KR20100002754A - Enhance scorch resistance of carcass rubber composition - Google Patents

Enhance scorch resistance of carcass rubber composition Download PDF

Info

Publication number
KR20100002754A
KR20100002754A KR1020080062773A KR20080062773A KR20100002754A KR 20100002754 A KR20100002754 A KR 20100002754A KR 1020080062773 A KR1020080062773 A KR 1020080062773A KR 20080062773 A KR20080062773 A KR 20080062773A KR 20100002754 A KR20100002754 A KR 20100002754A
Authority
KR
South Korea
Prior art keywords
rubber
weight
rubber composition
parts
vulcanization
Prior art date
Application number
KR1020080062773A
Other languages
Korean (ko)
Inventor
김영주
Original Assignee
금호타이어 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 금호타이어 주식회사 filed Critical 금호타이어 주식회사
Priority to KR1020080062773A priority Critical patent/KR20100002754A/en
Publication of KR20100002754A publication Critical patent/KR20100002754A/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0041—Compositions of the carcass layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a carcass rubber composition having improved scorch resistance, and more particularly, to a carcass rubber composition, N-cyclohexyl-2-2 of the following structural formula (1) as a vulcanization accelerator based on 100 parts by weight of raw material rubber The present invention relates to a carcass rubber composition having improved scorch resistance, including 0.5 to 1.5 parts by weight of benzothiazyl sulfenamide (N-Cyclohexyl-2-2-benzothiazyl sulfenamide).

Figure 112008047179189-PAT00001
... Formula (1)

Description

Enhance scorch resistance of carcass rubber composition

The present invention relates to a carcass rubber composition having improved scorch resistance, and more particularly, to a carcass rubber composition, N-cyclohexyl-2-2 of the following structural formula (1) as a vulcanization accelerator based on 100 parts by weight of raw material rubber The present invention relates to a carcass rubber composition having improved scorch resistance, including 0.5 to 1.5 parts by weight of benzothiazyl sulfenamide (N-Cyclohexyl-2-2-benzothiazyl sulfenamide).

Figure 112008047179189-PAT00002
... Formula (1)

Tire rubber compositions use various additives to improve the properties of raw rubber in addition to raw rubber.

In particular, since the tire rubber composition requires a slightly different characteristic depending on the position of each tire, in order to obtain a desired tire rubber, additives are used which are slightly different depending on the position of the tire.

Among these additives, vulcanization accelerators generally impart elasticity of raw rubber when vulcanizing various elastomers such as natural rubber, epoxidized natural rubber (ENR), diene rubber, and ethylene-propylene copolymer rubber with sulfur. Hazards are essential accelerators in the vulcanization process.

There are many kinds of vulcanization accelerators to assist the vulcanization of rubber components. Among them, sulfenamide vulcanization accelerators have excellent scorch resistance and increase the vulcanization speed, and also have good properties in terms of rubber properties such as tensile strength and elongation rate. It is used a lot as a vulcanization accelerator for betting.

Also, among the sulfenamide vulcanization accelerators, N-cyclohexylbenzothiazole-2-sulfenamide is generally used as a sulfenamide.

The present invention is to provide a carcass rubber composition having improved scorch resistance without using a separate scorch retardant by using a sulfenamide-based vulcanization accelerator effective for improving heat aging resistance and scorch resistance.

The present invention relates to N-cyclohexyl-2-2-benzothiazyl sulfenamide (N-Cyclohexyl-2-2-benzothiazyl) of the following structural formula (1) as a vulcanization accelerator in a carcass rubber composition: sulfenamide) to include 0.5 to 1.0 parts by weight to provide a carcass rubber composition with improved scratch resistance.

Figure 112008047179189-PAT00003
... Formula (1)

The carcass rubber composition of the present invention uses N-cyclohexyl-2-2-benzothiazyl sulfenamide as a vulcanization accelerator, thereby delaying separate scorch without lowering the vulcanization rate. Scorch resistance can be improved as a result of not lowering the scratch resistance without the use of a Scorch retarder.

The present invention shows a carcass rubber composition having improved scorch resistance.

