Process for preparing cellulose solution and equipment therefor

Abstract

The present invention provides a process for preparing a cellulose solution. NMMO with a relatively low concentration and non-activated pulp are continuously mixed online, the mixed premix is dewatered in evaporation dewatering equipment until an NMMO concentration suitable for swelling is achieved, then, sufficient swelling is carried out under this condition, and the uniformly-mixed and sufficiently swelled pre-swelling solution is subjected to depressurized evaporation dewatering and dissolving by thin-film-evaporation equipment thereby obtaining a high-concentration, uniformly-dissolved and excellently-uniformity cellulose solution. The present invention further provides continuous preparation equipment for the process for preparing a cellulose solution. According to the present invention, the conflict between uniform mixing and sufficient swelling during the preparation of a high-concentration cellulose solution is solved, and problems in storage and transportation safety caused by using high concentration NMMO in the conventional technologies are prevented.

Claims

1. A process for preparing a cellulose solution, comprising: (1) uniformly mixing cellulose pulp and N-methylmorpholine-N-oxide-aqueous solution with a temperature in a range from 70 C. to 100 C. to obtain a premix, wherein a mass of the N-methylmorpholine-N-oxide aqueous solution is 5 to 10 times that of the cellulose pulp, and the N-methylmorpholine-N-oxide aqueous solution has a water to N-methylmorpholine-N-oxide mass ratio in a range from 28:72 to 60:40; (2) subjecting the premix to dewatering by depressurized evaporation at a dewatering temperature in a range from 80 C. to 110 C. under a dewatering pressure in a nine from 4 kPa to 10 kPa to obtain a pre-swelling solution, wherein the pre-swelling solution has a water to N-methylmorpholine-N-oxide mass ratio in a range from 16:84 to 28:72; (3) subjecting the pre-swelling solution to heat preservation in a swelling kettle, the pre-swelling solution being sufficiently swelled in a temperature in a range from 55 C. to 95 C. for a residence time in a range from 3 min to 60 min to obtain a swelled solution inside the swelling kettle; and (4) subjecting the swelled solution to dewater by depressurized evaporation and dissolving to obtain the cellulose solution.

2. The process for preparing the cellulose solution according to claim 1, wherein in step (1), the N-methylmorpholine-N-oxide aqueous solution has the water toN-methylmorpholine-N-oxide mass ratio in a range from 28:72 to 50:50.

3. The process for preparing the cellulose solution according to claim 1, wherein in step (2), the pre-swelling solution has the water to N-methylmorpholine-N-oxide mass ratio in a range from 18:82 to 27:73.

4. The process for preparing the cellulose solution according, to claim 1, wherein in step (1), the mass of the N-methylmorpholine-N-oxide aqueous solution is 8 to 10 times that of the cellulose pulp, and the N-methylmorpholine-N-oxide aqueous solution has a temperature in a range from 80 C. to 90 C.

5. The process for preparing the cellulose solution according to claim 1, wherein in step (1), a process for uniformly mixing the cellulose pulp and the N-methylmorpholine-N-oxide aqueous solution comprises adding the cellulose pulp and the N-methylmorpholine-N-oxide aqueous solution into continuous mixing equipment and carrying out continuous mixing for 5 min to 30 min at a stirring linear speed in a range from 60 m/min to 80 m/min.

6. The process for preparing the cellulose solution according to claim 1, wherein in step (4), a process for dewatering by depressurized evaporation and dissolving is thin-film-evaporation dewatering and dissolving and is carried out at a, dewatering temperature in a range from 100 C. to 150 C. under a dewatering pressure in a range from 4 kPa to 10 kPa at a thin-film wiping linear speed in a range from 2 m/s to 6 m/s.

7. The process for preparing the cellulose solution according to claim 1, wherein in step (1), the N-methylmorpholine-N-oxide aqueous solution has the water to N-methylmorpholine-N-oxide mass ratio in a range from 28:72 to 35:65.

8. The process for preparing the cellulose solution according to claim 1, wherein in step (2), the pre-swelling solution has the water to N-methylmorpholine-N-oxide mass ratio in a range from 19:81 to 25:75.

9. The process for preparing the cellulose solution according to claim 1, wherein in step (3), the pre-swelling solution is sufficiently swelled in a temperature in a range from 65 C. to 95 C. for a residence time in a range from 10 min to 45 min to obtain a swelled solution inside the swelling kettle.

