KR100524854B1 - Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property - Google Patents
Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property Download PDFInfo
- Publication number
- KR100524854B1 KR100524854B1 KR10-2002-0063080A KR20020063080A KR100524854B1 KR 100524854 B1 KR100524854 B1 KR 100524854B1 KR 20020063080 A KR20020063080 A KR 20020063080A KR 100524854 B1 KR100524854 B1 KR 100524854B1
- Authority
- KR
- South Korea
- Prior art keywords
- layer
- parts
- weight
- resin
- resistance
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
- B32B2419/04—Tiles for floors or walls
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Floor Finish (AREA)
- Laminated Bodies (AREA)
Abstract
본 발명은 표면수지층으로서 올레핀계 아이오노머수지를 사용함으로써 내마모성, 내약품성, 내오염성 및 의장성이 우수한 바닥타일에 관한 것이다. 또한 본 발명의 바닥타일은 내부에 유리섬유층을 더 포함하여 양호한 치수안정성, 형태안정성 및 시공접착성을 얻을 수 있다.The present invention relates to a floor tile having excellent abrasion resistance, chemical resistance, fouling resistance and designability by using an olefin ionomer resin as a surface resin layer. In addition, the bottom tile of the present invention may further include a glass fiber layer therein to obtain good dimensional stability, form stability and construction adhesiveness.
Description
본 발명은 자외선 경화형 도료의 사용없이 올레핀계 아이오노머수지를 PVC 투명층 대신 사용함으로써 인쇄층의 인쇄 선명성을 증진시키고 내후성, 내마모성뿐만 아니라 내오염성이 우수하여 유지관리가 용이한 합성수지계 바닥타일에 관한 것이다.The present invention relates to a synthetic resin floor tile that is easy to maintain by improving the printing clarity of the printed layer and excellent weather resistance, abrasion resistance as well as stain resistance by using an olefin ionomer resin instead of a PVC transparent layer without the use of UV curing paint. .
일반적으로 인쇄시트가 포함된 PVC 바닥타일은 인쇄효과의 증진을 위해 인쇄시트 접촉면에 적어도 하나의 백색시트를 삽입하여 인쇄효과를 올리고 있다.In general, a PVC floor tile including a printing sheet has a printing effect by inserting at least one white sheet into the printing sheet contact surface to enhance the printing effect.
PVC 투명층을 갖고 있는 바닥타일의 경우 PVC 투명층이 완전히 투명하지 못하여 인쇄선명성이 저하되고 자외선에 노출시 황변현상이 발생하며 내마모성 및 내스크래치성 등이 취약하여 이의 극복을 위해 자외선 경화형 도료를 사용하여 초기 내오염성 및 내스크래치성을 보완하고 있으나 도막의 마모시 문제가 되고 있다.In the case of floor tiles with a PVC transparent layer, the PVC transparent layer is not completely transparent, resulting in poor print sharpness, yellowing when exposed to ultraviolet light, and weak resistance to abrasion and scratch. Complementing the stain resistance and scratch resistance, but has become a problem when the coating film wear.
따라서, 본 발명은 상기 언급한 바와 같은 종래의 문제점을 해결하기 위한 것으로, 내마모성, 내오염성, 내스크래치성 및 의장성이 우수한 바닥타일을 제공하는 것을 그 목적으로 한다.Accordingly, the present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a floor tile having excellent abrasion resistance, stain resistance, scratch resistance and designability.
본 발명의 다른 목적은 치수안정성, 형태안정성 및 시공접착성이 양호한 바닥타일을 제공하는 것이다.Another object of the present invention is to provide a floor tile having good dimensional stability, shape stability and construction adhesiveness.
상기한 목적을 달성하기 위하여, 본 발명의 바닥타일은 표면수지층으로서 아이오노머수지층을 사용한다.In order to achieve the above object, the bottom tile of the present invention uses an ionomer resin layer as a surface resin layer.
아이오노머(Ionomer)란 공유결합과 이온결합을 동시에 소유하고 있는 열가소성 플라스틱이며, 이온결합가지의 정전기력(Electrostatic Forces)이 매우 강하여 아이오노머 고유의 물성을 나타내며, 특히 강인성과 적당한 탄력성을 가진 내한성과 내마모성이 우수한 수지이다.Ionomer is a thermoplastic that possesses covalent and ionic bonds at the same time, and has very strong electrostatic forces of ion-bonded branches, showing the unique properties of ionomers, especially cold and abrasion resistance with toughness and moderate elasticity This is an excellent resin.
아이오노머는 폴리올레핀의 분자고리에 카본산기의 측고리가 있고 그 카본산기의 일부가 금속 양이온에 의해서 분자고리간에 가교되어 있는 구조로 되어 있다. 이 두개의 구조상 특징에 의해 많은 우수한 성질이 생긴다.The ionomer has a structure in which side chains of carboxylic acid groups are present in the molecular rings of the polyolefin, and a part of the carboxylic acid groups are crosslinked between the molecular rings by metal cations. These two structural features give rise to many excellent properties.
