CN104769032B - Resin combination and formed body - Google Patents
Resin combination and formed body Download PDFInfo
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- CN104769032B CN104769032B CN201380056904.XA CN201380056904A CN104769032B CN 104769032 B CN104769032 B CN 104769032B CN 201380056904 A CN201380056904 A CN 201380056904A CN 104769032 B CN104769032 B CN 104769032B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention provides a kind of resin combination, the resin combination contains resin component (A), amines (B) and inorganic filler (C), the resin component (A) is comprising at least one party as the construction unit of ethylene derivative and in the copolymer and its ionomer of construction unit as derived from unsaturated carboxylic acid, the amines (B) has more than 2 amino in an intramolecular, and fusing point is more than 30 DEG C.
Description
Technical field
The present invention relates to resin combination and formed body.
Background technology
All the time, the research of the anti-flammabilitys of resin such as raising thermoplastic resin, thermosetting resin is carried out.
For example, as can suppress mold deposits (mold deposit), ooze out (bleed out), products formed can be improved
The fire retardant resin composition of appearance characteristics, it is known that the flame retardant resin group containing specific guanamines compound or its salt and resin
Compound (for example, see Japanese Unexamined Patent Publication 2004-203846 publications).
In addition, as can improve polyacetal resin heat endurance, especially processing and forming when melt stability tree
Oil/fat composition, it is known that by polyacetal resin, ionomer resin and selected from urea or derivatives thereof and at least one of amidine derivative
The polyacetal resin composite that inhibitor is constituted (for example, see Japanese Unexamined Patent Publication 2000-239485 publications).
In addition, on being used as acrylic resin, polyurethane resin, polystyrene, polyolefin, vinyl chloride resin, polyphenylene oxide
Deng the useful compound of the fire retardant of organic material, it is known that two guanamines (diguanamine) compound of specific structure (is such as joined
See Japanese Unexamined Patent Publication 5-202007 publications).
The content of the invention
However, only adding above-mentioned guanamines compound, amidine derivative etc. into resin, it can not obtain sufficiently fire-retardant sometimes
Property.
The present invention is to complete in view of the foregoing.In the case of above-mentioned, it is desirable to the significantly excellent resin combination of anti-flammability
Thing and formed body.
The inventors discovered that：The resin combination of combination containing following component is with lacking at least one kind of in these compositions
Resin combination is compared, and shows extremely excellent anti-flammability, and the composition is：Comprising the construction unit by ethylene derivative and by not
At least one party in the copolymer and its ionomer of construction unit derived from saturated carboxylic acid；Amines is (at one point
There are more than 2 amino, fusing point is more than 30 DEG C in sub)；And inorganic filler.The present invention is completed based on above-mentioned discovery.
That is, it is as follows for solving the specific means of above-mentioned problem.
The ＞ resin combinations of ＜ 1, it contains：
Resin component (A), is comprising the construction unit and the construction unit as derived from unsaturated carboxylic acid as ethylene derivative
At least one party in copolymer and its ionomer；
Amines (B), has more than 2 amino in an intramolecular, and fusing point is more than 30 DEG C；With
Inorganic filler (C).
Resin combinations of the ＞ of ＜ 2 as described in the ＞ of ＜ 1, wherein, containing resin component total amount in, above-mentioned resin into
It is more than 80 mass % to divide the ratio shared by (A).
Resin combinations of the ＞ of ＜ 3 as described in the ＞ of ＜ 1 or the ＞ of ＜ 2, wherein, containing resin component total amount in, on
It is more than 90 mass % to state the ratio shared by resin component (A).
Resin combinations of the ＞ of ＜ 4 as any one of the ＞ of 1 ＞ of ＜~＜ 3, wherein, with above-mentioned resin component (A) and
When the total amount of above-mentioned amines (B) is 100 mass parts, the amount of above-mentioned resin component (A) is the mass parts of 99 mass parts~80, on
It is the mass parts of 1 mass parts~20 to state the amount of amines (B).
Resin combinations of the ＞ of ＜ 5 as any one of the ＞ of 1 ＞ of ＜~＜ 4, wherein, with above-mentioned resin component (A) and
When the total amount of above-mentioned amines (B) is 100 mass parts, the amount of inorganic filler (C) is the mass parts of 20 mass parts~100.
Resin combinations of the ＞ of ＜ 6 as any one of the ＞ of 1 ＞ of ＜~＜ 5, wherein, above-mentioned amines (B) it is molten
Point is more than 200 DEG C.
Resin combinations of the ＞ of ＜ 7 as any one of the ＞ of 1 ＞ of ＜~＜ 6, wherein, above-mentioned amines (B) has
Guanamines structure.