10. The process for preparing the cellulose solution according to claim 1, wherein in step (3), the pre-swelling solution is sufficiently swelled in a temperature in a range from 75 C. to 85 C. for a residence time in a range from 15 min to 30 min to obtain a swelled solution inside the swelling kettle.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flow diagram of a process of the present invention;

(2) FIG. 2 is a structural schematic diagram of continuous preparation equipment for a cellulose solution of the present invention.

REFERENCE SIGNS

(3) TABLE-US-00001 1. continuous pulp charging device 2. continuous NMMO aqueous solution charging device 3. continuous mixer 4. continuous depressurizing and heating equipment 5. swelling kettle 6. thin-film-evaporation dissolving equipment 7. molding equipment 8. vacuum device

DETAILED DESCRIPTION

Embodiment 1

(4) (1) 20 kg of cellulose pulp (dry-cut pulp COSMO DP500, moisture content 6%) and 167 kg of NMMO aqueous solution of 70 C. were continuously added into a continuous mixer 3 through a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2 respectively, and were stirred for 30 min in the continuous mixer 3 at a stirring linear speed of 60 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 28:72.

(5) (2) The premix was continuously pumped into continuous depressurizing and heating equipment 4 and was subjected to dewatering by depressurized evaporation to obtain a pre-swelling solution. In the continuous depressurizing and heating equipment 4, a dewatering pressure was 6 kPa and a dewatering temperature was 105 C. And the pre-swelling solution at an outlet of the continuous depressurizing and heating equipment 4 had a water/NMMO mass ratio of 19:81.

(6) (3) The pre-swelling solution was continuously fed into a swelling kettle 5. The pre-swelling solution was sufficiently swelled in the temperature of 80 C. for the residence time of 15 min inside the swelling kettle to obtain a swelled solution.

(7) (4) The swelled solution was continuously pumped into thin-film-evaporation dissolving equipment 6 and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 12%. In the thin-film-evaporation dissolving equipment 6, a dewatering temperature was 100 C., a dewatering pressure was 4 kPa and a thin-film wiping speed was 2 m/s.

(8) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 2

(9) (1) 20 kg of cellulose pulp (dry-cut pulp bamboo pulp DP500, moisture content 6%) and 200 kg of NMMO aqueous solution of 85 C. were continuously added into a continuous mixer 3 through a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2 respectively, and were stirred for 20 min in the continuous mixer 3 at a stirring linear speed of 120 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 40:60.

(10) (2) The premix was continuously pumped into continuous depressurizing and heating equipment 4 and was subjected to dewatering by depressurized evaporation to obtain a pre-swelling solution. In the continuous depressurizing and heating equipment 4, a dewatering pressure was 4 kPa and a dewatering temperature was 110 C. And the pre-swelling solution at an outlet of the continuous depressurizing and heating equipment 4 had a water/NMMO mass ratio of 21:79.

(11) (3) The pre-swelling solution was continuously fed into a swelling kettle 5. The pre-swelling solution was sufficiently swelled in the temperature of 85 C. for the residence time of 30 min inside the swelling kettle to obtain a swelled solution.

(12) (4) The swelled solution was continuously pumped into thin-film-evaporation dissolving equipment 6 and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 12%. In the thin-film-evaporation dissolving equipment 6, a dewatering temperature was 120 C., a dewatering pressure was 6 kPa and a thin-film wiping speed was 4 m/s.

(13) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 3

(14) (1) 20 kg of cellulose pulp (dry-cut pulp cotton pulp DP500, moisture content 6%) and 168 kg of NMMO aqueous solution of 90 C. were continuously added into a continuous mixer 3 through a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2 respectively, and were stirred for 5 min in the continuous mixer 3 at a stirring linear speed of 180 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 35:70.

(15) (2) The premix was continuously pumped into continuous depressurizing and heating equipment 4 and was subjected to dewatering by depressurized evaporation to obtain a pre-swelling solution. In the continuous depressurizing and heating equipment 4, a dewatering pressure was 4 kPa and a dewatering temperature was 80 C. And the pre-swelling solution at an outlet of the continuous depressurizing and heating equipment 4 had a water/NMMO mass ratio of 25:75.

(16) (3) The pre-swelling solution was continuously fed into a swelling kettle 5. The pre-swelling solution was sufficiently swelled in the temperature of 55 C. for the residence time of 60 min inside the swelling kettle to obtain a swelled solution.