The present invention relates to N-cyclohexyl-2-2-benzothiazyl sulfenamide (N-Cyclohexyl-2-2-benzothiazyl) of the following structural formula (1) as a vulcanization accelerator in a carcass rubber composition: sulfenamide) shows a carcass rubber composition having improved scorch resistance, including 0.5 to 1.5 parts by weight.

Figure 112008047179189-PAT00004
... Formula (1)

In the present invention, the raw material rubber may be any one or more selected from the group of natural rubber and synthetic rubber.

In the present invention, the raw rubber may be mixed rubber mixed with natural rubber and synthetic rubber in a weight ratio of 1: 9 to 9: 1.

In the above synthetic rubber, butyl rubber, modified butyl rubber, butyl halide rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, butadiene rubber (BR), nitrile rubber, hydrogenated nitrile rubber, nitrile butadiene Rubber (NBR), modified nitrile butadiene rubber, styrene butadiene rubber (SBR), modified styrene butadiene rubber, chlorinated polyethylene rubber, styrene ethylene butylene styrene (SEBS) rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber, Hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber , Group of ethylene propylene rubber and maleic acid nitrile butadiene rubber Any one or more selected from can be used.

As an example of the butyl halide rubber, chlorobutyl rubber and / or bromobutyl rubber may be used.

The natural rubber may be modified natural rubber, and as an example of such modified natural rubber, may be used an epoxy group modified epoxy oxide (Epoxidezed Natural Rubber, ENR).

As an example of the raw material rubber of the present invention can be used natural rubber.

As another example of the raw material rubber of the present invention, a mixed rubber in which natural rubber and butadiene rubber are mixed in a weight ratio of 1: 9 to 9: 1 may be used.

As an example of the raw material rubber of the present invention, an epoxy group-modified epoxy oxide natural rubber (Epoxidezed Natural Rubber, ENR) may be used instead of natural rubber.

In the present invention, the vulcanization accelerator uses N-cyclohexyl-2-2-benzothiazyl sulfenamide of the following structural formula (1).

Figure 112008047179189-PAT00005
... Formula (1)

During the vulcanization reaction, the vulcanization accelerators form several forms of intermediate reactants and these intermediate reactants react with zinc oxide (ZnO) to form zincated vulcanization accelerator complexes, which are then combined with sulfur to form sulfur and rubber. Induces a vulcanization reaction with.

N-cyclohexyl-2-2-benzothiazyl sulfenamide of formula (1) used as a vulcanization accelerator in the present invention is N-cyclohexylbenzotaazole-2-sulfenamide (N- The steric hindrance of the sulfur part is smaller than that of cyclohexylbenzothiazole-2-Sulfenamide, making it easier to combine with sulfur. In addition, N-cyclohexyl-2-2-benzothiazyl sulfenamide is located in the cyclohexyl group of the amine to increase the electrical activity of the amine to activate the role of the vulcanization accelerator. This causes a difference in the basicity of the amine group, and the vulcanization time and the vulcanization rate vary according to the difference, resulting in a difference in the reactivity of the promoter.

That is, N-cyclohexyl-2-2-benzothiazyl sulfenamide used as a vulcanization accelerator of the present invention is compared with the conventional vulcanization accelerator N-cyclohexylbenzotaazole-2-sulfenamide. The amine is located in place of cyclohexyl (Cyclohexyl) is not only because the steric hindrance is small, but the activity is enhanced by the amine (Amine) is characterized by more reactivity.

The carcass rubber composition of the present invention is N-Cyclohexyl-2-2-benzothiazyl sulfenamide of formula (1) as a vulcanization accelerator based on 100 parts by weight of raw rubber. 0.5 to 1.5 parts by weight.

In the present invention, when N-cyclohexyl-2-2-benzothiazyl sulfenamide of the formula (1) is used in an amount of less than 0.5 part by weight based on 100 parts by weight of the raw material rubber, the role as a vulcanization accelerator is negligible, and 1.5 parts by weight. If excessively used, there is a possibility that the physical properties of the rubber composition may decrease due to excessive vulcanization. Therefore, the carcass rubber composition of the present invention is N-cyclohexyl-2-2-benzothiazyl sulfenamide of formula (1) as a vulcanization accelerator based on 100 parts by weight of raw rubber. ) 0.5 to 1.5 parts by weight is recommended.