Resin combinations of the ＞ of ＜ 8 as any one of the ＞ of 1 ＞ of ＜~＜ 7, wherein, above-mentioned inorganic filler (C) includes
It is at least one kind of in calcium carbonate, clay, talcum and silica.
Resin combinations of the ＞ of ＜ 9 as any one of the ＞ of 1 ＞ of ＜~＜ 8, wherein, above-mentioned resin component (A) includes
Above-mentioned ionomer.
Resin combinations of the ＞ of ＜ 10 as any one of the ＞ of 1 ＞ of ＜~＜ 9, wherein, above-mentioned inorganic filler (C) includes
Calcium carbonate.
The ＞ formed bodys of ＜ 11, it includes the resin combination any one of the ＞ of 1 ＞ of ＜~＜ 10.
Pass through the present invention, it is possible to provide anti-flammability significantly excellent resin combination and formed body.
Embodiment
《Resin combination》
The resin combination of the present invention contains：Resin component (A), it is included by the construction unit of ethylene derivative and by not
At least one party in the copolymer and its ionomer of construction unit derived from saturated carboxylic acid (hereinafter also referred to as " sets
Fat composition (A) ")；Amines (B), it has more than 2 amino in an intramolecular, fusing point (the also abbreviation below that is more than 30 DEG C
For " amines (B) ")；With inorganic filler (C).
The resin combination of the present invention, by resin component (A) and the combination of amines (B) and inorganic filler (C), from
And show significantly excellent anti-flammability.
The reason on obtaining above-mentioned flame resistance effect, is still not clear, but is presumed as follows.
I.e., it is believed that by the present invention resin combination in addition to containing resin component (A) and amines (B)
Also contain inorganic filler (C), following state can be formed, i.e. the carboxyl or its salt contained in resin component (A) passes through amines
(B) a part of amino (such as 1 in more than 2 amino contained in a molecule of amines (B)) for containing in and hand over
The state of connection.Think in the crosslinking and the whole amino contained in amines (B) are not used, but only used a part
Amino.Think the degree for thus suppressing to be crosslinked to a certain extent, so the mobility of resin combination can be maintained to a certain extent,
As a result, resin component (A) and amines (B) are mixed with being had good uniformity.
And think, when the resin composition burns for wanting to make the present invention apply heat, the hot big portion of application
Point due to remaining (in the crosslinking untapped) amino that contains in amines (B) with it is uncrosslinked in resin component (A)
Carboxyl or its salt cross-linking reaction and be consumed, as a result, become to be difficult to reach burning (that is, anti-flammability is uprised).
Speculated by above content, resin combination of the invention, by resin component (A) and amines (B) and inorganic
The combination of filler (C), is presented significantly excellent anti-flammability.
In the resin combination of the present invention, when its being substituted for above-mentioned resin component (A) beyond above-mentioned resin component (A)
During his resin component (such as ethylene unsaturated carboxylic acid's ester copolymer), anti-flammability reduction.
In addition, in the resin combination of the present invention, being less than 30 DEG C and in a molecule when amines (B) is substituted for into fusing point
When inside there is the amines of more than 2 amino, anti-flammability reduction.On its reason, although indefinite, but it is regarded as following
Reason, when melting mixing resin component (A) and fusing point are less than 30 DEG C of amines, both poor compatibilities；Fusing point is less than
30 DEG C of amines volatilization；Etc..
It should be noted that in the present invention, " melting mixing " refers to, by the resin component (A) in molten condition and its
He mixes composition (such as amines (B), inorganic filler (C)).Now, although resin component (A) turn into molten condition, but
Other compositions necessarily turn into molten condition.
It is melting mixing it is preferable that melting mixing in the present invention.
In addition, in the resin combination of the present invention, when using as the usually used metal hydroxide of the fire retardant of resin
Thing (magnesium hydroxide, aluminium hydroxide etc.) replaces during amines (B), there is following tendency：The mobility of resin combination shows
Reduction is write, resin component (A) and metal hydroxides, which are mixed, itself becomes difficult.
In addition, in the resin combination of the present invention, when not containing inorganic filler (C), anti-flammability reduction.
In addition, according to the resin combination of the present invention, passing through resin component (A) and amines (B) and inorganic filler (C)
Combination, anti-flammability is improved, and wearability also improves.
The reason on obtaining above-mentioned wearability effect, although indefinite, but be presumed as follows.
That is, in resin combination of the invention, as described above, with the carboxyl contained in following states, i.e. resin component (A)
Or the state that its salt is crosslinked by a part of amino contained in amines (B), resin component (A) and amines
(B) mix with being had good uniformity, it is believed that this is favorably improved wearability.
In the resin combination of the present invention, when above-mentioned resin component (A) to be replaced with to its beyond above-mentioned resin component (A)
During his resin component (such as ethylene unsaturated carboxylic acid's ester copolymer), wearability reduction.