아이오노머는 교차이온결합(Ionically Crosslinked) 구조를 가진 열가소성 고분자 물질이며, 예를 들면 에틸렌과 메타크릴릭산의 공중합체(Ethylene/ Methacrylic Acid Copolymer)로부터 제조되므로 그 밀도나 가공성에 있어서 저밀도 폴리에틸렌(LDPE)이나 에틸렌 비닐아세테이트(EVA)와 비슷하나 전반적 물성은 더 우수하며, 일반 열가소성수지와 같이 성형이 가능하고 용해강도와 용해연신성이 우수하고 또한 고화상태에서는 이온결합이 더 강해지므로 강인성이 더 커진다. 교차이온결합은 열에 대해 안정하기 때문에 일반적인 가공온도인 175~290℃에서 가공할 수 있으므로 압출 및 Blown가공이 가능하다. 아이오노머수지는 각각 수지의 흐름(Melt Flow Index)도 다르고, 나트륨이나 아연 양이온 중 하나를 소유하므로 그 물리적 물성도 서로 다르고 가공성도 차이가 있다.Ionomer is a thermoplastic polymer with ionically crosslinked structure. For example, ionomer is made from copolymer of ethylene and methacrylic acid (Ethylene / Methacrylic Acid Copolymer). It is similar to ethylene vinyl acetate (EVA), but its overall physical properties are better, and it can be molded like general thermoplastic resin, and its toughness is increased because it has excellent solubility and dissolution elongation. Since cross-ion bonds are stable to heat, they can be processed at the general processing temperature of 175 ~ 290 ℃, so extrusion and blown processing are possible. The ionomer resin also has a different resin flow (Melt Flow Index), and because it possesses either sodium or zinc cations, its physical properties are different and processability is different.
즉, 아이오노머수지의 물성과 적용은 이온의 종류에 따라 결정될 수 있는데, 나트륨 이온형은 투명성, 내유성, 용융 점착성 등이 우수하고 아연이온형은 공압출시에 접착성능이 좋고 알루미늄 박에 압출코팅이 용이하다.In other words, the properties and application of the ionomer resin can be determined according to the type of ions. The sodium ion type has excellent transparency, oil resistance, melt adhesion, etc., and the zinc ion type has good adhesive performance during coextrusion and extrusion coating on aluminum foil. It is easy.
본 발명에서는 상술한 투명한 아이오노머수지를 표면수지층으로 사용함으로써, 아이오노머수지가 가지는 특징인 내마모성, 내오염성, 내스크래치성, 투명성과 같은 물성이 향상된 바닥타일을 제조할 수 있다.In the present invention, by using the above-described transparent ionomer resin as a surface resin layer, it is possible to produce a floor tile having improved physical properties such as wear resistance, stain resistance, scratch resistance, transparency, which is characteristic of the ionomer resin.
본 발명에서는 아이오노머수지로서 올레핀계 아이오노머수지를 사용하였으며, 바람직하기로는 금속이온과 염에 의해 부분적으로 중성화된 카르복시산그룹을 가진 올레핀과 α,β-불포화 카르복시산의 공중합체인 아이오노머수지로서, 예를 들면 듀폰(Dupont)사의 아연이온계(Zinc Ion Type) 또는 나트륨이온계(Sodium Ion Type) 아이오노머수지인 "Surlyn"(상품명), 엑손모빌(Exxon Mobil)사의 아연이온계 또는 나트륨이온계 아이오노머수지인 "Iotek"(상품명), 보다 바람직하기로는 아연이온계의 "Surlyn"이나 "Iotek"을 사용할 수 있다.In the present invention, an olefin-based ionomer resin is used as the ionomer resin, and is preferably an ionomer resin which is a copolymer of an olefin having a carboxylic acid group partially neutralized with a metal ion and a salt and an α, β-unsaturated carboxylic acid. For example, Dupont's Zinc Ion Type or Sodium Ion Ionomer resin "Surlyn" (trade name), Exxon Mobil's Zinc Ion or Sodium Ion Sub The ionomer resin "Iotek" (trade name), more preferably zinc ion-based "Surlyn" or "Iotek" can be used.
본 발명의 일 실시예에 따르면, 본 발명의 바닥타일은 상층으로부터 아이오노머수지층, 접착용수지층, 염화비닐수지 간지층, 기재층 및 이면층이 순차적으로 적층된 구조를 가진다.According to an embodiment of the present invention, the bottom tile of the present invention has a structure in which the ionomer resin layer, the adhesive resin layer, the vinyl chloride resin interlayer, the base layer and the back layer are sequentially stacked from the top layer.
