Long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for non-asphalt-based high-polymer waterproof coiled material and preparation method thereof
Technical Field
The invention relates to the technical field of waterproof coiled materials, in particular to a long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for a non-asphalt-based high-polymer waterproof coiled material and a preparation method thereof.
Background
The non-asphalt-based polymer waterproof coiled material was invented by GRACE waterproof company in the United states at the earliest and brought into the China market. Subsequently, the state releases relevant standards in 2008, popularizes the pre-paved waterproof coiled material system and the construction technology, and at the present stage, China has many cities to develop underground comprehensive pipe gallery construction and tunnel engineering construction, thereby providing a wide application field for non-asphalt-based polymer waterproof coiled materials.
After the non-asphalt-based high-polymer waterproof coiled material is laid and fixed, reinforcing steel bars need to be bound, or the construction period is delayed, so that concrete cannot be poured immediately, and the non-asphalt-based high-polymer waterproof coiled material is likely to be irradiated by sunlight for as long as one month or even longer. Therefore, GB/T23457-2017 Pre-paved waterproof coiled material clearly stipulates that the coiled material passes through 60W/m2(300 nm-400 nm) the stripping strength requirement of the treated xenon-arc lamp with post-pouring cement mortar. However, after the non-asphalt-based polymer waterproof roll material in the market is irradiated by sunlight for one or two months, even if all the detection items are qualified, the bonding surface of the non-asphalt-based polymer waterproof roll material has cracks of different degrees, the low-temperature flexibility and the peeling strength of the roll material are generally reduced to be below 40% of the original value, even lower, and the skin type waterproof effect of the roll material is greatly influenced or even completely destroyed.
Disclosure of Invention
Aiming at the problems that after the existing non-asphalt-based high polymer waterproof coiled material on the market is irradiated by sunlight for one or two months, the bonding surface has cracks, the low-temperature flexibility and the peeling strength of the coiled material are reduced, and the skin type waterproof effect is influenced, the invention provides the long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for the non-asphalt-based high polymer waterproof coiled material and the preparation method thereof, the invention adopts hydrogenated polystyrene-polyisoprene-polystyrene thermoplastic rubber (Styrene Ethylene Propylene block copolymer, SEPS for short) as a basic framework material, and adopts naphthenic oil, two kinds of polyisobutylene, terpene resin, hydrogenated carbon penta-petroleum resin and other auxiliary agents as auxiliary materials, the obtained hot-melt pressure-sensitive adhesive can meet the national standard requirements and has low cost, compared with other hot-melt pressure-sensitive adhesives on the market, the hot-melt pressure-sensitive adhesive has longer-acting weather resistance and low-temperature bending performance, and the production process is simple and easy, no need of special equipment and special process, and no toxicity and harm in the preparation process.
In a first aspect, the invention provides a long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for a non-asphalt-based high-molecular waterproof coiled material, which comprises the following raw materials:
SEPS, naphthenic oil, first polyisobutene, second polyisobutene, terpene resin, hydrogenated carbon penta petroleum resin, nano zinc oxide, an antioxidant, an ultraviolet absorbent and a light stabilizer.
Further, the pressure-sensitive adhesive comprises the following raw materials in percentage by weight:
further, the SEPS had a polystyrene content of 13%, a diblock content of 30%, and a melt index of 22g/10min (230 ℃ C., load of 5 kg).
Further, the molecular weight of the first polyisobutene is not more than 1300, the molecular weight of the second polyisobutene is a medium molecular polyisobutene, and the molecular weight distribution index is 3.0;
the terpene resin is light-colored aliphatic nonpolar resin;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent.
Further, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1-2: 1,
the hindered phenol antioxidant is preferably pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ],
the phosphite antioxidant is preferably tris [2, 4-di-tert-butylphenyl ] phosphite.
Further, the ultraviolet absorbent is one or a combination of more of 2- (5-chloro (2H) -benzotriazole-2-yl) -4- (methyl) -6- (tert-butyl) phenol, 2- (2H-benzotriazole-2-yl) -4-tert-butyl-6-sec-butyl phenol, 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazole-2-yl) phenol and 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol.
Further, the light stabilizer is a hindered amine light stabilizer,
preferably, the compound is one or a combination of more of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol) ester, and poly- { [6- [ (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) ] -imino ] }.
In a second aspect, the invention provides a preparation method of a hot-melt pressure-sensitive adhesive for a non-asphalt-based polymer waterproof coiled material, which comprises the following steps:
(1) adding naphthenic oil, first polyisobutene, second polyisobutene, an antioxidant, an ultraviolet absorbent and a light stabilizer into production equipment, charging nitrogen, stirring to uniformly mix materials, and heating to 165-175 ℃;
(2) adding SEPS, and stirring at a constant temperature until the rubber is completely melted;
(3) adding terpene resin and hydrogenated carbon five petroleum resin, keeping the temperature and stirring until the terpene resin and the hydrogenated carbon five petroleum resin are melted uniformly;
(4) adding nano zinc oxide, controlling the vacuum degree to be-0.06 MPa to-0.1 MPa, and stirring while keeping the temperature.