In addition, in the resin combination of the present invention, being less than 30 DEG C and in a molecule when amines (B) is replaced with into fusing point
When inside there is the amines of more than 2 amino, wearability reduction.
In addition, in the resin combination of the present invention, when not containing inorganic filler (C), wearability reduction.
Next, resin component (A), amines (B) and inorganic filler in the resin combination of the explanation present invention
(C) scope of preferred containing ratio, but the invention is not restricted to following preferred scope.
It is excellent during using the total amount of resin component (A) and amines (B) as 100 mass parts in the resin combination of the present invention
It is the mass parts of 99.9 mass parts~60 to select the amount of resin component (A), and the amount of amines (B) is the mass parts of 0.1 mass parts~40,
The more preferably amount of resin component (A) is the mass parts of 99 mass parts~80, and the amount of amines (B) is the mass parts of 1 mass parts~20.
When the amount of amines (B) is more than 0.1 mass parts, anti-flammability is further improved.In addition, from performance in practical use
And from the viewpoint of economy, it is sufficient that amount of amines (B) is below 40 mass parts.
In addition, the present invention resin combination in, using the total amount of above-mentioned resin component (A) and above-mentioned amines (B) as
During 100 mass parts, the amount of inorganic filler (C) is preferably the mass parts of 10 mass parts~200, the matter of more preferably 20 mass parts~100
Measure part.
When the amount of inorganic filler (C) is more than 10 mass parts, anti-flammability is further improved.
When the amount of inorganic filler (C) is below 200 mass parts, mouldability and resin characteristics become more preferable.
Hereinafter, each composition contained in the resin combination for illustrating the present invention.
＜ resin components (A) ＞
The resin combination of the present invention contains resin component (A), and the resin component (A) is comprised at least by ethylene derivative
Construction unit and as derived from unsaturated carboxylic acid the copolymer of construction unit (hereinafter also referred to " ethylene unsaturated carboxylic acid is common
Polymers ") and its ionomer at least one party.
Above-mentioned ethylene unsaturated carboxylic acid's copolymer is at least to be total to ethene and unsaturated carboxylic acid as copolymer composition
Poly- copolymer.
As copolymer, random copolymer, block copolymer etc., preferably random copolymer can be enumerated.
As above-mentioned unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, ethylacrylic acid, itaconic acid, clothing health can be enumerated
Acid anhydrides, fumaric acid, crotonic acid, maleic acid, maleic anhydride, maleic mono-ester (monomethyl maleate, ethyl maleate etc.), horse
Carry out the unsaturated carboxylic acid or half that the carbon numbers such as acid anhydride monoester (maleic anhydride mono-methyl, maleic anhydride monoethylester etc.) are 3~8
Ester.
Wherein preferred acrylic acid, methacrylic acid.
In above-mentioned ethylene unsaturated carboxylic acid's copolymer, for the content of construction unit as derived from unsaturated carboxylic acid
Speech, it is considered to during the easiness that industry is obtained, relative to the total amount of copolymer, the mass % of preferably 2 mass %~40, more preferably
The mass % of 2 mass %~40 mass %, particularly preferably 5 mass %~25.
When the content of construction unit is more than 2 mass % as derived from unsaturated carboxylic acid, anti-flammability is further improved.
In addition, in above-mentioned ethylene unsaturated carboxylic acid's copolymer, for the content by the construction unit of ethylene derivative,
Relative to the total amount of copolymer, the mass of preferably 40 mass %~98 mass %, more preferably 60 mass %~98 % is especially excellent
Elect the mass % of 70 mass %~95 as.
Above-mentioned ethylene unsaturated carboxylic acid's copolymer can also include the construction unit as derived from esters of unsaturated carboxylic acids.
As above-mentioned esters of unsaturated carboxylic acids, the Arrcostab of above-mentioned unsaturated carboxylic acid can be enumerated, preferably above-mentioned unsaturated carboxylic
The carbon number of acid is 2~5 Arrcostab, and the carbon number of more preferably above-mentioned unsaturated carboxylic acid is (different for 4 Arrcostab
Butyl ester, N-butyl etc.).
As above-mentioned esters of unsaturated carboxylic acids, specifically, methyl acrylate, ethyl acrylate, acrylic acid isopropyl can be enumerated
Ester, isobutyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EMA, methyl
Isobutyl acrylate, n-BMA, EHMA, dimethyl maleate etc..Wherein, preferred acrylic acid
Methyl esters, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, methyl-prop
The acrylic or methacrylics such as olefin(e) acid ethyl ester, Isobutyl methacrylate, n-BMA, EHMA
The lower alkyl esters of the Arrcostab of acid, more preferably acrylic or methacrylic acid (carbon number is 2~5 Arrcostab).
