CN105317196A - Composite floor containing microsphere-foamed silicate-modified PVC and manufacturing method thereof - Google Patents

Composite floor containing microsphere-foamed silicate-modified PVC and manufacturing method thereof Download PDF

Info

Publication number
CN105317196A
CN105317196A CN201510804801.8A CN201510804801A CN105317196A CN 105317196 A CN105317196 A CN 105317196A CN 201510804801 A CN201510804801 A CN 201510804801A CN 105317196 A CN105317196 A CN 105317196A
Authority
CN
China
Prior art keywords
microballon
layer
foaming
modification
floor
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN201510804801.8A
Other languages
Chinese (zh)
Other versions
CN105317196B (en
Inventor
周锡成
李玉荣
赵雅静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liangshan Xicheng New Material Co Ltd
Original Assignee
Liangshan Xicheng New Material Co Ltd
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 Liangshan Xicheng New Material Co Ltd filed Critical Liangshan Xicheng New Material Co Ltd
Priority to CN201510804801.8A priority Critical patent/CN105317196B/en
Publication of CN105317196A publication Critical patent/CN105317196A/en
Application granted granted Critical
Publication of CN105317196B publication Critical patent/CN105317196B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to the technical field of plastic processing, in particular to a composite plastic floor containing microsphere-foamed PVC. The composite floor comprises a microsphere-foamed damping layer, a reinforcing layer, a microsphere-foamed printing base layer, a printing layer, a modified PU wear-resisting layer, an embossing layer, a UV curing glazing layer and the like. The produced floor is high in strength, good in wear resistance and heat preservation performance and free of plasticizer overflowing, solves the technical problems existing in existing floor industry and can replace a wooden floor.