The carcass rubber composition of the present invention may include 40 to 80 parts by weight of a filler based on 100 parts by weight of the raw material rubber to improve the reinforcement of the rubber composition.

The filler is carbon black, syndiotactic-1,2-polybutadiene (SPB), silica, titanium oxide, clay, Any one or more selected from the group of layered silicate, tungsten, talc, mica, calcium carbonate, talc, vermiculite, and hydrotalcite may be used.

The syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 0.01 to 0.1 µm and a specific surface area of 80 to 90 m 2 / g.

The syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 1 to 10 µm and a specific surface area of 100 to 120 m 2 / g.

At least one selected from the group consisting of mica, calcium carbonate, talc, vermiculite, and hydrotalcite may each have a particle size of 0.1 to 20 μm.

In the above, any one or more selected from the group of mica, calcium carbonate, talc, vermiculite, and hydrotalcite may be used, each having an interlayer spacing of 0.1 to 10 nm.

At least one selected from the group of mica, calcium carbonate, talc, vermiculite, and hydrotalcite, respectively, represents a ratio of the plane width l to the thickness d, an aspect ratio (l / d). Is 5 or more can be used.

Any one or more selected from the group of mica, calcium carbonate, talc, vermiculite, and hydrotalcite may have a flattening ratio of 5 to 100.

Any one or more selected from the group consisting of mica, calcium carbonate, talc, vermiculite and hydrotal may be used having a particle size of 0.1 to 20 µm, an interlayer spacing of 0.1 to 10 nm, and a flat ratio of 5 to 100. .

If the filler is less than 40 parts by weight based on 100 parts by weight of the raw material rubber, reinforcement improvement is insignificant, and when used in excess of 80 parts by weight, the physical properties of the rubber composition may be reduced due to the use of excess filler. In the present invention, the filler is preferably used 40 to 80 parts by weight based on 100 parts by weight of the raw material rubber.

According to the present invention, various additives such as fillers, activators, process oils, vulcanizing agents, and vulcanization accelerators, which are used in conventional carcass rubber compositions, in addition to the above-mentioned raw rubbers, vulcanization accelerators, and fillers may be appropriately selected as necessary. Can be used. However, these are general components used in the conventional carcass rubber composition and are not essential components of the present invention, and thus the detailed description thereof will be omitted.

The present invention includes a rubber composed of the above-mentioned rubber composition.

The present invention includes a tire containing a rubber composed of the above-mentioned rubber composition.

The present invention includes a tire containing, as a carcass, a rubber composed of the above-mentioned rubber composition.

The present invention includes a tire containing a rubber made of the above-mentioned rubber composition, wherein the tire is any one selected from the group of automobile tires, truck tires, bus tires, anti-air tires and motorcycle tires. Indicates.

Hereinafter, the present invention will be described by the following examples, comparative examples and test examples. However, these are not limited to the scope of the present invention by these as an embodiment of the present invention.

<Example 1>

 50 parts by weight of carbon black (N330) based on 100 parts by weight of the raw material rubber consisting of 50 parts by weight of natural rubber (NR) and 50 parts by weight of butadiene rubber (BR), and an antioxidant (N- (1.3-Dimethylbutyl) -N'-phenyl- Banbury mixer by adding 5 parts by weight of p-phynylenediamine, 6PPD), 3 parts by weight of aromatic oil, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide (ZnO), 1 part by weight of antioxidant, 1.5 parts by weight of wax, and 5 parts by weight of adhesive. After mixing in the mixture for 5 minutes at 160 ℃ to obtain a rubber compound.

2 parts by weight of sulfur as a vulcanizing agent and 0.5 parts by weight of N-cyclohexyl-2-2-benzothiazyl sulfenamide of the following structural formula (1) as a vulcanizing agent to the rubber compound Part was added and vulcanized at 100 ° C. for 3 minutes to prepare a rubber.