The Arrcostab that the carbon number of further preferred acrylic or methacrylic acid is 4, wherein further preferred propylene
The carbon number of acid is 4 Arrcostab (particularly preferred isobutyl ester).
When above-mentioned ethylene unsaturated carboxylic acid's copolymer include the construction unit as derived from esters of unsaturated carboxylic acids when, for by
For the content of construction unit derived from esters of unsaturated carboxylic acids, relative to the total amount of copolymer, the matter of preferably 3 mass %~20
Measure %, the mass % of more preferably 5 mass %~20.
In above-mentioned ethylene unsaturated carboxylic acid's copolymer, relative to the construction unit by ethylene derivative, by unsaturated carboxylic acid
Derivative construction unit and as derived from esters of unsaturated carboxylic acids construction unit the mass % of total 100, can contain be more than 0 matter
Amount % and be below 30 mass %, preferably greater than 0 mass % and be below 25 mass % as derived from other co-polymerized monomers
Construction unit.
As other above-mentioned co-polymerized monomers, the beta-unsaturated esters (second such as vinyl acetate and propionate can be enumerated
Alkenyl esters), carbon monoxide, sulfur dioxide etc..
Ionomer in the present invention forms following structure, i.e. with foregoing ethylene unsaturated carboxylic acid's copolymerization
The knot that the carboxyl contained based on thing in polymer (base polymer), the base polymer is neutralized by metal ion
Structure.
Species for above-mentioned metal ion is not particularly limited, for example, can enumerate lithium (Li) ion, potassium (K) ion, sodium
(Na) polyvalent metal such as the alkali metal ion such as ion, calcium (Ca) ion, magnesium (Mg) ion, zinc (Zn) ion, aluminium (Al) ion from
Son etc..Especially, from the viewpoint of the easiness of the reaction with amines (B), preferred polyvalent metal ion, wherein, it is special
Not preferred zinc ion.
The degree of neutralization of above-mentioned ionomer is preferably 10%~90%, and more preferably 20%~80%.
For the resin component (A) in the present invention, it is contemplated that processability and mechanical strength, according to JIS K7210-
1999th, the melt flow rate (MFR) (MFR) measured under conditions of 190 DEG C, 2160g loads is preferably 0.01~1000g/10 points
Clock, more preferably 0.1~100g/10 minute.
The resin combination of the present invention can also include two or more only comprising a kind of resin component (A).
In the total amount of the resin component contained by resin combination in the present invention, the ratio shared by resin component (A) is excellent
Elect as more than 40 mass %.
The ratio of resin component (A) be more than 40 mass % refer to, the resin contained by resin combination of the invention into
Major part in point is resin component (A).Thus, anti-flammability is further improved.
The ratio of above-mentioned resin component (A) is more preferably more than 60 mass %, more preferably more than 80 mass %, is entered
One step is preferably more than 90 mass % more preferably more than 95 mass %, more preferably more than 98 mass %, optimal
Electing 100 mass % as, (that is, the resin component contained by resin combination of the invention is only made up of above-mentioned resin component (A)
Mode).
The resin combination of the present invention can include other resin components beyond at least one kind of resin component (A).
As other resin components, it is not particularly limited, such as polyethylene, ethylene unsaturated carboxylic acid's ester copolymerization can be enumerated
Thing, EVAc etc..It is used as other resin components, preferably polyethylene.
As polyethylene, high density polyethylene (HDPE) (HDPE), high-pressure process low-density polyethylene (LDPE), straight-chain can be enumerated low
Density polyethylene (LLDPE) etc..HDPE, LDPE and LLDPE can be used alone, can also be with mixture of more than two kinds
Form use.
In addition, from the viewpoint of further raising anti-flammability and wearability, resin component (A) preferably comprises above-mentioned ion
Cross-linked polymer.
When resin component (A) includes above-mentioned ionomer, relative to resin component (A) total amount, it is above-mentioned from
The ratio of sub- cross-linked polymer is preferably more than 40 mass %, more preferably more than 60 mass %, more preferably 80 matter
Measure more than %, more preferably more than 90 mass %, most preferably 100 mass % (above-mentioned resin component (A) only by it is above-mentioned from
The mode of sub- cross-linked polymer composition).
When the ratio of ionomer in above-mentioned resin component (A) is more than 40 mass %, anti-flammability is further
Improve.Its reason is although indefinite, but it is following reason to speculate：The reactivity raising of resin component (A) and amines (B),
Anti-flammability is improved.
In addition, when the ratio of the ionomer in above-mentioned resin component (A) is more than 40 mass %, wearability
Further improve.