Description

A kind of microballon foams silicate modified PVC composite floor board and preparation method thereof
Technical field
The present invention relates to technical field of plastic, relate to a kind of Combined floor of the silicate modified layer of PVC that foams containing microballon in particular.
Technical background
Current domestic floor annual requirement is greatly about 1,500,000,000 square meter, mainly based on wood floors and plastic floor, wood floors are divided into wooden floor, solid wooden compound floor and strengthening composite floor, solid wood and solid wooden compound floor account for more than 40%, strengthening composite floor 50%, especially family's installed floor is all adopt solid wooden compound floor and consolidated floor substantially, the rich Talents employing wooden floor of small part, because solid wood and solid wooden compound floor main raw material(s) are wooden boards, content of formaldehyde is less, but price is more expensive.Strengthening composite floor adopts wood powder, adhesive and veneer to make, and content of formaldehyde is higher.China is the poorer country of a timber resources, current China afforestation rate only has 16.5%, only be equivalent to that the World Forests coverage scale is 31.7% 52%, area of woods is only equivalent to about 1/8 of world's Per capita area per capita, a large amount of felling timber not only reduces timber resources and also destroys ecological environment, brings great harm to human habitat.Country has carried out to prohibit to the use of natural forest resource and to have cut down and limit cuts down policy for this reason, and country 13 planning puts into effect new policy again, " Green Development forbids the harvesting of wood and tree grafting growth ".Therefore the raw material producing wood floors from now on can be fewer and feweri, price also can be more and more expensive, can cause great market has openings to Floor Industry very soon, the fitment material for family therefore researching and developing alternative wood floors is very important, is also the top priority of material development person.
For this reason Jin Liangnian lot of domestic and international enterprise begin one's study develop various formula different structure PVC plastic floor replace wood floors, main formula is divided to be divided into foaming floor and floor of not foaming by technique, current foaming floor mostly is AC foaming, AC foaming floor cell uniformity is poor, intensity is lower, wear no resistance, application life is short, oxynitrides and carbon monoxide is discharged after AC blowing agent decomposes, document announcement has mutagenesis, stimulation can be produced toxic, there is corrosion, contact scar air, suck human body or contact raw material and can cause major injury or lethal, for head it off, the present invention proposes application microballon blowing agent and foams to PVC, the PVC uniform pore diameter of microballon foaming agent foam, medium density, yield rate is high, also improve intensity and the anti-wear performance of material simultaneously, and it is nontoxic, environmental protection, improve from structure on the other hand, all add microballon foamed damping layer up and down at enhancement layer, increase the elasticity on floor, the casing play on protection floor is injury-free, extends the application life on floor.
Divide by structure and be mainly divided into the common extrusion molding of individual layer ' structure, homogeneous penetrating structure and multi-layer combined structure, need in PVC floor manufacturing process to add the heavy metal salt stabilizing agents such as the plasticizing agent of gross weight about 50% and lead, tin, in use plasticizing agent and heavy metal stabilizer can constantly be separated out, be released slowly in indoor environment, esophagus, respiratory tract, skin three kinds of approach are had to enter human body by entering human body, all can cause serious injury to human reproductive systems, internal system and nervous system, even the fetus in pregnant woman's abdomen be damaged.Also have above-mentioned reason to cause PVC floor also not obtain the accreditation of people in house ornamentation field just, market consumption is little.Present invention employs microballon foaming multi-layer compound structure, do not add plasticizing agent, be provided with UV cured layer at floor top layer simultaneously, the spilling of low-molecular material and additive in PVC floor can well be stoped like this, solve the problem of PVC floor wholesomeness from structure, also can save a large amount of costs.
Summary of the invention
The subject matter that the present invention solves is that the above-mentioned technology existed for existing Floor Industry and fault in material provide that a kind of good springiness, mechanical property are good, long service life, the elastomer floor of alternative wood floors.
The invention provides a kind of microballon foaming PVC Combined floor, at least comprise microballon foamed damping layer sets gradually enhancement layer, microballon foaming printed substrate, modification PU wearing layer and UV cured layer;
Printed layers can be provided with between described microballon foaming printed substrate and modification PU wearing layer.
Embossed layers can be provided with between modification PU wearing layer and UV cured layer.
Enhancement layer can be obtained by silicate modified PVC;
Microballon foamed damping layer and microballon foaming printed substrate can be adopt microballon blowing agent to carry out foaming to silicate modified PVC to obtain, and described microballon refers to: the one of polyurethane granular, polyvinyl chloride microballon, polyacrylic acid microballon, polyolefin microballon, fluororesin microballon, polystyrene microbeads or several mixing composition;
Modification PU wearing layer can be adopt TPU, TPVC, acrylic acid, acrylonitrile, epoxy resin, polysiloxanes, carborundum, silicate, silica, calcium carbonate one or more modification carried out to polyurethane obtain, improve the anti-wear performance of polyurethane;
A kind of preparation method of microballon foaming PVC Combined floor comprises: blending and modifying, coating, foaming, embossing;
Concrete steps are as follows:
(1) add in PVC by the silicate through surface active, carry out strength modified to polyvinyl chloride resin, improve its intensity, through mixing, extruding, roll, the operation such as press polish or mold pressing completes the making of enhancement layer;