본 발명의 다른 실시예에 따르면, 본 발명의 바닥타일은 치수안정성, 형태안정성 및 시공접착성의 향상을 고려하여 유리섬유층을 더 포함할 수 있다. 구체적으로 기재층 내부에 유리섬유층이 더 적층된 구조로서, 상층으로부터 아이오노머수지층, 접착용수지층, 염화비닐수지 간지층, 제1기재층, 유리섬유층, 제2기재층 및 이면층이 순차적으로 적층된 구조를 가진다.According to another embodiment of the present invention, the bottom tile of the present invention may further include a glass fiber layer in consideration of the improvement in dimensional stability, shape stability and construction adhesiveness. Specifically, the glass fiber layer is further laminated inside the base layer, and the ionomer resin layer, the adhesive resin layer, the vinyl chloride resin interlayer, the first base layer, the glass fiber layer, the second base layer and the back layer are sequentially formed from the top layer. It has a laminated structure.
이하 첨부도면에 의거하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
도 1a는 본 발명의 일 실시예에 따른 바닥타일의 단면도로서, 상층으로부터 아이오노머수지층(1), 접착용수지층(2) 및 염화비닐수지 간지층(3)으로 구성되는 표면층(4), 기재층(5) 및 이면층(6)이 순차적으로 적층되어 있다.1A is a cross-sectional view of a floor tile according to an embodiment of the present invention, which includes a surface layer 4 composed of an ionomer resin layer 1, an adhesive resin layer 2, and a vinyl chloride resin interlayer 3 from an upper layer; The base material layer 5 and the back layer 6 are laminated | stacked sequentially.
도 1b는 본 발명의 다른 실시예에 따른 바닥타일의 단면도로서, 상기 기재층(5a, 5b) 사이에 필요시 유리섬유층(7)을 삽입하여 치수의 보강이 가능하다.Figure 1b is a cross-sectional view of the floor tile according to another embodiment of the present invention, it is possible to reinforce the dimensions by inserting the glass fiber layer (7) between the base layer (5a, 5b) if necessary.
각층의 제조방법을 살펴보면, 염화비닐수지 간지층(3)은 중합도가 800~1,300인 염화비닐수지 100 중량부, 제품의 유연성 보강을 위한 가소제인 DOP 10~30 중량부, 내열안정제인 Ba-Zn계 화합물 3~5 중량부, 장기저온 내열 보강용 에폭시수지(두유(豆油)를 사용하므로 경화제는 필요없음) 2~7 중량부, 제품의 경도 및 분산성 확보를 위한 충진제인 탄산칼슘 20~50 중량부 및 인쇄선명성과 백색에 가깝게 하기 위한 안료인 산화티탄 3~6 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 카렌다로 압연하여 0.1~0.2 ㎜ 두께의 시트로 제조한 후, 그라비아 인쇄, 플렉소(Flexo) 인쇄 또는 전사인쇄 기법을 사용하여 원하는 패턴과 디자인으로 인쇄한다.Looking at the manufacturing method of each layer, the vinyl chloride resin interlayer (3) is 100 parts by weight of vinyl chloride resin having a polymerization degree of 800 ~ 1,300, DOP 10 ~ 30 parts by weight plasticizer for reinforcing the flexibility of the product, heat stabilizer Ba-Zn 3 to 5 parts by weight of the compound, 2 to 7 parts by weight of epoxy resin for long-term low temperature heat-resistant reinforcement (no curing agent is required because it uses soymilk), and calcium carbonate as a filler to secure the hardness and dispersibility of the product. 3 parts by weight to 6 parts by weight of titanium oxide, a pigment for bringing the printability and the whiteness close to white, into a half-barrier mixer and kneaded and heated and softened by calender to produce a sheet having a thickness of 0.1 to 0.2 mm, followed by gravure. Print with the desired patterns and designs using printing, flexo printing or transfer printing techniques.
기재층(5)은 중합도가 800~1,300인 염화비닐수지 100 중량부, 유연성 확보를 위한 가소제인 DOP 30~50 중량부, 내열안정제인 Ba-Zinc계 화합물 3~5 중량부, 장기저온 내열 보강용 에폭시수지(두유(豆油)를 사용하므로 경화제는 필요없음) 2~7 중량부, 제품의 경도 및 분산성 확보를 위한 충진제인 탄산칼슘 200~450 중량부 및 색상을 넣기 위한 흑색안료인 카본블랙을 2~8 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 130~175℃에서 카렌다로 압연하여 1.0~2.5 ㎜ 두께의 시트로 제조한다.The base layer 5 is 100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, DOP 30 to 50 parts by weight as a plasticizer for securing flexibility, 3 to 5 parts by weight of Ba-Zinc compound as a heat stabilizer, and long-term low temperature heat reinforcement. 2 ~ 7 parts by weight of epoxy resin (soymilk is used, no curing agent required), 200 ~ 450 parts by weight of calcium carbonate, a filler for securing hardness and dispersibility of the product, and carbon black, which is a black pigment to add color To 2 to 8 parts by weight in a half-barrier mixer, kneaded and heat-softened compound is rolled with a calendar at 130 ~ 175 ℃ to prepare a sheet of 1.0 to 2.5 mm thick.