Figure 112008047179189-PAT00006
... Formula (1)

<Example 2>

A rubber was manufactured in the same manner as in Example 1, except that 1.0 part by weight of N-cyclohexyl-2-2-benzothiazyl sulfenamide was used as a vulcanization accelerator. .

<Example 3>

A rubber was prepared in the same manner as in Example 1, except that 1.5 parts by weight of N-cyclohexyl-2-2-benzothiazyl sulfenamide was used as a vulcanization accelerator. .

Comparative Example

N-Cyclohexylbenzothiazole-2-sulfenamide (N-Cyclohexylbenzothiazole-2-Sulfenamide instead of N-Cyclohexyl-2-2-benzothiazyl sulfenamide as a vulcanization accelerator) A rubber was manufactured in the same manner as in Example 1, except that 0.5 parts by weight was used.

Table 1. Rubber Composition of Comparative Examples and Examples (unit: parts by weight)

Item Comparative example Example 1 Example 2 Example 3 Natural rubber 50 50 50 50 Butadiene rubber 50 50 50 50 Carbon black 50 50 50 50 Anti-aging 5 5 5 5 Aromatic oils 3 3 3 3 Stearic acid One One One One Zincification 3 3 3 3 Antioxidant One One One One Wax 1.5 1.5 1.5 1.5 adhesive 5 5 5 5 brimstone 2 2 2 2 Vulcanization accelerator * 0.5 - - - Vulcanization accelerator ** - 0.5 1.0 1.5

* Vulcanization accelerator: N-Cyclohexylbenzothiazole-2-Sulfenamide

** Vulcanization accelerator: N-Cyclohexyl-2-2-benzothiazyl sulfenamide

<Test Example 1>

Among the rubbers of Examples 1 to 3, the rubbers prepared in Example 1 and the rubbers prepared in Comparative Examples were measured for physical properties by ASTM-related regulations, and the results are shown in Table 2 below.

Table 2. Physical Properties of Rubber of Comparative Example and Example 1

Item Comparative example Example 1  Rheometer (160 ℃) Max. Torque 31 33 Min. Torque 23.2 23.5 T90 (min) 54 55 Tensile Properties (160 ℃) Hardness 54 55 300% modulus 171 175 Tensile Strength Kg / cm3 205 210

As shown in Table 2, it can be seen that the rubber prepared by the rubber composition of Example 1 of the present invention has superior physical properties compared to the rubber manufactured by the rubber composition of the conventional comparative example.

<Test Example 2>

The rubber composition prepared in Comparative Example and Example 1 was used to measure the scorch time and the vulcanization time, the vulcanization rate, and the maximum toco value, and the results are shown in Table 3. The measurement of the scorch time is the same as the Mooney Viscosty method. In addition, the vulcanization characteristics were carried out at 160 ° C using a moving die rheometer (MDR) to measure the vulcanization time (t 90 ), the vulcanization speed (t 9 -t 10 ) and the maximum torque value.

Table 3. MDR Physical Property Results for the Rubber Compositions of Comparative Example and Example 1

Item Comparative example Example 1 Scorch time (minutes) 15.1 18.2 Vulcanization time (t 90 , min) 8.8 8.4 Vulcanization Rate (t 9 -t 10 , Min) 5.2 4.5 Torque (dNm) 20.8 21.5

In Table 3, the scorch time is a numerical value representing scorch stability, which means that the longer the scorch time, the better the scorch stability and the better the coach resistance.

In addition, the vulcanization time, vulcanization speed, and maximum torque were measured by using MDR to determine the vulcanization characteristics. Value.

It is displayed on the rheometer curve and represents a straight line parallel to the time axis through the maximum and minimum values of torque. The vulcanization rate is the vulcanization time t 90 The lower the value of t and t 10, the faster the vulcanization rate and the shorter the time for vulcanization during rubber bonding.

From the results of Table 3, in the case of N-Cyclohexyl-2-2-benzothiazyl sulfenamide than N-Cyclohexylbenzothiazole-2-Sulfenamide which is generally used as a vulcanization accelerator according to the present invention, the scorch resistance can be improved to shorten the scorch time. have.