(2) adopt reverse roll roll application to apply the silicate modified PVC of one deck microballon foaming at enhancement layer upper surface, then through oily heat roller tube heated gel, complete the making of microballon foaming printed substrate;
(3) adopt 12 look continuous intaglio plate, soft version or net roller printing line, print in microballon foaming printed substrate according to different designs scheme, form printed layers;
(4) in order to improve floor abrasion resistance and application life, adopting floating scraper cladding process to apply one deck in above-mentioned surface of semi-finished in modified PU slurry, forming modification PU wearing layer;
(5) apply material reversing frame and above-mentioned semiproduct are reversed 180 °, adopt reverse roll cladding process, apply the PVC of one deck microballon foaming at enhancement layer soffit, through gel baking oven, complete the making of microballon foamed damping layer;
(6) above-mentioned semiproduct are through being furnished with the gel blowing oven of CTS bottom nozzle, TP top jet nozzle and roll-type transfer system, microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is foamed, complete the foam process of microballon foaming PVC Combined floor, the foaming precision controlling of the thickness of microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is at ± 0.15mm;
(7) apply knurling rolls and the modification PU wearing layer upper epidermis after foaming is carried out embossing, make the top of modification PU wearing layer become embossed layers, promote non-skid property and the aesthetic property on floor;
(8) at embossed layers surface coating one deck maskable plasticizer and the UV glazing layer protecting indoor environment, and solidify, form UV cured layer, obtain a kind of microballon foaming PVC Combined floor.
(9) the said goods is carried out detect, cutting edge, rolling, packaging, to store after detection.
Step (4) can be: first adopt the tape casting to make film material on modification PU layer, is compounded in online above printed layers extruding, after printing process.
accompanying drawing illustrates:
Fig. 1 is structural representation of the present invention.
specific embodiment:
In Fig. 1,1, UV cured layer, 2, embossed layers, 3, modification PU wearing layer, 4, printed layers, 5, microballon foaming printed substrate, 6, silicate modified PVC enhancement layer, 7, microballon foamed damping layer.
A kind of microballon foaming PVC Combined floor, comprise microballon foamed damping layer sets gradually enhancement layer, microballon foaming printed substrate, modification PU wearing layer and UV cured layer, microballon foamed damping layer thickness is at 1 ~ 2.5mm, enhancement layer 1 ~ 2.5mm, microballon foaming printed substrate is at 0.8 ~ 1mm, modification PU wearing layer 0.5 ~ 1mm, UV cured layer 0.2 ~ 1mm.Ultraviolet curing layer is mixed and made into UV coating by polyurethane, epoxy resin and methyl acrylate wherein one or more;
Printed layers is provided with between described microballon foaming printed substrate and modification PU wearing layer.
Embossed layers is provided with between modification PU wearing layer and UV cured layer.
Enhancement layer is obtained by silicate modified PVC.
Microballon foamed damping layer and microballon foaming printed substrate adopt microballon blowing agent to carry out foaming to silicate modified PVC to obtain, described microballon refers to: the one of polyurethane granular, polyvinyl chloride microballon, polyacrylic acid microballon, polyolefin microballon, fluororesin microballon, polystyrene microbeads or several mixing composition, and described blowing agent refers to: one or more mixing compositions wherein such as sodium carbonate, sodium acid carbonate, ammonium hydrogencarbonate, citric acid, sodium antimonate, sodium nitrate, potassium nitrate, alkane.The particle diameter of microballon blowing agent is 40 ~ 80 μm, and consumption is 0.1%;
Modification PU wearing layer adopts TPU, TPVC, acrylic acid, acrylonitrile, epoxy resin, polysiloxanes, carborundum, silicate, silica, calcium carbonate mixture to carry out modification to polyurethane and obtain;
A kind of preparation method of microballon foaming PVC Combined floor comprises: blending and modifying, coating, foaming, embossing;
Concrete steps are as follows:
(1) by the French chalk of surface active, wollastonite in powder, kaolin in 2:1:1 ratio, addition is 50%, add in PVC, and undertaken blended by mixing up machine, the material mixed is joined in extruder and extrudes, the temperature of extruder is set in the scope of 155-165 DEG C, then complete enhancement layer through the prior art operation such as calendering, press polish or mold pressing and make, now the intensity of material can improve 8% than simple PVC;
(2) adopt reverse roll cladding process to apply the silicate modified PVC of one deck microballon foaming at enhancement layer upper surface, then through oil heating roller heated gel, temperature is 80 DEG C, and the time is 2S, completes the making of microballon foaming printed substrate;
(3) adopt 12 look continuous intaglio plate, soft version or net roller printing line, print in microballon foaming printed substrate according to different designs scheme, form printed layers;
(4) adopt floating scraper cladding process to apply one deck in above-mentioned surface of semi-finished in modified PU slurry, form modification PU wearing layer;
(5) apply material reversing frame and above-mentioned semiproduct are reversed 180 °, adopt reverse roll roll application, apply the PVC of one deck microballon foaming at enhancement layer soffit, through gel baking oven, temperature is 80 DEG C, and the time is 4S, completes the making of microballon foamed damping layer;
(6) above-mentioned semiproduct are through being furnished with the gel blowing oven of CTS bottom nozzle, TP top jet nozzle and roll-type transfer system, microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is foamed, the temperature of blowing oven is 160 DEG C, the length of baking oven is 15m, complete the foam process of microballon foaming PVC Combined floor, the foaming precision controlling of the thickness of microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is at ± 0.15mm;
(7) apply knurling rolls and the modification PU wearing layer upper epidermis after foaming is carried out embossing, make the top of modification PU wearing layer become embossed layers;
(8) at embossed layers surface coating one deck UV glazing layer, and solidify, form UV cured layer, obtain a kind of microballon foaming PVC Combined floor.
(9) the said goods is carried out detect, cutting edge, rolling, packaging, to store after detection.

