Claims (11)
一種鋰離子二次電池電極結合劑用樹脂，其主要成分為選自以下述通式(1)~(3)之任一者表示之構成單位中之至少一個構成單位，通式(1)所示之構成單位之含量(a)、通式(2)所示之構成單位之含量(b)與通式(3)所示之構成單位之含量(c)具有下述式(A)之關係，且於30℃時之對數黏度為0.02~2.0dl/g；0<a/(a+b+c)≦0.55(莫耳比) (A)(式(A)中，b>0，c>0)；
(上述通式(1)~(3)中，R為下述通式(4)所示
之2價芳香族基，Ar1
為下述通式(5)所示之2價芳香族基，Ar2
為下述通式(6)所示之3價芳香族基，不同構成單位中之各R、各Ar1
及各Ar2
相互獨立)；
(上述通式(4)中，X表示直接鍵結、-O-、-S-、-CO-、-SO2
-、-C(CH3
)2
-或-C(CF3
)2
-，p表示0~3之整數；上述通式(5)中，Y表示直接鍵結、-O-、-CO-、-SO2
-、-CH2
-、-C(CH3
)2
-或-C(CF3
)2
-，q表示0或1；上述通式(6)中，Z表示直接鍵結、-O-、-CO-、-COO-、-OCO-、-SO2
-、-CH2
-、-C(CH3
)2
-或-C(CF3
)2
-，r表示0或1；上述通式(4)、(5)及(6)中，各苯環可任意地含有選自由碳數1~4之烷基、碳數1~4之氟烷基、氯原子、溴原子、硝基及氰基所組成之群中之至少一個取代基)。A resin for a lithium ion secondary battery electrode binder, wherein a main component is at least one constituent unit selected from the group consisting of any one of the following general formulae (1) to (3), and the general formula (1) The content (a) of the constituent unit shown, the content (b) of the constituent unit represented by the formula (2), and the content (c) of the constituent unit represented by the formula (3) have the relationship of the following formula (A). And the logarithmic viscosity at 30 ° C is 0.02 ~ 2.0 dl / g; 0 < a / (a + b + c) ≦ 0.55 (Mo Er ratio) (A) (in the formula (A), b > 0, c >0);
(In the above formulae (1) to (3), R is represented by the following formula (4)
Divalent aromatic group, Ar1
Is a divalent aromatic group represented by the following formula (5), Ar2
It is a trivalent aromatic group represented by the following general formula (6), and each of the different constituent units R and each of Ar1
And each Ar2
Independent);
(In the above formula (4), X represents a direct bond, -O-, -S-, -CO-, -SO2
-, -C (CH3
)2
-or-C(CF3
)2
-, p represents an integer from 0 to 3; in the above formula (5), Y represents a direct bond, -O-, -CO-, -SO2
-, -CH2
-, -C (CH3
)2
-or-C(CF3
)2
-, q represents 0 or 1; in the above formula (6), Z represents direct bonding, -O-, -CO-, -COO-, -OCO-, -SO2
-, -CH2
-, -C (CH3
)2
-or-C(CF3
)2
-, r represents 0 or 1; in the above formulae (4), (5) and (6), each benzene ring may optionally contain a fluorocarbon selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and a carbon number of 1 to 4. At least one substituent of the group consisting of a chlorine atom, a bromine atom, a nitro group and a cyano group).
如申請專利範圍第1項之鋰離子二次電池電極結合劑用
樹脂，其含有上述通式(1)~(3)中之R為4,4’-二胺基二苯醚殘基之構成單位及R為m-苯二胺殘基之構成單位，樹脂中之4,4’-二胺基二苯醚殘基之含量(x)與m-苯二胺殘基之含量(y)具有下述關係：1.5≦x/y≦4(莫耳比)。
For example, the lithium ion secondary battery electrode binder for the first application of the patent scope is
a resin comprising R in the above formulas (1) to (3) as a constituent unit of a 4,4'-diaminodiphenyl ether residue and R as a constituent unit of an m-phenylenediamine residue, in a resin The content (x) of the 4,4'-diaminodiphenyl ether residue and the content (y) of the m-phenylenediamine residue have the following relationship: 1.5 ≦ x / y ≦ 4 (mole ratio).
