Classifications

• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

• the present invention relates to a pressure-sensitive adhesive composition, and more particularly to an acrylic pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape formed by applying the pressure-sensitive adhesive composition to a substrate.
• An acrylic pressure-sensitive adhesive containing a (meth) acrylate monomer is excellent in weather resistance, transparency, heat resistance, solvent resistance, and the like, and easily changes the adhesive force by changing the composition of the constituent monomers.
• Patent Documents 1 to 3 show that it has the advantage of being controllable.
• adhesability As a typical practical characteristic required as an adhesive tape, there are generally three basic characteristics of adhesive strength (peeling strength), tack (adhesiveness), and holding power (cohesive strength). Depending on the application, in addition to the basic characteristics, a characteristic called fixability may be required. As an example of such fixability, for example, loosening or warping of a sticking material that occurs when sticking a sticking material (for example, paper such as a poster) to a predetermined surface to be pasted (for example, a wall surface).
• fixity is not a characteristic of the adhesive itself, but can withstand predetermined external forces such as stress, gravity, and repulsive force as described above (even if a predetermined external force is applied) That can maintain the same state).
• the basic properties required for the pressure-sensitive adhesive tape as described above are at a practical level, but the fixing property which is one of the properties described above.
• the acrylic adhesive composition that has been proposed so far is capable of obtaining an adhesive tape with excellent fixability. There was a problem that it was not possible.
• the present invention has been made in view of the above problems, and an object thereof is to provide an acrylic pressure-sensitive adhesive composition capable of obtaining a pressure-sensitive adhesive tape excellent in fixability.
• the present inventors have used an acrylic ABA type triblock copolymer as a base polymer, and at least a part of this triblock copolymer has a segment B.
• an adhesive composition containing 2-ethylhexyl acrylate as a constituent monomer and containing a polymer blend in which a predetermined tackifying resin is contained in the base polymer excellent fixability is obtained. It has been found that an adhesive tape can be obtained, and the present invention has been completed based on this finding.
• the present invention provides an ABA type triblock copolymer (a) comprising a segment A mainly composed of methacrylic acid ester and a segment B mainly composed of acrylate ester,
• a tackifying resin (c) having a softening point of 110 ° C.
• the triblock polymer (a) preferably has a weight average molecular weight of 60,000 or more and 400,000 or less.
• the amount of the tackifier resin (c) is 15 when the total of the triblock copolymer (a) and the triblock copolymer (b) is 100 parts by mass. It is preferable that it is not less than 40 parts by mass.
• the constituent monomers of the segment B of the triblock copolymer (b) are n-butyl acrylate and 2-ethylhexyl acrylate.
• the pressure-sensitive adhesive composition may further contain a softener (d) having compatibility with the triblock copolymer (a) and the triblock copolymer (b).
• the softener (d) is a group consisting of an AB type diblock copolymer having the same segment as the segment A and segment B of the triblock copolymer (a), an acrylic oligomer, and a liquid rubber.
• the tackifier resin (c) is preferably a rosin resin.
• this invention is an adhesive tape formed by apply
• an acrylic triblock copolymer having a predetermined structure is used as a base polymer, and a pressure-sensitive adhesive composition containing a polymer blend in which a predetermined tackifying resin is contained in the base polymer is used.
• a pressure-sensitive adhesive composition containing a polymer blend in which a predetermined tackifying resin is contained in the base polymer is used.
• the pressure-sensitive adhesive composition according to the present invention will be described in the following order.
• 1 Composition of pressure-sensitive adhesive composition 1-1 Triblock copolymer (a) 1-2 Triblock copolymer (b) 1-3 Tackifying resin (c) 1-4 Optional component 2
• Form of pressure-sensitive adhesive composition 3 Use of pressure-sensitive adhesive composition
• the pressure-sensitive adhesive composition according to the present invention contains two types of ABA-type triblock copolymers (a) and (b) as a base polymer, and further contains at least a tackifier resin (c). Yes, in addition to the properties such as adhesive strength, tack, and holding power, the above-described fixing property is excellent.
• a ABA-type triblock copolymers ABA-type triblock copolymers
• c tackifier resin
• the triblock copolymer (a) is an ABA type triblock copolymer composed of a segment A mainly composed of methacrylic acid ester and a segment B mainly composed of acrylate ester.
• the “segment” in the present invention means a structural unit constituting each block in the triblock copolymer.
• a structural unit (polymer or oligomer) A composed of monomer a and monomer b