(17) (4) The swelled solution was continuously pumped into thin-film-evaporation dissolving equipment 6 and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 13%. In the thin-film-evaporation dissolving equipment 6, a dewatering temperature was 150 C., a dewatering pressure was 10 kPa and a thin-film wiping speed was 3 m/s.

(18) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 4

(19) (1) 20 kg of cellulose pulp (dry-cut pulp COSMO DP450, moisture content 6%) and 100 kg of NMMO aqueous solution of 100 C. were continuously added into a continuous mixer 3 through a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2 respectively, and were stirred for 15 min in the continuous mixer 3 at a stirring linear speed of 120 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 45:55.

(20) (2) The premix was continuously pumped into continuous depressurizing and heating equipment 4 and was subjected to dewatering by depressurized evaporation to obtain a pre-swelling solution. In the continuous depressurizing and heating equipment 4, a dewatering pressure was 4 kPa and a dewatering temperature was 90 C. And the pre-swelling solution at an outlet of the continuous depressurizing and heating equipment 4 had a water/NMMO mass ratio of 22:78.

(21) (3) The pre-swelling solution was continuously fed into a swelling kettle 5. The pre-swelling solution was sufficiently swelled in the temperature of 95 C. for the residence time of 3 min inside the swelling kettle to obtain a swelled solution.

(22) (4) The swelled solution was continuously pumped into thin-film-evaporation dissolving equipment 6 and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 15%. In the thin-film-evaporation dissolving equipment 6, a dewatering temperature was 120 C., a dewatering pressure is 6 kPa and a thin-film wiping speed was 6 m/s.

(23) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 5

(24) (1) 25 kg of cellulose pulp (wet-powder pulp COSMO DP500, moisture content 25%) and 167 kg of NMMO aqueous solution of 85 C. were continuously added into a continuous mixer 3 through a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2 respectively, and were stirred for 30 min in the continuous mixer 3 at a stirring linear speed of 120 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 28:72.

(25) (2) The premix was continuously pumped into continuous depressurizing and heating equipment 4 and was subjected to dewatering by depressurized evaporation to obtain a pre-swelling solution. In the continuous depressurizing and heating equipment 4, a dewatering pressure was 5 kPa and a dewatering temperature was 105 C. And the pre-swelling solution at an outlet of the continuous depressurizing and heating equipment 4 had a water/NMMO mass ratio of 20:80.

(26) (3) The pre-swelling solution was continuously fed into a swelling kettle 5. The pre-swelling solution was sufficiently swelled in the temperature of 80 C. for the residence time of 25 min inside the swelling kettle to obtain a swelled solution.

(27) (4) The swelled solution was continuously pumped into thin-film-evaporation dissolving equipment 6 and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 12%. In the thin-film-evaporation dissolving equipment 6, a dewatering temperature was 130 C., a dewatering pressure was 10 kPa and a thin-film wiping speed was 4 m/s.

(28) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 6

(29) A process for preparing a cellulose solution comprises the following steps:

(30) (1) Cellulose pulp and an NMMO aqueous solution of 70 C. were uniformly mixed to obtain a premix, wherein the mass of the NMMO aqueous solution was 5 times that of the cellulose pulp, and the NMMO aqueous solution had a water/NMMO mass ratio of 60:40.

(31) (2) The premix was subjected to dewatering by evaporation to obtain a pre-swelling solution. The pre-swelling solution had a water/NMMO mass ratio of 16:84.

(32) (3) The pre-swelling solution was subjected to heat preservation in a swelling kettle for sufficient swelling to obtain a swelled solution.

(33) (4) The swelled solution was subjected to dewatering by depressurized evaporation and dissolving to obtain the cellulose solution.

(34) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 7

(35) A process for preparing a cellulose solution comprises the following steps:

(36) (1) Cellulose pulp and an NMMO aqueous solution of 100 C. were uniformly mixed to obtain a premix. The mass of the NMMO aqueous solution was 10 times that of the cellulose pulp, and the NMMO aqueous solution had a water/NMMO mass ratio of 35:65.

(37) (2) The premix was subjected to dewatering by evaporation to obtain a pre-swelling solution. The pre-swelling solution had a water/NMMO mass ratio of 27:73.

(38) (3) The pre-swelling solution was subjected to heat preservation in a swelling kettle for sufficient swelling to obtain a swelled solution.

(39) (4) The swelled solution was subjected to dewatering by depressurized evaporation and dissolving to obtain the cellulose solution.