Further, the preparation method comprises the following steps:
(1) adding 10-20% of naphthenic oil, 13-26% of first polyisobutylene, 3-10% of second polyisobutylene, 0.3-0.5% of antioxidant, 0.3-0.5% of ultraviolet absorbent and 0.5-1% of light stabilizer into production equipment, charging nitrogen, stirring at the rotating speed of 30-40 r/min to uniformly mix materials, and heating to 165-175 ℃;
(2) adding 15-30% SEPS, and stirring for 30-40 min under heat preservation until the rubber is completely melted;
(3) adding 20-35% of terpene resin and 10-25% of hydrogenated carbon penta petroleum resin, keeping the temperature and stirring for 30-40 min, and dissolving the mixture evenly;
(4) adding 0.5-3% of nano zinc oxide, controlling the vacuum degree to be-0.06 MPa-0.1 MPa, and stirring for 30-60 min under the condition of heat preservation.
Further, the preparation method also comprises the following steps:
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
The beneficial effect of the invention is that,
① the invention discloses a hot melt pressure sensitive adhesive for non-asphalt base high polymer waterproof coiled material, which contains light stabilizer, ultraviolet absorbent, nanometer zinc oxide and other additives, the adhesive uses SEPS as base material, the SEPS is a hydrogenated material, the saturation degree of the rubber segment is high, no crystallization is existed, the pressure sensitive adhesive has better heat resistance and ultraviolet aging resistance, the absorption rate of nanometer zinc oxide to ultraviolet ray is more than 95%, especially the absorption action to ultraviolet ray is strongest in the middle and long wave segment, the radiation intensity of the SEPS molecular segment in the hot melt pressure sensitive adhesive is weakened, thus protecting the hot melt pressure sensitive adhesive, the hindered amine light stabilizer can effectively trap the free radical generated by SEPS molecular segment itself caused by ultraviolet ray, preventing the chain reaction which causes the aging of the molecular segment, the ultraviolet absorbent can strongly absorb high energy ultraviolet ray (280 nm-400 nm), the energy conversion is carried out, the energy is released by the light with longer wavelength of heat energy or the long wavelength, thus further protecting the SEPS from being damaged, the adhesive surface of the hot melt high polymer waterproof coiled material from being damaged, and the adhesive strength of the hot melt pressure sensitive adhesive is obviously maintained after the sunlight is exposed to the excellent.
② the hot melt pressure sensitive adhesive for non-asphalt base macromolecule waterproof coiled material, PS and hydrogenated polyisoprene PI which are incompatible two-phase structure in SEPS, PS is dispersed in PI continuous phase to play the role of 'vulcanization' and reinforcement, because of the influence of side chain methyl of polyisoprene in the middle block, the hot melt pressure sensitive adhesive has good cohesion and adhesive property, low modulus, good elasticity, small melt viscosity and easy coating, the glass transition temperature of PI phase is-60 ℃, the glass transition temperature of PS phase is 95 ℃, and the glass transition temperature of PI phase is lower, so that the finally prepared pressure sensitive adhesive has better low temperature property and certain elasticity.
③ the hot melt pressure sensitive adhesive for non-asphalt base macromolecule waterproof coiled material adopts the formulation of naphthenic oil (naphthenic base rubber oil) and first polyisobutene as plasticizer, the molecular weight of the naphthenic oil is small, when the non-asphalt base macromolecule waterproof coiled material is stored and used for a long time, especially in a higher temperature environment, a part of the naphthenic oil is migrated and volatilized, thereby easily causing the initial viscosity of the pressure sensitive adhesive layer to be deteriorated, hardened and even lose adhesion, the molecular weight of the first polyisobutene is relatively large, and the first polyisobutene is used in combination with the naphthenic oil (the mass ratio of the naphthenic oil to the first polyisobutene is 10-20: 13-26), thereby not only ensuring the coiled material to have long-acting initial viscosity, but also improving the adhesive force between the pressure sensitive adhesive and the macromolecule substrate.
