruments, such as FT-IR spectrometer 200.

[0048] The words “a,” “an” and “the” are intended to include plural forms of elements unless specifically referenced as a single element. The term “at least” preceding a listing of elements denotes any one or any combination of the elements in the listing. In other words, the expression “at least one of ...” when preceding a list of elements, modifies the entire list of elements and does not modify the individual elements of the list.

[0049] While this disclosure has been shown and described with reference to examples thereof, it will be understood by one of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope as defined by the claims.

Claims

CLAIMS:

1. A toner composition comprising: toner particles, at least one toner particle among the toner particles including a binder resin, a colorant, and a releasing agent; and an additive disposed on a surface of the at least one toner particle, the additive comprising silica particles treated with an isocyanate to hydrophobize the silica particles.

2. The toner composition according to claim 1 , wherein the hydrophobic silica particles treated with the isocyanate are further treated with an alkyl chain.

3. The toner composition according to claim 2, wherein the isocyanate is a silyl isocyanate treated with an alkyl chain from any one of Trimethyl as Trimethyl silyl Isocyanate, (Dimethyl)butyl as (Dimethyl)butyl silyl Isocyanate, or (Dimethyl)octyl as (Dimethyl)octyl silyl Isocyanate.

4. The toner composition according to claim 1 , wherein the isocyanate is treated with an alkly chain from any one of Tert-Butyl as Tert-Butyl isocyanate, Trimethyl phenyl as Trimethyl phenyl isocyanate, or Perfluoro-tert-Butyl as Perfluoro-tert-Butyl isocyanate.

5. The toner composition according to claim 3, wherein a size of a silica particle among the silica particles is about 10nm to about 150nm.

6. An external additive of a toner particle in toner composition, comprising: an additive particle treated with an isocyanate to hydrophobize the additive particles, the hydrophobic additive particles to be applied in form of an external surface to the toner particle.

7. The external additive according to claim 6, wherein the additive particle is any one of silica particles forming a silica powder, inorganic oxide particles, or organic-inorganic composite materials.

8. The external additive according to claim 6, wherein the isocyanate is a silyl isocyanate treated with an alkyl chain from any one of Trimethyl as Trimethyl silyl isocyanate, (Dimethyl)butyl as (Dimethyl)butyl silyl isocyanate, or (Dimethyl)octyl as (Dimethyl)octyl silyl isocyanate.

9. The external additive according to claim 6, the isocyanate is treated with an alkly chain from any one of Tert-Butyl as Tert-Butyl isocyanate, Trimethyl phenyl as Trimethyl phenyl isocyanate, or Perfluoro-tert-Butyl as Perfluoro-tert- Butyl isocyanate.

10. The external additive according to claim 8, wherein a size of a silica particle among the silica particles is about 10nm to about 150nm.

11 . A cartridge to contain a toner composition, the cartridge comprising: toner particles, at least one toner particle among the toner particles including, a binder resin, a colorant, a releasing agent, and an additive disposed on a surface of the at least one toner particle, the additive comprising silica particles treated with an isocyanate to hydrophobize the silica particles.

12. The cartridge according to claim 11 , wherein the hydrophobic silica particles treated with the isocyanate are further treated with an alkyl chain.

13. The cartridge according to claim 12, wherein the isocyanate is a silyl Isocyanate treated with an alkyl chain from any one of Trimethyl as Trimethyl silyl isocyanate, (Dimethyl)butyl as (Dimethyl)butyl silyl isocyanate, or (Dimethyl)octyl as (Dimethyl)octyl silyl isocyanate.

14. The cartridge according to claim 11 , wherein the isocyanate is treated with an alkly chain from any one of Tert-Butyl as Tert-Butyl isocyanate, Trimethyl phenyl as Trimethyl phenyl isocyanate, or Perfluoro-tert-Butyl as Perfluoro-tert-Butyl isocyanate.

15. The cartridge according to claim 13, wherein a size of a silica particle among the silica particles is about 10nm to about 150nm.