Claims (10)

1. microballon foams a silicate modified PVC Combined floor, it is characterized in that: at least comprise microballon foamed damping layer sets gradually enhancement layer, microballon foaming printed substrate, modification PU wearing layer and UV cured layer.
2. the silicate modified PVC Combined floor that foams of a kind of microballon according to right 1 is characterized in that: be provided with printed layers between described microballon foaming printed substrate and modification PU wearing layer.
3. the silicate modified PVC Combined floor that foams of a kind of microballon according to right 1 is characterized in that: be provided with embossed layers between modification PU wearing layer and UV cured layer.
4. the silicate modified PVC Combined floor that foams of a kind of microballon according to right 1 is characterized in that: enhancement layer is obtained by silicate modified PVC.
5. the silicate modified PVC Combined floor that foams of a kind of microballon according to right 1 is characterized in that: microballon foamed damping layer and microballon foaming printed substrate are that to adopt microballon blowing agent to carry out foaming to silicate modified PVC obtained, described microballon refers to: polyurethane granular, polyvinyl chloride microballon, polyacrylic acid microballon, polyolefin microballon, fluororesin microballon, the one of polystyrene microbeads or several mixing composition, described blowing agent refers to: sodium carbonate, sodium acid carbonate, ammonium hydrogencarbonate, citric acid, sodium antimonate, sodium nitrate, potassium nitrate, one or more mixing compositions wherein such as alkane.
6. silicate modified its spy of PVC Combined floor that foams is a kind of microballon according to right 1: modification PU wearing layer to adopt in TPU, TPVC, acrylic acid, acrylonitrile, epoxy resin, polysiloxanes, carborundum, silicate, silica, calcium carbonate one or more to carry out modification to polyurethane to obtain.
7. microballon foams a preparation method for silicate modified PVC Combined floor, it is characterized in that: comprising: blending and modifying, coating, foaming, embossing;
Concrete steps are as follows:
(1) silicate through surface active is added in PVC, carry out strength modified to polyvinyl chloride resin, complete the making of enhancement layer through molding procedure;
(2) adopt reverse roll roll application to apply the silicate modified PVC of one deck microballon foaming at enhancement layer upper surface, then through oily heat roller tube heated gel, complete the making of microballon foaming printed substrate;
(3) print in microballon foaming printed substrate according to different designs scheme, form printed layers;
(4) adopt floating scraper cladding process to apply one deck in above-mentioned surface of semi-finished in modified PU slurry, form modification PU wearing layer;
(5) apply material reversing frame and above-mentioned semiproduct are reversed 180 °, adopt reverse roll cladding process, apply the PVC of one deck microballon foaming at enhancement layer soffit, through gel baking oven, complete the making of microballon foamed damping layer;
(6) above-mentioned semiproduct are through being furnished with the gel blowing oven of CTS bottom nozzle, TP top jet nozzle and roll-type transfer system, microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is foamed, complete the foam process of microballon foaming PVC Combined floor, foaming precision controlling is at ± 0.15mm;
(7) apply knurling rolls and the modification PU wearing layer upper epidermis after foaming is carried out embossing, make the top of modification PU wearing layer become embossed layers;
(8) at embossed layers surface coating one deck UV glazing layer, and solidify, form UV cured layer, obtain a kind of microballon and to foam silicate modified PVC Combined floor.
8. a kind of microballon according to right 7 foams the preparation method of silicate modified PVC Combined floor: it is characterized in that: also comprise the following steps: the said goods to carry out after step (8) to detect, cutting edge, rolling, packaging, to store after detection.
9. a kind of microballon according to right 7 foams the preparation method of silicate modified PVC Combined floor: it is characterized in that: step (4) is: first adopt the tape casting to make film material on modification PU layer, is compounded in online above printed layers extruding, after printing process.
10. a kind of microballon according to right 7 foams the preparation method of silicate modified PVC Combined floor: it is characterized in that: in step (4), and the foaming precision controlling of the thickness of microballon foamed damping layer, enhancement layer and microballon foaming printed substrate is at ± 0.15mm.
CN201510804801.8A 2015-11-20 2015-11-20 Silicate modified PVC composite floor boards of a kind of microballon foaming and preparation method thereof Expired - Fee Related CN105317196B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510804801.8A CN105317196B (en) 2015-11-20 2015-11-20 Silicate modified PVC composite floor boards of a kind of microballon foaming and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510804801.8A CN105317196B (en) 2015-11-20 2015-11-20 Silicate modified PVC composite floor boards of a kind of microballon foaming and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105317196A true CN105317196A (en) 2016-02-10
CN105317196B CN105317196B (en) 2017-12-05