According to the present invention, by using N-cyclohexyl-2-2-benzothiazyl sulfenamide as a vulcanization accelerator, a separate scorch retarder can be obtained without lowering the vulcanization rate. It is possible to provide a carcass rubber composition that does not lower the scorch resistance even without using the scavenger, thereby improving the scorch resistance.

Claims (4)

In the carcass rubber composition, Containing 0.5 to 1.5 parts by weight of N-cyclohexyl-2-2-benzothiazyl sulfenamide of the following structural formula (1) as a vulcanization accelerator based on 100 parts by weight of the raw material rubber Carcass rubber composition with improved scorch resistance.
Figure 112008047179189-PAT00007
... Formula (1) The carcass rubber composition of claim 1, wherein the raw material rubber is natural rubber or mixed rubber in which natural rubber and butadiene rubber are mixed. Rubber consisting of the rubber composition of claim 1. A tire comprising a rubber comprising the rubber composition of claim 1.
KR1020080062773A 2008-06-30 2008-06-30 Enhance scorch resistance of carcass rubber composition KR20100002754A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020080062773A KR20100002754A (en) 2008-06-30 2008-06-30 Enhance scorch resistance of carcass rubber composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020080062773A KR20100002754A (en) 2008-06-30 2008-06-30 Enhance scorch resistance of carcass rubber composition

Publications (1)

Publication Number Publication Date
KR20100002754A true KR20100002754A (en) 2010-01-07

Family

ID=41812749

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020080062773A KR20100002754A (en) 2008-06-30 2008-06-30 Enhance scorch resistance of carcass rubber composition

Country Status (1)

Country Link
KR (1) KR20100002754A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150329710A1 (en) * 2012-12-18 2015-11-19 Bridgestone Corporation Method of producing rubber tyre compounds
KR20200097120A (en) 2019-02-07 2020-08-18 맹근호 Scorch-proof press device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150329710A1 (en) * 2012-12-18 2015-11-19 Bridgestone Corporation Method of producing rubber tyre compounds
US9592704B2 (en) * 2012-12-18 2017-03-14 Bridgestone Corporation Method of producing rubber tyre compounds
KR20200097120A (en) 2019-02-07 2020-08-18 맹근호 Scorch-proof press device

Similar Documents

Publication Publication Date Title
JP5172537B2 (en) Rubber composition for tire and method for producing the same
EP1801147B1 (en) Rubber composition for sidewall
US8466222B2 (en) Rubber composition for sidewalls and pneumatic tire produced using the same
KR100988539B1 (en) Rubber composition for side walls, method of producing the same, and pneumatic tire
JP5478816B2 (en) Rubber composition for tire
EP2006121B1 (en) Rubber composition for side wall, as well as pneumatic tire
DE112008002808T5 (en) tires
JP5872125B1 (en) Rubber composition and tire
JP2013514428A (en) High silica content for heavy vehicle tires
EP1988120B1 (en) Tire with tire tread structure including cap tread and base tread
JPH0748476A (en) Rubber composition for tire tread
KR101016367B1 (en) Tire rubber composition with improved antidegradant property
JP2016078520A (en) Pneumatic tire
JP2011032302A (en) Rubber composition for tread and pneumatic tire
KR20090100099A (en) Tire sidewall rubber composition
KR101142550B1 (en) Rubber composition for tire tread and tire manufactured by using the same
KR20100002754A (en) Enhance scorch resistance of carcass rubber composition
KR101196308B1 (en) Tire inner liner rubber composition comprising liquid phase polybutene for improving anti-air permeability
JP4467605B2 (en) Rubber composition, clinch and tire
JP5472772B2 (en) Clinch rubber composition and pneumatic tire using the same
JP7040159B2 (en) Rubber composition for tires
KR101023757B1 (en) Tire rubber composition with improved antidegradant property
KR20070037216A (en) Rubber composition for tire including nano-filler and coupling agent
JP6378100B2 (en) Rubber composition for tire and tire
KR100913596B1 (en) Tire apex rubber composition

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E90F Notification of reason for final refusal
E601 Decision to refuse application