(40) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 8

(41) A process for preparing a cellulose solution comprises the following steps:

(42) (1) Cellulose pulp and an NMMO aqueous solution of 85 C. were uniformly mixed to obtain a premix. The mass of the NMMO aqueous solution was 8 times that of the cellulose pulp, and the NMMO aqueous solution had a water/NMMO mass ratio of 28:72.

(43) (2) The premix was subjected to evaporation dewatering to obtain a pre-swelling solution. The pre-swelling solution had a water/NMMO mass ratio of 19:81.

(44) (3) The pre-swelling solution was subjected to heat preservation in a swelling kettle for sufficient swelling to obtain a swelled solution.

(45) (4) The swelled solution was subjected to depressurized evaporation dewatering and dissolving to obtain the cellulose solution. Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 9

(46) A process for preparing a cellulose solution comprises the following steps:

(47) (1) Cellulose pulp and an NMMO aqueous solution of 90 C. were uniformly mixed to obtain a premix. The mass of the NMMO aqueous solution was 9 times that of the cellulose pulp, and the NMMO aqueous solution had a water/NMMO mass ratio of 29:62.

(48) (2) The premix was subjected to evaporation dewatering to obtain a pre-swelling solution, w The pre-swelling solution had a water/NMMO mass ratio of 20:79.

(49) (3) The pre-swelling solution was subjected to heat preservation in a swelling kettle for sufficient swelling to obtain a swelled solution.

(50) (4) The swelled solution was subjected to dewatering by depressurized evaporation and dissolving to obtain the cellulose solution.

(51) Proven by test, the solution had outstanding uniformity. Under the condition that the prepared cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the cellulose solution was excellent in spinning stability and was free of broken ends in a period of spinning time of 2 hours.

Embodiment 10

(52) Referring to FIG. 2, continuous preparation equipment for a cellulose solution, provided by the present invention, comprises continuous feeding equipment, a continuous mixer 3, continuous depressurizing and heating equipment 4, a swelling kettle 5 and thin-film-evaporation dissolving equipment 6. Wherein, the continuous feeding equipment comprises a continuous pulp charging device 1 and a continuous NMMO aqueous solution charging device 2, and the continuous pulp charging device 1 and the continuous NMMO aqueous solution charging device 2 are respectively connected with feeding sections of the continuous mixer 3. A discharging end of the continuous mixer 3 is connected with a charging end of the continuous depressurizing and heating equipment 4 through a pipeline. A discharging end of the continuous depressurizing and heating equipment 4 is connected with a charging end of the swelling kettle 5 through a pipeline, and a discharging end of the swelling kettle 5 is connected with a charging end of the thin-film-evaporation dissolving equipment.

(53) The continuous mixer 3 can be equipment with a continuous mixing function, such as a single-shaft continuous mixer, a twin-shaft continuous mixer or a twin-screw kneading-type continuous mixer.

(54) The continuous depressurizing and heating equipment 4 is selected from a continuous mixer equipped with a vacuum heating device. The thin-film-evaporation dissolving equipment 6 can be vertical type thin-film-evaporation dissolving equipment. Each of the continuous depressurizing and heating equipment 4 and the thin-film-evaporation dissolving equipment 6 is connected with a vacuum device 8.

(55) The continuous preparation equipment for the cellulose solution, provided by the present invention, may further comprise molding equipment 7. A charging end of the molding equipment 7 is connected with a discharging end of the thin-film-evaporation dissolving equipment.

(56) The continuous preparation equipment for the cellulose solution may further comprise a storage kettle and a first conveying pump. The storage kettle and the first conveying pump are successively arranged on a pipeline between the continuous mixer 3 and the continuous depressurizing and heating equipment 4.

(57) The continuous preparation equipment for the cellulose solution may further comprise a second conveying pump. The second conveying pump is arranged on a pipeline between the swelling kettle 5 and the thin-film-evaporation dissolving equipment 6.

(58) A specific implementation mode of the continuous preparation equipment for the cellulose solution is as follows:

(59) (1) Cellulose pulp and an NMMO aqueous solution were added into the continuous mixer 3 through the continuous pulp charging device 1 and the continuous NMMO aqueous solution charging device 2 respectively, and were sufficiently and uniformly mixed in the continuous mixer 3 to obtain a premix, and the premix was continuously added into the storage kettle.