• a structural unit (polymer or oligomer) B consisting of the monomer B
• a structural unit (polymer or oligomer) A consisting of the monomer a
• the structural units A and B are segments.
• a and B (the same applies to the triblock copolymer (b) described later).
• the segment A of the triblock copolymer (a) is not particularly limited as long as it has a methacrylic acid ester as a main component monomer.
• a methacrylic acid ester include methyl methacrylate, Ethyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 1-methylcyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, 3-methacrylic acid 3- Methylcyclohexyl, 4-methylcyclohexyl methacrylate, 2-phenoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2- (N, N-dimethylamino) ethyl methacrylate, trimethacrylate Fluoromethyl,
• the main constituent monomers of segment A include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, It is preferable to use a monomer such as an ester of methacrylic acid and an alcohol having 3 or less carbon atoms, such as isopropyl methacrylate.
• the content is 90% or more.
• monomers that can be used in addition to the above-mentioned methacrylic acid ester include, for example, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N Methacrylamides such as isopropyl methacrylamide, N, N-dimethyl methacrylamide, N, N-diethyl methacrylamide, acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N, N-dimethyl acrylamide , Acrylamides such as N, N-diethylacrylamide, vinyl monomers having a carboxyl group such as methacrylic acid, acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, styrene, ⁇ -methyl Styrene, p- methyl and aromatic vinyl monomers such as styrene
• the segment B of the triblock copolymer (a) is not particularly limited as long as it has an acrylate ester as a main constituent monomer.
• an acrylate ester include an acrylic ester.
• examples of monomers that can be used in addition to the above-mentioned acrylic ester include, for example, alkyl methacrylate (for example, methyl methacrylate, ethyl methacrylate, methacrylic ester).
• methacrylamide methacrylamide, N-methylmethacrylamide, Methacrylamides such as N-ethylmethacrylamide, N-isopropylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, acrylamide, N-methylacrylamido Acrylamides such as N-ethylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, methacrylic acid, acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, etc.
• Vinyl monomers having a carboxyl group aromatic vinyl monomers such as styrene, o-methylstyrene and p-methylstyrene, conjugated diene monomers such as butadiene and isoprene, olefins such as ethylene and propylene, and ⁇ - Examples include lactones such as caprolactone and valerolactone.
• the pressure-sensitive adhesive composition according to the present invention has excellent fixability, but this fixability is affected by the weight average molecular weight of the triblock copolymer (a).
• the weight average molecular weight of the triblock copolymer (a) is preferably 60,000 or more and 400,000 or less.
• the weight average molecular weight of the triblock copolymer (a) is less than 60,000, it is preferable because not only general properties such as adhesive strength, cohesive strength, and tack of the pressure-sensitive adhesive composition are lowered, but also fixing properties are lowered. Absent.
• the weight average molecular weight of the triblock copolymer (a) is more preferably 110,000 or more, further preferably 130,000 or more, and 150,000. The above is particularly preferable.
• the weight average molecular weight of the triblock copolymer (a) is preferably set to 400,000 or less. In order to further enhance the above effect, the triblock copolymer (a) preferably has a weight average molecular weight of 300,000 or less.
• required from the polystyrene conversion molecular weight measured by gel permeation chromatography (GPC) is used.
• the content of the hard segment in the triblock copolymer (a) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass based on the total mass of the triblock copolymer (a). 10 to 20% by mass is particularly preferred.
• the triblock copolymer (a) may be synthesized by polymerizing raw material monomers, or a commercially available one may be used.
• the polymerization method is not particularly limited, and for example, an anionic polymerization method, an atom transfer radical polymerization method (ATRP) or the like can be used.
• ATRP atom transfer radical polymerization method
• an anionic polymerization method for example, an organic alkali metal compound is used as a polymerization initiator in the presence of a mineral salt such as an alkali metal or alkaline earth metal salt.
• Known methods such as a polymerization method, a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound, and a method of anionic polymerization using an organic rare earth metal complex as a polymerization initiator can be used.
• a known method such as a polymerization method using an organic halide or a sulfonyl halide compound as an initiator in the presence of a transition metal compound or a nitrogen-containing compound can be used.
• Examples of commercially available products include “Clarity (registered trademark) series” manufactured by Kuraray Co., Ltd.
• the triblock copolymer (b) is an ABA type triblock composed of a segment A mainly composed of a methacrylic acid ester and a segment B mainly composed of an acrylate ester. It is a copolymer.