이면층(6)은 중합도가 800~1,300인 염화비닐수지 100 중량부, 제품의 유연성 확보를 위한 가소제인 DOP 30~50 중량부, 내열안정제인 Ba-Zinc계 화합물 3~5 중량부, 장기저온 내열 보강용 에폭시수지(두유(豆油)를 사용하므로 경화제는 필요없음) 2~7 중량부, 제품의 경도 및 분산성 확보를 위한 충진제인 탄산칼슘 30~65 중량부 및 색상을 넣기 위한 안료인 카본블랙 3~5 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 130~170℃의 카렌다로 압연하여 0.15~0.7 ㎜ 두께의 시트로 제조한다.The backing layer 6 is 100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, 30 to 50 parts by weight of DOP, a plasticizer for securing flexibility of the product, 3 to 5 parts by weight of Ba-Zinc compound, which is a heat stabilizer, and long-term low temperature Epoxy resin for heat-resistant reinforcement (Soy milk is used, no curing agent required) 2-7 parts by weight, 30-65 parts by weight of calcium carbonate, a filler for securing hardness and dispersibility of the product, and carbon, a pigment for adding color 3 to 5 parts by weight of black is added to a half-barrier mixer, kneaded and heat-softened, and rolled with a calendar of 130 to 170 ° C. to prepare a sheet having a thickness of 0.15 to 0.7 mm.
유리섬유층(7)은 30~70 g/1㎡의 것이 적절하며 잠재경화성이 있는 우레탄계 처리제로 함침한 것을 사용한다.As for the glass fiber layer 7, the thing of 30-70 g / 1m <2> is suitable, and what impregnated with the latent urethane type treatment agent is used.
본 발명의 바닥타일은 상기에서 각각 제조한 아이오노머수지층(1), 접착용수지층(2), 인쇄된 염화비닐수지 간지층(3), 기재층(5, 5a, 5b), 이면층(6) 및 유리섬유층(7)을 권취한 후 각각 약 1 m ×1 m 크기로 재단하여 프레스가공을 위해 적층하고 3~5 kgf/㎠의 압력으로 130~170℃에서 약 20~40분간 예열한 후 상온까지 냉각하여 적층체를 얻고 재단하여 완성한다. 이때 다양한 엠보판의 사용으로 여러 엠보효과가 부여된 바닥타일을 얻을 수 있다.The bottom tile of the present invention is the ionomer resin layer (1), the adhesive resin layer (2), the printed vinyl chloride resin interlayer (3), the base layer (5, 5a, 5b), the back layer (manufactured above, respectively) 6) After winding the glass fiber layer (7) and cut to a size of about 1 m × 1 m respectively, laminated for press processing and preheated for 20 to 40 minutes at 130 ~ 170 ℃ at a pressure of 3 ~ 5 kgf / ㎠ After cooling to room temperature to obtain a laminate to cut and complete. At this time, it is possible to obtain a floor tile to which various embossing effects are applied by using various emboss plates.
도 2는 종래의 바닥타일의 단면도로서, 본 발명의 아이오노머수지층 및 접착용수지층 대신 염화비닐수지 투명시트층(8)과 자외선 경화형 표면처리층(9)이 적층되어 있다.2 is a cross-sectional view of a conventional floor tile, in which a vinyl chloride resin transparent sheet layer 8 and an ultraviolet curable surface treatment layer 9 are laminated instead of the ionomer resin layer and the adhesive resin layer of the present invention.
이하 실시예를 들어 본 발명을 구체적으로 설명한다. 그러나 하기 실시예에 의해 본 발명의 권리범위가 한정되지 않는다.The present invention will be described in detail with reference to the following Examples. However, the scope of the present invention is not limited by the following examples.
실시예 1: 도 1a의 바닥타일의 제조Example 1 Preparation of the Floor Tile of FIG. 1A
아이오노머수지로서 듀폰사의 올레핀계 아이오노머수지(상품명: Surlyn), 접착용수지로서 듀폰사의 EVA 변성수지(상품명: Bynel)를 사용하였으며, 공압출하여 300 ㎛ 두께의 투명한 아이오노머수지층(1) 및 30 ㎛ 두께의 접착용수지층(2)을 제조하였다.Dupont's olefinic ionomer resin (trade name: Surlyn) was used as the ionomer resin, and DuPont EVA modified resin (trade name: Bynel) was used as the adhesive resin, and it was coextruded to form a transparent ionomer resin layer having a thickness of 300 μm (1). And a 30 μm thick adhesive resin layer 2 was prepared.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 30 중량부, Ba-Zn계 화합물 4 중량부, 에폭시수지 4 중량부, 탄산칼슘 30 중량부 및 산화티탄 6 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.1 ㎜ 두께로 백색의 염화비닐수지 간지층(3)을 제조한 후, 상기 간지층 상에 그라비아 인쇄를 실시하였다.100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, 30 parts by weight of DOP, 4 parts by weight of Ba-Zn-based compound, 4 parts by weight of epoxy resin, 30 parts by weight of calcium carbonate and 6 parts by weight of titanium oxide were added to the Banbari mixer. The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a white vinyl chloride resin interlayer 3 having a thickness of 0.1 mm, and then gravure printing was performed on the interlayer.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 40 중량부, Ba-Zn계 화합물 3 중량부, 에폭시수지 4 중량부, 탄산칼슘 300 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 170℃의 카렌다로 압연하여 1.2 ㎜ 두께의 기재층(5)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800 to 1,300, 40 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 4 parts by weight of epoxy resin, 300 parts by weight of calcium carbonate and 5 parts by weight of carbon black to a Banbari mixer The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a base material layer 5 having a thickness of 1.2 mm.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 35 중량부, Ba-Zn계 화합물 3 중량부, 에폭시수지 4 중량부, 탄산칼슘 65 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.3 ㎜ 두께의 이면층(6)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800 to 1,300, 35 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 4 parts by weight of epoxy resin, 65 parts by weight of calcium carbonate and 5 parts by weight of carbon black to a Banbari mixer The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a back layer 6 having a thickness of 0.3 mm.