In addition, the content for the resin component (A) in the resin combination of the present invention is not particularly limited, relative to tree
The mass % of oil/fat composition total amount, preferably 20 mass %~99.9 mass %, more preferably 40 mass %~90, particularly preferably
The mass % of 50 mass %~80.
＜ amines (B) ＞
The resin combination of the present invention contains amines (B), the amines (B) an intramolecular have 2 with
Upper amino, fusing point is more than 30 DEG C.
From the viewpoint of further raising anti-flammability, the fusing point of amines (B) is preferably more than 200 DEG C, more preferably
For more than 250 DEG C.
When the fusing point of amines (B) is more than 200 DEG C, when with resin component (A) melting mixing, amine compounds can be suppressed
The dissolving or decomposition of thing (B), are preferably mixed therefore, it is possible to uniformity with the above-mentioned resin component (A) in molten condition.By
This, anti-flammability when forming resin combination is further improved.
As amines (B), it is not particularly limited, such as guanamines (alias can be enumerated：2,4- diaminostilbenes, 3,5-
Triazine) (more than 300 DEG C of fusing point, molecular weight 111.11), CTU guanamines (alias：3,9- pairs [2- (3,5- diaminourea -2,4,
6- triazines base) ethyl] -2,4,8,10- tetra- oxaspiro [5.5] hendecanes) (270 DEG C of fusing point, molecular weight 434.46),
Acetylguanamine (alias：2,4- diaminourea -6- methyl isophthalic acids, 3,5- triazines) (274 DEG C~276 DEG C of fusing point, molecular weight
125.13), benzoguanamine (alias：2,4- diaminourea -6- phenyl -1,3,5-triazines) (fusing point 219 DEG C~221 DEG C, point
Son amount 187.2), hexamethylene diamine (39 DEG C~42 DEG C of fusing point, molecular weight 116.20), 2,4- diaminotoluenes (fusing point 99
DEG C, molecular weight 122.17), 4,4 '-diaminodiphenyl-methane (alias：4,4 '-methylene dianiline (MDA)) (fusing point 91 DEG C, point
Son amount 198.26), 4,4 '-diamino-diphenyl ethane (136 DEG C~138 DEG C of fusing point, molecular weight 212.29) etc..
In addition, as amines (B), can also enumerate the guanamines described in Japanese Unexamined Patent Publication 2004-203846 publications
Urea, the derivative of urea and amidine derivative and Japan described in compound and its salt, Japanese Unexamined Patent Publication 2000-239485 publications
Fusing point is more than 30 DEG C and has 2 in an intramolecular in bisguanides amines described in Unexamined Patent 5-202007 publications
The compound of above amino.
It is used as amines (B), it is however preferred to have the compound of triazine structure, more preferably the chemical combination with guanamines structure
Thing.
Herein, as the compound with triazine structure, as long as there is at least one triazine structure in an intramolecular,
It is not particularly limited.In addition, as the compound with guanamines structure, as long as there is at least one guanamines structure in an intramolecular
, it is not particularly limited.
Herein, guanamines structure is the structure shown in following formula (1).
In formula (1), * represents the bonding position with hydrogen atom or carbon atom.
As the compound with guanamines structure, guanamines, CTU guanamines, acetylguanamine, benzoguanamine can be enumerated.
In the compound with guanamines structure, particularly preferred fusing point is the chemical combination of more than 200 DEG C (preferably more than 250 DEG C)
Thing.As such compound, guanamines, CTU guanamines, acetylguanamine, benzoguanamine, preferably guanamines, CTU guanamines, second can be enumerated
Acyl guanamines.
It is not particularly limited for the molecular weight of amines (B), from the viewpoint for the effect for more effectively playing the present invention
Consider, preferably less than more than 100 1000, more preferably less than more than 200 600, particularly preferably less than more than 400 500.
The resin combination of the present invention can also include two or more only comprising a kind of amines (B).
In addition, the content for the amines (B) in the resin combination of the present invention is not particularly limited, relative to tree
Oil/fat composition total amount, preferably 0.05 mass %~40 mass %, more preferably 0.1 mass %~40 mass %, it is further excellent
Elect the mass % of 0.5 mass %~20 as, the matter of more preferably 1 mass %~20 mass %, particularly preferably 1 mass %~10
Measure %.
＜ inorganic fillers (C) ＞
The resin combination of the present invention contains inorganic filler (C).
The resin combination of the present invention can also include two or more only comprising a kind of inorganic filler (C).
As inorganic filler (C), it is not particularly limited, known inorganic filler can be used.
As inorganic filler (C), specifically, calcium carbonate, clay, talcum, silica, reinforcing fiber (glass can be enumerated
Glass fiber, carbon fiber etc.), sheet glass (glass flake), mica etc..As inorganic filler (C), the inorganic of synthesis can be used
Filler, it is possible to use commercially available product.