• the triblock copolymer (b) has a structure different from that of the triblock copolymer (a) in that it has 2-ethylhexyl acrylate as a constituent monomer of the segment B.
• the pressure-sensitive adhesive composition according to the present invention has, as a constituent monomer of the segment B of the ABA type triblock, a Tg further than that of n-butyl acrylate.
• the triblock copolymer (b) As an effect obtained by blending the triblock copolymer (b), the original (such as paper such as cardboard), which occurs when the patch (such as cardboard) is fixed in a predetermined shape such as a cylindrical shape, The characteristics (resilience fixability) that can withstand the repulsive force to return to the shape (the adhesives do not peel apart) can be remarkably improved.
• the triblock copolymer (b) will be described in detail.
• segment A Since the segment A of the triblock copolymer (b) is the same as the segment A of the triblock copolymer (a) described above, detailed description thereof is omitted here.
• the segment A of the triblock copolymer (a) and the segment A of the triblock copolymer (b) may be the same or different. However, considering the compatibility of the triblock copolymer (a) and the triblock copolymer (b), it is preferable that the two segments A are the same.
• the segment B of the triblock copolymer (b) must have 2-ethylhexyl acrylate as a constituent monomer and may have “another constituent monomer”.
• the “other constituent monomer” those usable as the constituent monomer of the segment B of the triblock copolymer (a) can be used.
• n-butyl acrylate as “another constituent monomer”. That is, it is preferable that the constituent monomer of the segment B of the triblock copolymer (b) is n-butyl acrylate and 2-ethylhexyl acrylate.
• acrylate-n-butyl may be used as a constituent monomer of segment B.
• another constituent monomer” in the segment B of the triblock copolymer (b) and a constituent monomer of the segment B in the triblock copolymer (a) are: Although it may be the same or different, in consideration of the compatibility of the triblock copolymer (a) and the triblock copolymer (b), it is preferable that the constituent monomers of both are the same.
• the weight average molecular weight of the triblock copolymer (b) in the pressure-sensitive adhesive composition according to the present invention is practically preferably 30,000 to 200,000, more preferably 150,000, from the viewpoint of stable production. It is as follows. When the weight average molecular weight is less than 30,000, the adhesive strength is too low and there is a problem in practical use. When the weight average molecular weight exceeds 200,000, the viscosity is too high and there is a problem in manufacturing.
• required from the polystyrene conversion molecular weight measured by gel permeation chromatography (GPC) is used.
• the content of the hard segment in the triblock copolymer (b) is preferably 10 to 40% by mass, more preferably 15 to 30% by mass based on the total mass of the triblock copolymer (b). 20 to 25% by mass is particularly suitable.
• the triblock copolymer (b) may be synthesized by polymerizing raw material monomers, or a commercially available one may be used. Although it does not restrict
• the mixing ratio of the triblock copolymer (a) and the triblock copolymer (b) (triblock copolymer (triblock copolymer ( The blending ratio of the triblock copolymer (b) to the total amount of a) and the triblock copolymer (b) must be 0.1% by mass or more. Thereby, the improvement effect of the fixability of an adhesive composition increases notably.
• the blending ratio of the triblock copolymer (b) is too high, the performance as a base polymer is reduced, so that not only general properties such as adhesive strength, tack, and holding power are reduced, The fixability of the pressure-sensitive adhesive composition also decreases. Therefore, it is preferable to increase the blending ratio of the triblock copolymer (a). Specifically, the blending ratio of the triblock copolymer (b) needs to be 50% by mass or less.
• the lower limit of the blending amount of the triblock copolymer (b) is preferably 1% by mass or more and more preferably 3% by mass or more in order to further enhance the effect of improving the fixability.
• the upper limit of the amount of the triblock copolymer (b) is preferably set to 40% by mass or less in order to further enhance the effect of improving the fixability and suppress the decrease in general characteristics. It is more preferable to set it as 30 mass% or less, and it is especially preferable to set it as 20 mass% or less.
• the pressure-sensitive adhesive composition according to the present invention further contains a tackifying resin (c) as an essential component in addition to the above-described base polymer.
• a tackifying resin (c) as an essential component in addition to the above-described base polymer.
• the pressure-sensitive adhesive composition according to the present invention increases the adhesive strength to a practically sufficient level by containing the tackifier resin (c), and is generally used as a pressure-sensitive adhesive such as adhesive strength, tack, and holding power. It meets the characteristics.