최종적으로, 상기에서 제조한 아이오노머수지층(1)과 접착용수지층(2)의 공압출물, 인쇄된 염화비닐수지 간지층(3), 기재층(5), 이면층(6)을 1 m ×1 m로 재단한 후 순서대로 적층하여 160℃에서 예열한 다음 5 kgf/㎠의 압력으로 30분간 예열한 후 상온까지 냉각하여 도 1a의 바닥타일을 제조하였다.Finally, the co-extruded product of the ionomer resin layer 1 and the adhesive resin layer 2 prepared above, the printed vinyl chloride resin interlayer 3, the base layer 5, and the back layer 6 were 1 m. After cutting to 1m and laminated in order, preheated at 160 ℃ and then preheated for 30 minutes at a pressure of 5 kgf / ㎠ and cooled to room temperature to prepare the bottom tile of Figure 1a.
실시예 2: 도 1b의 바닥타일의 제조Example 2 Preparation of the Bottom Tile of FIG. 1B
아이오노머수지로서 듀폰사의 올레핀계 아이오노머수지(상품명: Surlyn), 접착용수지로서 듀폰사의 EVA 변성수지(상품명: Bynel)를 사용하였으며, 공압출하여 300 ㎛ 두께의 투명한 아이오노머수지층(1) 및 30 ㎛ 두께의 접착용수지층(2)을 제조하였다.Dupont's olefinic ionomer resin (trade name: Surlyn) was used as the ionomer resin, and DuPont EVA modified resin (trade name: Bynel) was used as the adhesive resin, and it was coextruded to form a transparent ionomer resin layer having a thickness of 300 μm (1). And a 30 μm thick adhesive resin layer 2 was prepared.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 30 중량부, Ba-Zn계 화합물 4 중량부, 에폭시수지 4 중량부, 탄산칼슘 30 중량부 및 산화티탄 6 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.1 ㎜ 두께로 백색의 염화비닐수지 간지층(3)을 제조한 후, 상기 간지층 상에 그라비아 인쇄를 실시하였다.100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, 30 parts by weight of DOP, 4 parts by weight of Ba-Zn-based compound, 4 parts by weight of epoxy resin, 30 parts by weight of calcium carbonate and 6 parts by weight of titanium oxide were added to the Banbari mixer. The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a white vinyl chloride resin interlayer 3 having a thickness of 0.1 mm, and then gravure printing was performed on the interlayer.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 40 중량부, Ba-Zn계 화합물 3 중량부, 에폭시수지 4 중량부, 탄산칼슘 300 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 170℃의 카렌다로 압연하여 1.2 ㎜ 두께의 기재층(5a), (5b)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800 to 1,300, 40 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 4 parts by weight of epoxy resin, 300 parts by weight of calcium carbonate and 5 parts by weight of carbon black to a Banbari mixer The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare substrate layers 5a and 5b having a thickness of 1.2 mm.
치수보강을 위하여 유리섬유시트에 잠재경화성이 있는 우레탄을 함침시켜 우레탄 함침 유리섬유층(7)을 제조하였다.The urethane-impregnated glass fiber layer 7 was prepared by impregnating a urethane with a latent curability into the glass fiber sheet for dimensional reinforcement.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 35 중량부, Ba-Zn계 화합물 3 중량부, 에폭시수지 4 중량부, 탄산칼슘 65 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.3 ㎜ 두께의 이면층(6)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800 to 1,300, 35 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 4 parts by weight of epoxy resin, 65 parts by weight of calcium carbonate and 5 parts by weight of carbon black to a Banbari mixer The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a back layer 6 having a thickness of 0.3 mm.
최종적으로, 상기에서 제조한 아이오노머수지층(1)과 접착용수지층(2)의 공압출물, 인쇄된 염화비닐수지 간지층(3), 기재층(5a, 5b), 함침 유리섬유층(7), 이면층(6)을 1 m ×1 m로 재단한 후 순서대로 적층하여 160℃에서 예열한 다음 5 kgf/㎠의 압력으로 30분간 예열한 후 상온까지 냉각하여 도 1b의 바닥타일을 제조하였다.Finally, the coextruded product of the ionomer resin layer 1 and the adhesive resin layer 2 prepared above, the printed vinyl chloride resin interlayer 3, the base layer 5a, 5b, the impregnated glass fiber layer 7 After cutting the back layer 6 to 1 m × 1 m, they were laminated in order, preheated at 160 ° C., preheated at a pressure of 5 kgf / cm 2 for 30 minutes, and cooled to room temperature, thereby manufacturing the bottom tile of FIG. 1b. .