Family

ID=55245431

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510804801.8A Expired - Fee Related CN105317196B (en) 2015-11-20 2015-11-20 Silicate modified PVC composite floor boards of a kind of microballon foaming and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105317196B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108527984A (en) * 2018-03-22 2018-09-14 苏州和记荣达新材料有限公司 A kind of PVC composite boards
CN109109335A (en) * 2017-06-22 2019-01-01 陆钉毅 Plastic floor forming method and its finished product with back pad

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1533043A1 (en) * 2003-11-21 2005-05-25 Parkett Franz GmbH Method and plant for coating wood or wooden materials
CN201390084Y (en) * 2009-03-09 2010-01-27 何庭佳 Glass light-reflection film composite plate
DE102009008381B3 (en) * 2009-02-11 2010-08-05 Flooring Technologies Ltd. Method for finishing wood-based material board i.e. high density fiber board, utilized as floor laminate, involves pressing layer structure, where ground coat, primer, sealing and decorative layer are dried before applying one after another
CN203285021U (en) * 2012-11-08 2013-11-13 刘宝宣 Digital ink-jet printing cork composite flooring
CN103950267A (en) * 2013-05-02 2014-07-30 张家港爱丽塑料有限公司 PVC expanded plastic composite board and production method and application thereof
CN204225409U (en) * 2014-10-31 2015-03-25 泰州市华丽塑料有限公司 High abrasion sound insulation wood-plastic decorative board
CN204401956U (en) * 2014-12-30 2015-06-17 泰州市华丽塑料有限公司 A kind of damping and silencing snap close Wood-plastic floor
CN204401938U (en) * 2014-12-30 2015-06-17 泰州市华丽塑料有限公司 A kind of high abrasion sound insulation wood-plastic decorative board
US20150275528A1 (en) * 2014-03-31 2015-10-01 Proverum Ag Method for working a useful surface of a floor covering
CN204781797U (en) * 2015-06-04 2015-11-18 山东乐得仕软木科技有限公司 Soft wood composite floor is moulded to PVC wood
CN205259534U (en) * 2015-11-20 2016-05-25 凉山州锡成新材料股份有限公司 Modified PVC laminate flooring of microballon foaming silicate