如申請專利範圍第1項之鋰離子二次電池電極結合劑用樹脂，其中上述通式(1)~(3)中之任一者表示之各構成單位之含量具有下述式(B)之關係：0.05≦a/(a+b+c)≦0.55(莫耳比) (B)。
The resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, wherein the content of each constituent unit represented by any one of the above formulas (1) to (3) has the following formula (B) Relationship: 0.05 ≦ a / (a + b + c) ≦ 0.55 (mole ratio) (B).
如申請專利範圍第1項之鋰離子二次電池電極結合劑用樹脂，其具有0.05~0.40mmol/g之殘存羧基量。
A resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, which has a residual carboxyl group amount of 0.05 to 0.40 mmol/g.
如申請專利範圍第1項之鋰離子二次電池電極結合劑用樹脂，其中於280℃之大氣中加熱2小時後，以下述式(7)表示之膠化活性度為3.0重量%以下，膠化活性度(重量%)=(N-甲基-2-吡咯烷酮不溶份重量/樣本重量)×100 (7)。
The resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, wherein the gelation activity expressed by the following formula (7) is 3.0% by weight or less after heating in an atmosphere at 280 ° C for 2 hours. Activity (% by weight) = (N-methyl-2-pyrrolidone insoluble weight / sample weight) × 100 (7).
一種鋰離子二次電池電極結合劑用樹脂組成物，其含有如申請專利範圍第1至5項中任一項之鋰離子二次電池電極結合劑用樹脂5~30重量%，以及極性溶劑。
A resin composition for a lithium ion secondary battery electrode binder, which comprises 5 to 30% by weight of a resin for a lithium ion secondary battery electrode binder according to any one of claims 1 to 5, and a polar solvent.
一種鋰離子二次電池電極材料用糊，其含有如申請專利範圍第1至5項中任一項之鋰離子二次電池電極結合劑用樹脂，極性溶劑以及鋰離子二次電池電極活性物質粒子，且相對於鋰離子二次電池電極活性物質粒子含量100重量份而言，鋰離子二次電池電極結合劑用樹脂之含量為1~20重量份。
A paste for a lithium ion secondary battery electrode material, comprising a resin for a lithium ion secondary battery electrode binder according to any one of claims 1 to 5, a polar solvent, and a lithium ion secondary battery electrode active material particle The content of the lithium ion secondary battery electrode binder resin is from 1 to 20 parts by weight based on 100 parts by weight of the lithium ion secondary battery electrode active material particle content.
如申請專利範圍第7項之鋰離子二次電池電極材料用糊，其含有鋰離子二次電池負極活性物質粒子，且該粒子，相對於在鋰離子吸著前之體積100而言，在鋰離子充滿電時之體積為130以上250以下。
A paste for a lithium ion secondary battery electrode material according to claim 7, which comprises a lithium ion secondary battery negative electrode active material particle, and the particle is in lithium relative to a volume 100 before lithium ion sorption When the ions are fully charged, the volume is 130 or more and 250 or less.
一種鋰離子二次電池電極，其含有集電體以及塗布於該集電體上之如申請專利範圍第7或8項之鋰離子二次電池電極材料用糊。
A lithium ion secondary battery electrode comprising a current collector and a paste for a lithium ion secondary battery electrode material coated on the current collector according to claim 7 or 8.
如申請專利範圍第9項之鋰離子二次電池電極，其中上述集電體為金屬箔。
A lithium ion secondary battery electrode according to claim 9, wherein the current collector is a metal foil.
如申請專利範圍第9項之鋰離子二次電池電極，其中上述糊為乾燥狀態。A lithium ion secondary battery electrode according to claim 9, wherein the paste is in a dry state.