From it is further improve anti-flammability from the viewpoint of, inorganic filler (C) preferably comprise selected from calcium carbonate, clay, talcum,
And it is at least one kind of in silica, preferably comprise it is at least one kind of in calcium carbonate, clay and talcum, more preferably comprising carbon
Sour calcium.
In addition, by making inorganic filler (C) comprising at least one kind of in calcium carbonate, clay, talcum and silica
(be more preferably selected from calcium carbonate, clay and talcum it is at least one kind of, more preferably calcium carbonate), so as to also improve wear-resisting
Property.
When inorganic filler (C) includes calcium carbonate, inorganic filler (C) can only wrap inorganic filler calciferous,
Can be inorganic comprising calcium carbonate and other inorganic fillers (being selected from least one kind of in clay, talcum and silica)
Filler.
When inorganic filler (C) includes calcium carbonate, relative to inorganic filler (C) total amount, the ratio of the amount of calcium carbonate is preferred
For more than 50 mass %, more preferably more preferably more than 80 mass %, most preferably more than 90 mass %, 100 matter
Measure % (mode that above-mentioned inorganic filler (C) is only made up of calcium carbonate).
Content for the inorganic filler (C) in the resin combination of the present invention is not particularly limited, relative to resin group
Compound total amount, preferably 10 mass %~70 mass %, preferably 10 mass %~60 mass %, more preferably 10 mass %~
50 mass %.
＜ other compositions ＞
In the range of the purpose of the present invention is not damaged, resin combination of the invention can be also included beyond mentioned component
Other compositions.
As other compositions, can enumerate antioxidant, antiaging agent, light stabilizer, heat stabilizer, ultra-violet absorber,
Lubricant (Metallic stearates such as zinc stearate), anticaking agent, plasticizer, adhesive, colouring agent (pigment, dyestuff),
Fire retardant (such as metal hydroxides (magnesium hydroxide, aluminium hydroxide)), flame retardant, foaming agent, blowing promotor, dimeric dibasic acid
(or its metal salt) etc..
In addition, from the viewpoint of the effect for more effectively playing the present invention, relative to resin combination total amount, resin into
The total amount for dividing (A), amines (B) and inorganic filler (C) is preferably more than 80 mass % more preferably more than 85 mass %,
Particularly preferably more than 90 mass %.
For the resin combination of the present invention, according to JIS K7210-1999, in 230 DEG C, the condition of 10kg loads
Under the melt flow rate (MFR) (MFR) that measures be preferably 0.01~1000g/10 minutes, more preferably 0.1~100g/10 minutes.
＜ manufacture methods ＞
As the method for the resin combination of the manufacture present invention, as long as will at least resin component (A), amines (B)
And the method for inorganic filler (C) mixing, it is not particularly limited.
As the example of the method for the resin combination of the manufacture present invention, following methods can be enumerated：
(method 1) is molten by resin component (A), amines (B) and inorganic filler (C) (and other compositions as needed)
Melt the method for mixing；
(method 2) first, by resin component (A) and amines (B) melting mixing, nothing is added into obtained mixture
Machine filler (C) (and other compositions as needed), the method for further carrying out melting mixing；Etc..
Wherein, from the viewpoint of with more preferable uniformity, each composition is mixed, method for optimizing 2.
It is used as the mode of the melting mixing in method 1 and method 2, preferred molten mixing.
For the melting mixing in method 1 and method 2, known mixing arrangement (such as Single screw extrusion can be used
The kneading devices such as machine, double screw extruder, Banbury mixer, kneader) carry out.
It is used as resin temperature during melting mixing in the above method 1, preferably less than more than 150 DEG C 250 DEG C.
In the above method 2, as by resin temperature when resin component (A) and amines (B) melting mixing, it is preferably
Less than more than 200 DEG C 350 DEG C, particularly preferably more preferably less than more than 200 DEG C 330 DEG C, less than more than 250 DEG C 300 DEG C.
It is mixed as the mixture of resin component (A) and amines (B) and inorganic filler (C) are melted in the above method 2
Resin temperature during conjunction, preferably less than more than 150 DEG C 250 DEG C, also, be preferably to compare resin component (A) and amines
(B) the low temperature of resin temperature during melting mixing.
《Formed body》
The formed body of the present invention is constituted comprising resin combination of the invention, is to be sent out this using known method
Formed by bright resin combination shaping.
As the method for shaping, hot-forming, extrusion molding (melting extrusion shaping), injection moulding can be enumerated, be blow molded into
The various methods such as type, drawing and forming.