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1533043A1 (en) * 2003-11-21 2005-05-25 Parkett Franz GmbH Method and plant for coating wood or wooden materials
DE102009008381B3 (en) * 2009-02-11 2010-08-05 Flooring Technologies Ltd. Method for finishing wood-based material board i.e. high density fiber board, utilized as floor laminate, involves pressing layer structure, where ground coat, primer, sealing and decorative layer are dried before applying one after another
CN201390084Y (en) * 2009-03-09 2010-01-27 何庭佳 Glass light-reflection film composite plate
CN203285021U (en) * 2012-11-08 2013-11-13 刘宝宣 Digital ink-jet printing cork composite flooring
CN103950267A (en) * 2013-05-02 2014-07-30 张家港爱丽塑料有限公司 PVC expanded plastic composite board and production method and application thereof
US20150275528A1 (en) * 2014-03-31 2015-10-01 Proverum Ag Method for working a useful surface of a floor covering
CN204225409U (en) * 2014-10-31 2015-03-25 泰州市华丽塑料有限公司 High abrasion sound insulation wood-plastic decorative board
CN204401956U (en) * 2014-12-30 2015-06-17 泰州市华丽塑料有限公司 A kind of damping and silencing snap close Wood-plastic floor
CN204401938U (en) * 2014-12-30 2015-06-17 泰州市华丽塑料有限公司 A kind of high abrasion sound insulation wood-plastic decorative board
CN204781797U (en) * 2015-06-04 2015-11-18 山东乐得仕软木科技有限公司 Soft wood composite floor is moulded to PVC wood
CN205259534U (en) * 2015-11-20 2016-05-25 凉山州锡成新材料股份有限公司 Modified PVC laminate flooring of microballon foaming silicate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109109335A (en) * 2017-06-22 2019-01-01 陆钉毅 Plastic floor forming method and its finished product with back pad
CN108527984A (en) * 2018-03-22 2018-09-14 苏州和记荣达新材料有限公司 A kind of PVC composite boards

Also Published As

Publication number Publication date
CN105317196B (en) 2017-12-05

Similar Documents

Publication Publication Date Title
CN105908946B (en) Coextru-lamination stone moulds PVC floor
CN106977833A (en) Polyvinyl chloride composite materials and its processing method
CN103358629A (en) Straw wood-plastic composite board
CN205259534U (en) Modified PVC laminate flooring of microballon foaming silicate
CN105317196A (en) Composite floor containing microsphere-foamed silicate-modified PVC and manufacturing method thereof
CN103362274A (en) PVC composite shingle
CN109605770A (en) A kind of production technology of cork stone plastic floor
CN105860318A (en) A co-extruded double-foaming polymer composite material floor and a processing method thereof
CN105346172A (en) Composite panel and production method thereof
CN103897299A (en) Microlite PVC foam floor
CN203924604U (en) A kind of PVC composite floor board
CN104929333A (en) Waterproof panel and manufacturing method thereof
CN108019028A (en) A kind of SPC solid wooden compound floors
CN104987613A (en) Wood plastic floor veneer
CN206220423U (en) A kind of solid wood paster plastic floor
CN201078075Y (en) Plastic and wood composite floor
CN111410507B (en) Fireproof and waterproof biomass floor and preparation method thereof
CN108003514A (en) A kind of production method of improved PVC wood plastic boards supporting substrates and PVC wood plastic wall board
CN106832654A (en) Novel wood-plastic Wood-emulating floor and preparation method thereof
CN206636117U (en) Petrified wood waterproof laminate floor
CN110105691A (en) A kind of floor SPC and its production technology
CN206034848U (en) Wood -plastic board
CN102557522A (en) Material for building decoration and artificial floor manufactured by material for building decoration
CN205604649U (en) Waterproof type multilayer laminate flooring
CN109593298A (en) The LVT musculus cutaneus and its manufacture craft and production line of a kind of Wood-plastic floor

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20171205

Termination date: 20191120

CF01 Termination of patent right due to non-payment of annual fee