비교예 1: 도 2의 바닥타일의 제조Comparative Example 1: Preparation of the bottom tile of Figure 2
염화비닐수지 투명시트층(8)은 중합도가 800~1,300인 염화비닐수지 100 중량부, 제품의 유연성 보강을 위한 가소제인 DOP 30 중량부, 내열안정제인 Ba-Zn계 화합물 5 중량부, 장기저온 내열보강을 위한 에폭시수지(두유(豆油)를 사용하므로 경화제가 필요없음) 5 중량부, 가공성을 향상시키기 위한 가공조제인 메틸메타크릴레이트 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 160℃의 카렌다로 압연하여 0.3 ㎜ 두께의 투명시트층을 제조하였다.The vinyl chloride resin transparent sheet layer 8 is 100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, 30 parts by weight of DOP as a plasticizer for reinforcing flexibility of the product, 5 parts by weight of Ba-Zn compound as a heat stabilizer, and long-term low temperature. 5 parts by weight of epoxy resin for heat-resistant reinforcement (no need for curing agent because it uses soymilk) and 5 parts by weight of methyl methacrylate, a processing aid to improve processability, in a half-barrier mixer The sheet was rolled with a calendar at 160 ° C. to prepare a 0.3 mm thick transparent sheet layer.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 30 중량부, Ba-Zn계 화합물 4 중량부, 에폭시수지 4 중량부, 탄산칼슘 30 중량부 및 산화티탄 6 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.1 ㎜ 두께로 백색의 염화비닐수지 간지층(3)을 제조한 후, 상기 간지층 상에 그라비아 인쇄를 실시하였다.100 parts by weight of vinyl chloride resin having a polymerization degree of 800 to 1,300, 30 parts by weight of DOP, 4 parts by weight of Ba-Zn-based compound, 4 parts by weight of epoxy resin, 30 parts by weight of calcium carbonate and 6 parts by weight of titanium oxide were added to the Banbari mixer. The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a white vinyl chloride resin interlayer 3 having a thickness of 0.1 mm, and then gravure printing was performed on the interlayer.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 40 중량부, Ba-Zn계 화합물 3 중량부, 탄산칼슘 300 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열 연화시킨 컴파운드를 170℃의 카렌다로 압연하여 1.2 ㎜ 두께의 기재층(5)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800-1,300, 40 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 300 parts by weight of calcium carbonate and 5 parts by weight of carbon black in a half-barrier, kneaded and heat-softened Was rolled with a calendar at 170 ° C. to prepare a substrate layer 5 having a thickness of 1.2 mm.
중합도가 800~1,300인 염화비닐수지 100 중량부, DOP 35 중량부, Ba-Zn계 화합물 3 중량부, 에폭시수지 4 중량부, 탄산칼슘 65 중량부 및 카본블랙 5 중량부를 반바리 믹서에 투입하여 혼련하고 가열연화시킨 컴파운드를 170℃의 카렌다로 압연하여 0.3 ㎜ 두께의 이면층(6)을 제조하였다.100 parts by weight of vinyl chloride resin having a degree of polymerization of 800 to 1,300, 35 parts by weight of DOP, 3 parts by weight of Ba-Zn compound, 4 parts by weight of epoxy resin, 65 parts by weight of calcium carbonate and 5 parts by weight of carbon black to a Banbari mixer The kneaded and heat-softened compound was rolled with a calendar at 170 ° C. to prepare a back layer 6 having a thickness of 0.3 mm.
최종적으로, 상기에서 제조한 염화비닐수지 투명시트층(8), 인쇄된 염화비닐수지 간지층(3), 기재층(5), 이면층(6)을 1 m ×1 m로 재단한 후 순서대로 적층하여 160℃에서 예열한 다음 5 kgf/㎠의 압력으로 30분간 예열한 후 상온까지 냉각한 다음, 상기 적층물을 자외선 경화형 도료를 사용하여 25 ㎛의 두께로 표면처리하여 도 2의 바닥타일을 제조하였다.Finally, the vinyl chloride resin transparent sheet layer 8, the printed vinyl chloride resin interlayer 3, the substrate layer 5, and the back layer 6 prepared above were cut to 1 m × 1 m, and then, in sequence. After preheating at 160 ° C. and preheating for 30 minutes at a pressure of 5 kgf / cm 2, cooling to room temperature, the laminate was surface-treated to a thickness of 25 μm using an ultraviolet curable paint, and the bottom tile of FIG. 2. Was prepared.