• the tackifying resin (c) is formed so that the triblock copolymer (a) and the triblock copolymer (b) can form a polymer blend with the triblock copolymer (a) and the triblock copolymer (a).
• This resin is compatible with the coalescence (b).
• the resin having such compatibility is not particularly limited, and for example, rosin type, terpene type and the like can be used.
• the rosin resin include rosin ester, hydrogenated rosin ester, disproportionated rosin ester, polymerized rosin ester, gum rosin, tall oil rosin, maleated rosin, maleic acid modified rosin, etc.
• terpene phenol resins examples thereof include terpene phenol resins, hydrogenated terpene phenol resins, aromatic modified terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene resins, ⁇ -pinene, ⁇ -pinene, limonene and the like.
• a rosin resin as the tackifier resin according to the present invention.
• the tackifier resin (c) As the tackifier resin (c) according to the present invention, at least one resin having a softening point of 100 ° C. or higher is used. By blending such a tackifying resin (c) having a high softening point, the fixability can be remarkably improved in addition to the properties generally required as an adhesive such as adhesive strength, tack, and holding power. In particular, when a sticking material (for example, paper such as a poster) is applied to a predetermined surface to be applied (for example, a wall surface) by blending a tackifying resin (c) having a high softening point (100 ° C. or higher).
• a sticking material for example, paper such as a poster
• a predetermined surface to be applied for example, a wall surface
• the softening point of the tackifier resin (c) is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher.
• the softening point of the tackifying resin (c) is preferably 200 ° C. or less, more preferably 170 ° C. or less, further preferably 165 ° C. or less, and most preferably 160 ° C. or less. preferable.
• the tackifying resin having a suitable softening point is preferably a main component (50% by mass or more based on the total mass of all tackifying resins).
• the amount of the tackifier resin (c) is 15 parts by mass or more and 40 parts by mass or less when the total of the triblock copolymer (a) and the triblock copolymer (b) is 100 parts by mass. It is preferable. When the compounding amount of the tackifying resin (c) is less than 15 parts by mass, the effect of adding it (adhesive force or improvement effect of fixability) may be insufficient. From the viewpoint of remarkably improving the adhesive strength and fixability of the pressure-sensitive adhesive composition, it is more preferable that the amount of the tackifier resin (c) is 25 parts by mass or more. On the other hand, if the amount of the tackifier resin (c) exceeds 40 parts by mass, the tack may be reduced.
• the pressure-sensitive adhesive composition according to the present invention may further contain a softener (d) as an optional component in addition to the above-described base polymer.
• a softener (d) Only the above-mentioned triblock copolymer (a) and triblock copolymer (b) can have a function as the pressure-sensitive adhesive composition according to the present invention, but the adhesive force is low and practically insufficient. There is a case. Accordingly, the pressure-sensitive adhesive composition according to the present invention contains the softener (d), thereby increasing the adhesive strength to a practically sufficient level, and general properties as a pressure-sensitive adhesive such as adhesive strength, tack, and holding power. To meet.
• the softening agent (d) is a triblock copolymer (a) and a triblock copolymer so that a polymer blend can be formed with the triblock copolymer (a) and the triblock copolymer (b).
• This resin is compatible with (b).
• the compound having such compatibility is not particularly limited.
• an AB type diblock copolymer having segments similar to the segment A and the segment B of the triblock copolymer (a).
• Acrylic polymer acrylic oligomer, liquid rubber (for example, polybutene, polyisobutylene, polyisoprene), process oil, phthalic acid esters, adipic acid esters, sebacic acid esters, aliphatic esters, polyethers, etc. It is done.
• These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
• the diblock copolymer since the compatibility with the triblock copolymer (a) and the triblock copolymer (b) is good, the diblock copolymer is used alone, or the diblock copolymer and the acrylic oligomer are used. It is particularly preferable to use in combination.
• the diblock copolymer is not particularly limited as long as it has the same segment as the segment A and segment B of the triblock copolymer (a) described above.
• the segments A and B of the diblock copolymer are respectively separated from the triblock copolymer. It is preferable to consist of the same constituent monomer as the segments A and B of the polymer (a). In this case, the constituent monomer of the segment A of the triblock copolymer (b) is the same as the segment A of the diblock copolymer and the triblock copolymer, and the segment B of the triblock copolymer (b).
• the above “other constituent monomer” is the same as the segment B of the diblock copolymer and the triblock copolymer because the compatibility becomes the highest.