As described above, resin combination excellent in flame retardance of the invention, therefore, the resin combination is molded and obtained
Formed body can be widely applied to the buildings such as ceiling materials, baseboard material, engineering materials；Automobile component；OA equipment；It is electrically electric
Subassembly, household electrical appliances article component, solar cell component parts (such as back-sheet, encapsulant) or their keeping
Containing box；Stationery；The purposes such as commodity.
Embodiment
Next, the present invention is illustrated by embodiment in further detail, but the present invention is not by any limit of these examples
System.
Hereinafter, " part " represents mass parts.
In addition, the melt flow rate (MFR) (MFR) of the resin component as raw material according to JISK7210-1999,190 DEG C,
It is measured under conditions of 2160g loads.
In addition, " ethylene contents " refer to from the construction unit of the ethene content (quality %) overall relative to copolymer
(other records on " content " are similarly).
＜ raw materials ＞
The raw material used in the present embodiment is as follows.
- resin component-
Ionomer 1：
Ethylene methacrylic acid copolymer (the mass % of ethylene contents=85, methacrylic acid content=15 mass %)
Zinc ionomer (degree of neutralization=59%, MFR=0.9g/10 minute)
Ionomer 2：
Ethylene methacrylic acid copolymer (the mass % of ethylene contents=85, methacrylic acid content=15 mass %)
Sodium ionomer (degree of neutralization=54%, MFR=0.9g/10 minute)
Ionomer 3：
(the mass % of ethylene contents=80, methacrylic acid contain ethylene methacrylic acid isobutyl acrylate copolymer
Measure=10 mass %, the mass % of i-butyl ester content=10) zinc ionomer (degree of neutralization=70%, MFR=
1g/10 minutes)
Ionomer 4：
Ethylene methacrylic acid copolymer (the mass % of ethylene contents=85, methacrylic acid content=15 mass %)
Zinc ionomer (degree of neutralization=21%, MFR=16g/10 minute)
·EMAA1：
Ethylene methacrylic acid copolymer (the mass % of the mass % of ethylene contents=85, methacrylic acid content=15,
MFR=25g/10 minutes)
·EMAA2：
(the mass % of ethylene contents=80, methacrylic acid contain ethylene methacrylic acid isobutyl acrylate copolymer
Measure=10 mass %, mass %, MFR=35g/10 minute of i-butyl ester content=10)
·EMAA3：
(the mass % of ethylene contents=80, methacrylic acid contain ethylene methacrylic acid isobutyl acrylate copolymer
Measure=10 mass %, mass %, MFR=30g/10 minute of i-butyl ester content=10)
·EEA1：
Ethylene ethyl acrylate copolymer (the mass % of the mass % of ethylene contents=82, ethyl acrylate content=18,
MFR=6g/10 minutes)
·EEA2：
Ethylene ethyl acrylate copolymer (the mass % of the mass % of ethylene contents=84, ethyl acrylate content=16,
MFR=1g/10 minutes)
·EVA1：
EVAc (the mass % of the mass % of ethylene contents=81, vinyl acetate content=19,
MFR=2.5g/10 minutes)
·EVA2：
EVAc (the mass % of the mass % of ethylene contents=83, vinyl acetate content=17,
MFR=0.8g/10 minutes)
·PE：
Straight-chain low density polyethylene (LDPE) (LLDPE) ((strain) Prime Polymer EVOLUE SP0511；Density=
903kg/m3, MFR=1.2g/10 minutes)
In above-mentioned resin component, ionomer 1, ionomer 2, ionomer 3, ion are handed over
The resin component (A) that linked polymer 4, EMAA1, EMAA2 and EMAA3 belong in the present invention.
- amines-
·Aceto：Acetylguanamine (274 DEG C~276 DEG C of fusing point)
·CTU：CTU guanamines (270 DEG C of fusing point)
4,4 '-diaminodiphenyl-methane (91 DEG C of fusing point)
1,3-BAC：1,3- double aminomethyl cyclohexanes (- 70 DEG C of fusing point)
Ethylenediamine (9 DEG C of fusing point)
In above-mentioned amines, Aceto, CTU and 4, the amine compounds that 4 '-diaminodiphenyl-methane belongs in the present invention
Thing (B).
- inorganic filler-
Calcium carbonate (CaCO3；Day eastern efflorescence industrial (strain) system (trade name；NCC#110))
Clay (Northeast chemistry (strain) system (trade name；KAOLIN))
(loose village's industry (strain) makes (trade name to talcum；HiFiller#5000PJ))
Silica (SiO2；FUJI SILYSIA CHEMICAL LTD. system (trade names；SYLYSIA 450))
- other compositions-
Zinc stearate (and Wako Pure Chemical Industries (strain) system)
Magnesium hydroxide (Mg (OH)2；" KISUMA5A " for chemical industry (strain) system of coordinating)
(embodiment 1)
The making ＞ of ＜ resin combinations
The ionomer 1 of resin component (95 mass parts) and Aceto (5 mass as amines will be used as
Part) melting mixing 15 minutes under 275 DEG C of resin temperature, using obtained mixture (100 mass parts) and it is used as inorganic filler
CaCO3(50 mass parts) melting mixing 10 minutes under 200 DEG C of resin temperature, have obtained resin combination.