표면처리층(9)의 조성물은 우레탄아크릴레이트 올리고머 40~70 중량부, 올리고머의 희석, 점도조절, 부착증대를 위한 아크릴계 모노머 20~50 중량부, 광개시제인 벤조페논 1~5 중량부, 실리콘타입 소포제 0.5~2 중량부, 메팅제인 훈연된 실리카(Fumed Silica) 0.5~7 중량부를 혼합한 것이다.The composition of the surface treatment layer 9 is 40 to 70 parts by weight of urethane acrylate oligomer, 20 to 50 parts by weight of acrylic monomer for dilution, viscosity control, and adhesion increase of oligomer, 1 to 5 parts by weight of benzophenone as a photoinitiator, silicone type 0.5 to 2 parts by weight of the defoaming agent, 0.5 to 7 parts by weight of the fumed silica (Fumed Silica) is a mixing agent.
표면처리층(9)은 염화비닐수지 투명시트층(8) 상부에 10~30 ㎛ 두께로 에어나이프코팅이나 메쉬롤 또는 러버롤을 사용하여 코팅한 후 출력이 200~300 watt/in인 중압수은램프 4~10개를 사용하여 5~25 m/min의 라인스피드로 경화시켰다.The surface treatment layer 9 is coated with air knife coating, mesh roll, or rubber roll with a thickness of 10 to 30 μm on the transparent sheet layer of vinyl chloride resin transparent sheet 8, and the medium pressure mercury having an output of 200 to 300 watt / in. 4-10 lamps were used to cure to a line speed of 5-25 m / min.
시험예Test Example
상기 실시예 1 및 비교예 1의 샘플에 대하여 아래와 같은 시험을 수행하였으며, 그 결과는 표 1과 같다.The following tests were performed on the samples of Example 1 and Comparative Example 1, and the results are shown in Table 1.
1. 내마모성1. Wear resistance
KS M 3802에 준하여 H-22 마모휠을 사용하여 테이버 마모시험기에 1,000회 회전시키고 마모감량(g)을 측정하였다.In accordance with KS M 3802, using a H-22 wear wheel was rotated 1,000 times in a taper wear tester and the wear loss (g) was measured.
2. 내오염성2. Pollution resistance
구두약, 볼펜, 검정유성 매직을 사용하여 오염시킨 후 30분 경과시 에탄올을 사용하여 오염원을 제거하였다.Contaminants were removed using shoe polish, ballpoint pen, and black oil magic, and 30 minutes later, ethanol was used to remove the contaminants.
3. 스크래치성3. Scratchability
KS M 3802에 준하여 긁기시험을 실시하여 폭 1.4 ㎜ 두께로 표면손상시의 하중(g)을 측정하였다.A scratch test was carried out in accordance with KS M 3802 to measure the load (g) at the time of surface damage with a thickness of 1.4 mm.
4. 박리강도4. Peel strength
샘플을 2×15 ㎠으로 재단한 후 샘플을 취하여 각 샘플의 긴 변의 한 끝에서 5 cm를 박리시켜 박리한 부분을 인장시험기 그립부에 끼우고 200 ㎜/min의 속도로 인장하여 그때의 강도를 측정하였다. 이때 강도가 5 kgf 이상이면 합격, 미만이면 불합격으로 표시하였다.After cutting the sample to 2 × 15 cm 2, the sample was taken, peeled 5 cm from one end of the long side of each sample, and the peeled part was inserted into the tension tester grip part and tensioned at a speed of 200 mm / min to measure the strength at that time. It was. At this time, when the strength was 5 kgf or more, the result was passed.
표 1에서 보는 바와 같이, 아이오노머수지를 사용한 본 발명의 합성수지계 바닥타일은 내마모성, 내오염성, 스크래치성, 박리강도 등에서 우수한 물성을 나타내었고 외관도 염화비닐수지 투명시트를 사용한 종래의 바닥타일에 비하여 우수하였다.As shown in Table 1, the synthetic resin floor tile of the present invention using the ionomer resin showed excellent physical properties in abrasion resistance, stain resistance, scratch resistance, peeling strength, etc. It was excellent compared to.
이상한 설명한 바와 같이, 본 발명의 바닥타일은 표면수지층으로서 올레핀계 아이오노머수지를 사용함으로써 내마모성, 내약품성, 내오염성 및 의장성이 우수하며, 또한 유리섬유층을 더 적층할 경우 양호한 치수안정성, 형태안정성 및 시공접착성을 얻을 수 있다.As described strangely, the floor tile of the present invention is excellent in wear resistance, chemical resistance, stain resistance and designability by using an olefin ionomer resin as the surface resin layer, and good dimensional stability and shape when further laminating the glass fiber layer. Stability and construction adhesiveness can be obtained.
도 1a는 본 발명의 일 실시예에 따른 바닥타일의 단면도,1A is a cross-sectional view of a floor tile according to an embodiment of the present invention;
도 1b는 본 발명의 다른 실시예에 따른 바닥타일의 단면도,1B is a cross-sectional view of a floor tile according to another embodiment of the present invention;
도 2는 종래의 바닥타일 단면도.Figure 2 is a cross-sectional view of a conventional bottom tile.