• the acrylic oligomer and liquid rubber are preferable because the compatibility with the triblock copolymer (a) and the triblock copolymer (b) is increased.
• a softener (d) may be blended.
• the blending amount of the softening agent (d) is preferably 250 parts by mass or less when the total of the triblock copolymer (a) and the triblock copolymer (b) is 100 parts by mass.
• the amount of the softening agent (d) exceeds 250 parts by mass, the holding power of the pressure-sensitive adhesive composition may be lowered. Therefore, in order to improve the fixability, the amount is more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less.
• a lower limit is not specifically limited, For example, it is 50 mass parts.
• the pressure-sensitive adhesive composition according to the present invention includes a filler, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, and foaming as long as the effects of the present invention are not impaired.
• the pressure-sensitive adhesive composition includes the above-described triblock copolymer (a), triblock copolymer (b), and tackifier resin ( c), a solution-type pressure-sensitive adhesive composition in which the softener (d) and an optional component (pressure-sensitive adhesive material) are dissolved in a predetermined solvent, or a hot melt obtained by melting and kneading the pressure-sensitive adhesive material. It can also be set as a pressure-sensitive adhesive composition.
• organic solvents such as toluene and ethyl acetate, can be used, for example.
• the pressure-sensitive adhesive composition according to the present invention as described above can be used for applications such as pressure-sensitive adhesive tapes (one side or both sides).
• coating the adhesive composition mentioned above to both surfaces of a base material as an example of the use of the adhesive composition which concerns on this invention is demonstrated.
• the adhesive is applied to one side of the substrate.
• the above-mentioned pressure-sensitive adhesive composition is applied to both surfaces of a substrate, and the surface of the pressure-sensitive adhesive composition is a release paper as necessary. Is attached.
• the substrate is not particularly limited as long as it is in the form of a film or sheet to which the adhesive composition can be applied, for example, paper such as kraft paper, Japanese paper, crepe paper, rayon, cotton, acetate, Nonwoven fabric made of polyethylene (PE), polypropylene (PP), etc., cellophane, vinyl chloride, PE, expanded polypropylene (OPP), polyethylene terephthalate (PET), tetrafluoroethylene, polyimide, polycarbonate (PC), polystyrene (PS) Resin films such as polyurethane, PE, butyl rubber, metal foils such as aluminum and copper, rubber sheets such as natural rubber, SBR, butyl rubber, and the like.
• PE polyethylene
• PP polypropylene
• PGP expanded polypropylene
• PET polyethylene terephthalate
• PC polystyrene
• Resin films such as polyurethane, PE, butyl rubber, metal foils such as aluminum and copper, rubber sheets such as natural rubber,
• the method for applying the pressure-sensitive adhesive composition to the base material is not particularly limited, but a method of applying the pressure-sensitive adhesive material by dissolving it in an organic solvent (spreading method), thinning with a plurality of hot rolls, and applying Well-known techniques such as a technique (calender method) for applying and a method of applying a hot-melt adhesive material (hot-melt method) can be used.
• Triblock copolymer (a) Triblock copolymer (a-1): Methyl methacrylate (MMA) / n-butyl acrylate (n-BA) copolymer (triblock, hard segment (segment A) is MMA, soft segment (segment B) ) Is n-BA, hard segment content 16% by mass), molecular weight 140,000
• Double-sided pressure-sensitive adhesive tapes were prepared by the melting method with the above raw materials in the blending amounts shown in Table 1 below (unit: parts by mass). Specifically, the raw materials were added to toluene in the blending amounts shown in Table 1 below, and the raw materials were dissolved by stirring to prepare a solution-type pressure-sensitive adhesive composition (solid content concentration 50% by mass). Next, the obtained pressure-sensitive adhesive composition was glued to release paper with an applicator. After drying in an oven at 100 ° C. for 3 minutes, the nonwoven fabric (I) was bonded to the pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive composition was glued on the release paper in the same manner as described above, dried, and then bonded to the nonwoven fabric side of (I) to prepare a double-sided pressure-sensitive adhesive tape.
• the coating amount of the pressure-sensitive adhesive composition was 25 g / m 2 on both sides.
• peeling time is 6 days or more

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Adhesive Tapes (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=53681447

Family Applications (1)

Country Status (4)

Cited By (6)

Families Citing this family (2)

Citations (3)

Family Cites Families (4)

• 2015
  • 2015-01-22 WO PCT/JP2015/051627 patent/WO2015111646A1/ja active Application Filing
  • 2015-01-22 CN CN201580003157.2A patent/CN105829479B/zh active Active
  • 2015-01-22 KR KR1020167022372A patent/KR102228806B1/ko active IP Right Grant
  • 2015-01-22 JP JP2015559099A patent/JP6431854B2/ja active Active

Patent Citations (3)

Also Published As

Similar Documents

Legal Events