(60) (2) The premix in the storage kettle was pumped into the continuous depressurizing and heating equipment 4 through a first conveying pump such that the premix is further intensively stirred and mixed. A stirring component of the continuous depressurizing and heating equipment 4 heat the premix through a contact face, the premix was subjected to dewatering by depressurized evaporation under certain vacuum until a predetermined volume of moisture was evaporated, and thus, an NMMO concentration reached an optimal swelling concentration range to obtain a pre-swelling solution.

(61) (3) The pre-swelling solution was continuously added into the swelling kettle 5 through a pipeline, and was sufficiently swelled under proper temperature conditions after a certain residence time so as to be converted into a swelled solution, and a temperature of an outer jacket of the swelling kettle was regulated and controlled through a heat medium.

(62) (4) The swelled solution was continuously pumped into the thin-film-evaporation dissolving equipment 6 through a second conveying pump, was spread out on the surface of a vertical type internal wall of the thin-film-evaporation dissolving equipment 6 to form a thin layer shape and was further dewatered under proper temperature and vacuum conditions to be converted into a cellulose solution with a concentration of 10% to 15%.

(63) (5) The cellulose solution was added into the molding equipment 7 and could be converted into products such as fibers, films and nonwoven fabrics.

COMPARATIVE EXAMPLE

(64) (1) 50 kg of cellulase activated pulp (COSMO DP500, moisture content 53%) and 178 kg of NMMO aqueous solution of 85 C. were stirred for 30 min at a stirring linear speed of 120 m/min to be uniformly mixed to obtain a premix. The NMMO aqueous solution had a water/NMMO mass ratio of 84:16.

(65) (2) The premix was added into a swelling kettle, was heated to a temperature of 85 C., and was subjected to heat preservation for 30 min for sufficient swelling to obtain a swelled solution.

(66) (3) The swelled solution was added into thin-film-evaporation dissolving equipment and was subjected to dewatering by depressurized evaporation and dissolving to obtain a cellulose solution with a cellulose concentration of 12%. The thin-film-evaporation dissolving equipment had a dewatering temperature of 130 C., a dewatering pressure of 10 kPa and a thin-film wiping speed of 4 m/s.

(67) Proven by test, the solution had poorer uniformity as compared with the solutions of the embodiments and had a larger gel-particle particle size. Under the same condition of not being filtered by filtering equipment, and under the condition that the cellulose solution was used for spinning by spinning equipment with a draft multiple of 5, the solution was poorer in spinning stability, and broken ends occurred frequently in a period of spinning time of 2 hours.

(68) The uniformity of the cellulose solution can be characterized through observing the dissolving condition of cellulose in the solution by a polarized microscope and detecting the particle size and particle size distribution of gel particles in the solution by a laser particle size analyzer. The smaller the particle size of the gel particles in the solution is and the narrower the particle size distribution is, the greater the uniformity of the solution is. And when the gel particles in the solution is relatively large in size and relatively wide in particle size distribution, the spinning stability of the solution will be affected, and a thread breaking phenomenon will occur when the draft multiple is relatively large.

(69) TABLE-US-00002 Solution uniformity Spinning stability Laser particle The spinning solution is not size analyzer filtered by filtering equipment, Polarized D50 D90 and is subjected to spinning for 2 Microscope um um hours with a draft multiple of 5 Embodiment 1 No insolubles 9 30 Stable spinning, no broken thread Embodiment 2 No insolubles 11 29 Stable spinning, no broken thread Embodiment 3 No insolubles 8 31 Stable spinning, no broken thread Embodiment 4 No insolubles 10 28 Stable spinning, no broken thread Embodiment 5 No insolubles 8.5 27 Stable spinning, no broken thread Embodiment 6 No insolubles 9.5 28 Stable spinning, no broken thread Embodiment 7 No insolubles 8 30 Stable spinning, no broken thread Embodiment 8 No insolubles 8.5 29 Stable spinning, no broken thread Embodiment 9 No insolubles 10 30 Stable spinning, no broken thread Comparative No insolubles 35 122 poorer stability, more frequent Example thread breaking

(70) It can be observed from the table above that the cellulose solution prepared by the process provided by the present invention is excellent in uniformity and high in spinning stability and is free of a thread breaking phenomenon in 2 hours of spinning.

(71) The embodiments of the present invention are described in detail above, however, the mentioned contents are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent variations, improvements, etc. made according to the scope of application of the present invention should shall all be covered within the scope of the present invention.