④ the hot melt pressure sensitive adhesive for the non-asphalt based high polymer waterproof coiled material increases the initial adhesion and the peeling strength of the pressure sensitive adhesive by selecting the tackifying resin (hydrogenated carbon five petroleum resin and terpene resin) compatible with the rubber phase in the SEPS molecular structure, and the initial adhesion and the peeling strength increase with the increase of the dosage of the tackifying resin in a certain range, on one hand, the tackifying resin reduces the cohesive force and the modulus of the pressure sensitive adhesive, on the other hand, the vitrification temperature of the rubber phase also increases, and in order to ensure the good low temperature performance of the pressure sensitive adhesive or the coiled material, the reduction of the low temperature performance is compensated by adopting a method of compounding the second polyisobutylene and the tackifying resin according to a certain proportion (the mass ratio of the second polyisobutylene to the tackifying resin is 3-10: 30-60), and the viscous base force of the pressure sensitive adhesive is enhanced at the same time.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
20kg of SEPS, 17.5kg of naphthenic oil, 20.2kg of first polyisobutene, 8kg of second polyisobutene, 25.1kg of terpene resin, 20kg of hydrogenated carbon penta petroleum resin, 1kg of nano zinc oxide, 0.5kg of antioxidant, 0.5kg of ultraviolet absorbent and 0.75kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is a compound of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 1: 1;
the ultraviolet absorbent is 2- (5-chloro (2H) -benzotriazole-2-yl) -4- (methyl) -6- (tert-butyl) phenol;
the light stabilizer is bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 17.5kg of naphthenic oil, 20.2kg of first polyisobutene, 8kg of second polyisobutene, 0.5kg of antioxidant, 0.5kg of ultraviolet absorbent and 0.75kg of light stabilizer into a reaction kettle, introducing nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 20kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 25.1kg of terpene resin and 20kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 1kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Example 2
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
33kg of SEPS, 19.1kg of naphthenic oil, 32.2kg of first polyisobutene, 5kg of second polyisobutene, 28.5kg of terpene resin, 14kg of hydrogenated carbon penta petroleum resin, 3kg of nano zinc oxide, 0.6kg of antioxidant, 0.5kg of ultraviolet absorbent and 1kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is a compound of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 2: 1;
the ultraviolet absorbent is 2- (2H-benzotriazole-2-yl) -4-tert-butyl-6-sec-butyl phenol;
the light stabilizer is poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 19.1kg of naphthenic oil, 32.2kg of first polyisobutene, 5kg of second polyisobutene, 0.6kg of antioxidant, 0.5kg of ultraviolet absorbent and 1kg of light stabilizer into a reaction kettle, charging nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 33kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 28.5kg of terpene resin and 14kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 3kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Example 3
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
40kg of SEPS, 31kg of naphthenic oil, 24.5kg of first polyisobutene, 5.5kg of second polyisobutene, 36.5kg of terpene resin, 28kg of hydrogenated carbon penta petroleum resin, 5kg of nano zinc oxide, 0.75kg of antioxidant, 0.7kg of ultraviolet absorbent and 1.5kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is a compound of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 1.5: 1;
the weight ratio of the ultraviolet absorbent is 1: 1 of a complex of 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol;
the light stabilizer is poly- { [6- [ (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) ] -imino ] }.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 31kg of naphthenic oil, 24.5kg of first polyisobutene, 5.5kg of second polyisobutene, 0.75kg of antioxidant, 0.7kg of ultraviolet absorbent and 1.5kg of light stabilizer into a reaction kettle, charging nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 40kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 36.5kg of terpene resin and 28kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 5kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Comparative example 1
Comparative example 1 is a hot melt pressure sensitive adhesive for a non-asphalt-based polymer waterproof coiled material produced by a domestic brand manufacturer.
Comparative example 2
Comparative example 2 is a non-asphalt-based polymer waterproof roll manufactured by domestic famous brand manufacturers.
Comparative example 3
Comparative example 3 is different from example 1 in that an ultraviolet absorber is used, and the ultraviolet absorber used in comparative example 3 is UV-531([ 2-hydroxy-4- (octyloxy) phenyl ] phenyl ketone);
comparative example 4
Comparative example 4 is different from example 1 in the amounts of the ultraviolet absorber and the light stabilizer, and in comparative example 4, the amount of the ultraviolet absorber was 0kg and the amount of the light stabilizer was 1.25 kg.
Comparative example 5
Comparative example 5 is different from example 1 in the amount of the ultraviolet absorber and the light stabilizer, and comparative example 4 is 0.25kg of the ultraviolet absorber and 1.0kg of the light stabilizer.
Test example 1
The pressure-sensitive adhesives of examples 1-3 and comparative examples 1, 3-5 are respectively coated on HDPE sheets to prepare non-asphalt-based polymer waterproof rolls, and the specific preparation method is as follows:
(1) adding the hot-melt pressure-sensitive adhesive block into a melt adhesive box and heating to a molten state;
(2) starting the auxiliary heating equipment to coat the HDPE sheet;
(3) and (4) starting a sanding device, uniformly covering the isolation sand on the adhesive layer, compacting by adopting a composite compression roller, and rolling to obtain the coiled material.
The performance of the non-asphalt-based polymer waterproof roll and the non-asphalt-based polymer waterproof roll of the comparative example 2 were tested, and the test results are shown in table 1 below.
TABLE 1 waterproofing membranes Performance test results
As can be seen from Table 1, the ultraviolet-resistant hot-melt pressure-sensitive adhesive for the non-asphalt-based polymer waterproof roll has excellent performances. Compared with comparative examples 1-5, the pressure-sensitive adhesive has stronger and longer-acting ultraviolet resistance, particularly, the peeling strength of the coiled material after being irradiated by sunlight for 2 months in summer with post-poured cement mortar can still be kept above 70%, and no crack appears on the bonding surface.
The pressure-sensitive adhesive has various physical and chemical indexes meeting the specified requirements of GB/T23457-2017 Pre-laid waterproof coiled material, and has the advantages of low cost, simple production process and wide application prospect.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.