※ 도면의 주요 부분에 대한 부호의 설명※ Explanation of codes for main parts of drawing
1: 아이오노머수지층 2: 접착용수지층1: ionomer resin layer 2: adhesive resin layer
3: 염화비닐수지 간지층 4: 표면층3: vinyl chloride resin interlayer 4: surface layer
5, 5a, 5b: 기재층 6: 이면층5, 5a, 5b: base material layer 6: back layer
7: 유리섬유층 8: 염화비닐수지 투명시트층7: glass fiber layer 8: vinyl chloride resin transparent sheet layer
9: 자외선 경화형 표면처리층9: UV curable surface treatment layer
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0063080A KR100524854B1 (en) | 2002-10-16 | 2002-10-16 | Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0063080A KR100524854B1 (en) | 2002-10-16 | 2002-10-16 | Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20040033815A KR20040033815A (en) | 2004-04-28 |
KR100524854B1 true KR100524854B1 (en) | 2005-10-28 |
Family
ID=37333212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR10-2002-0063080A KR100524854B1 (en) | 2002-10-16 | 2002-10-16 | Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100524854B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100851365B1 (en) | 2007-08-09 | 2008-08-08 | (주) 화인테크놀리지 | Glass tile for bottom and method for preparation of the same |
WO2017099294A1 (en) * | 2015-12-09 | 2017-06-15 | 주식회사 녹수 | Floor tile including fabric material and manufacturing method therefor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08254004A (en) * | 1995-03-15 | 1996-10-01 | Dainippon Printing Co Ltd | Floor material |
JP2000226933A (en) * | 1999-02-08 | 2000-08-15 | Suminoe Textile Co Ltd | Floor material and manufacturing method thereof |
KR20010015875A (en) * | 1998-10-16 | 2001-02-26 | 사가라 아스히코 | Interior resin article |
-
2002
- 2002-10-16 KR KR10-2002-0063080A patent/KR100524854B1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08254004A (en) * | 1995-03-15 | 1996-10-01 | Dainippon Printing Co Ltd | Floor material |
KR20010015875A (en) * | 1998-10-16 | 2001-02-26 | 사가라 아스히코 | Interior resin article |
JP2000226933A (en) * | 1999-02-08 | 2000-08-15 | Suminoe Textile Co Ltd | Floor material and manufacturing method thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100851365B1 (en) | 2007-08-09 | 2008-08-08 | (주) 화인테크놀리지 | Glass tile for bottom and method for preparation of the same |
WO2017099294A1 (en) * | 2015-12-09 | 2017-06-15 | 주식회사 녹수 | Floor tile including fabric material and manufacturing method therefor |
US11536036B2 (en) | 2015-12-09 | 2022-12-27 | Nox Corporation | Floor tile including fabric material and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
KR20040033815A (en) | 2004-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2402159B1 (en) | Decorative material | |
CN104968499B (en) | graphic article | |
KR100876787B1 (en) | Decorative sheet for floor material and decorative material for floor using the same | |
KR102299068B1 (en) | Films with enhanced scuff resistance, clarity, and conformability | |
JP5545331B2 (en) | Building material decorative sheet | |
JP6065709B2 (en) | Cosmetic sheet and cosmetic material | |
JP2630159B2 (en) | Method for producing embossed decorative sheet | |
KR101930708B1 (en) | Transparent film for floor material, method for preparing the same and floor material comprising the same | |
JP5870799B2 (en) | Decorative sheet | |
KR100524854B1 (en) | Laminate synthetic resin tile having enhanced abrasion resistance, pollution resistance and decorative property | |
JP2833484B2 (en) | Decorative sheet | |
WO2012173313A1 (en) | Decorative glass using korean paper and method for fabricating same | |
JPH08230113A (en) | Decorative sheet and manufacture thereof | |
JP2001129937A (en) | Decorative sheet for building material | |
JP4992564B2 (en) | Decorative sheet | |
JPH05229066A (en) | Decorative sheet | |
JP2000301680A (en) | Decorative sheet and decorative material using the same | |
JP4723704B2 (en) | Building material decorative sheet | |
JP3139439B2 (en) | Decorative sheet | |
WO1999006485A1 (en) | Acrylic resin film and laminated film containing the same | |
JP3089957B2 (en) | Decorative sheet and method for producing the same | |
JPH1024538A (en) | Decorative sheet | |
JP3903555B2 (en) | Embossed decorative sheet and manufacturing method thereof | |
JP3345681B2 (en) | Decorative sheet | |
WO2014192722A1 (en) | Film for decorative molding, and method for manufacture of decorative molded article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20120927 Year of fee payment: 8 |
|
FPAY | Annual fee payment |
Payment date: 20130930 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20140924 Year of fee payment: 10 |
|
FPAY | Annual fee payment |
Payment date: 20150923 Year of fee payment: 11 |
|
FPAY | Annual fee payment |
Payment date: 20170828 Year of fee payment: 13 |