The making of ＜ formed bodys and evaluation ＞
Hot pressing is carried out to obtained resin combination under 180 DEG C of resin temperature, thick 3mm experiment sheet material has been obtained
1 (formed body).
From the obtained experiment test film in sheet material 1, cutting out 80mm × 6.5mm × thickness 3mm, for the test film, enter
Evaluation of the following evaluation as anti-flammability is gone.
Evaluation result is shown in table 1 below.
(measure of oxygen index (OI) (O.I))
For above-mentioned test film, combustion test is carried out according to JIS K7201-1995, oxygen index (OI) (O.I) is determined.
The value of the oxygen index (OI) measured is bigger, represents that anti-flammability is more excellent (i.e. anti-flammability is high).
(evaluation of drippage (drip))
When being burnt in above-mentioned combustion test, visually confirm have without dripping off.
Represent excellent in flame retardance without dripping off (i.e. anti-flammability is high).
(embodiment 2~12)
In embodiment 1, change as shown in table 1 resin component species and amount, the species of amines and amount and
The species and amount of inorganic filler, in addition, make resin combination, carry out similarly to Example 1 similarly to Example 1
The making and evaluation of formed body.
Evaluation result is shown in table 1 below.
(embodiment 13)
In example 4, resin component and amines and inorganic filler are melted under 200 DEG C of resin temperature simultaneously
Mixing 10 minutes, in addition, makes resin combination similarly to Example 4, and formed body is carried out similarly to Example 4
Make and evaluate.
Evaluation result is shown in table 1 below.
(comparative example 1)
In embodiment 1, without using amines and inorganic filler, the ionomer as resin component is used
1 makes formed body, in addition, and the making and evaluation of formed body are carried out similarly to Example 1.
Evaluation result is shown in table 1 below.
(comparative example 2,17 and 20)
In comparative example 1, the species of resin component is changed as shown in table 1, in addition, is entered in the same manner as comparative example 1
The making and evaluation of row formed body.
Evaluation result is shown in table 1 below.
(comparative example 3~13,15,16,18,19,21,22 and 23)
In embodiment 1, change as shown in table 1 resin component species and amount, the species of amines and amount and
The species and amount of inorganic filler, in addition, make resin combination, carry out similarly to Example 1 similarly to Example 1
The making and evaluation of formed body.
Herein, it is the resin combination in the example (example of amines is not used) of 0 mass parts to make the amount of amines
Thing, by the way that melting mixing 10 minutes makes under 200 DEG C of resin temperature by resin component and inorganic filler.
In addition, making the amount of inorganic filler be the resin combination in the example (example of inorganic filler is not used) of 0 mass parts
Thing, by the way that melting mixing 15 minutes makes under 275 DEG C of resin temperature by resin component and amines.
Evaluation result is shown in table 1 below.
(comparative example 14)
The ionomer 1 of resin component (95 mass parts) and 1,3-BAC (5 matter as amines will be used as
Measure part) melting mixing 15 minutes under 200 DEG C of resin temperature, filled out using obtained mixture (100 mass parts) and as inorganic
The CaCO of material3(50 mass parts) melting mixing 10 minutes under 200 DEG C of resin temperature, make resin combination, with embodiment 1
Similarly carry out the making and evaluation of formed body.
Evaluation result is shown in table 1 below.
[table 1]
- explanation of table 1-
The amount (part) of each composition is mass parts.
As shown in table 1, the embodiment 1~13 of resin component (A), amines (B) and inorganic filler (C) has been used, with
At least one kind of comparative example 1~23 lacked in resin component (A), amines (B) and inorganic filler (C) is compared, oxygen index (OI)
Height, excellent in flame retardance.
In detail, imitated for using ionomer 1 to be improved as the anti-flammability in the case of resin component (A)
Really, it can for example be confirmed by embodiment 2, comparative example 1, comparative example 3 and comparative example 7.
That is, compared with the comparative example 1 (oxygen index (OI) 19.0) of ionomer 1 is used alone, in ionomeric
In the comparative example 7 (oxygen index (OI) 19.0) that amines (B) is only with the addition of in thing 1, oxygen index (OI) does not increase.In addition, with the comparative example 1
Compare, oxygen index (OI) in the comparative example 3 (oxygen index (OI) 21.5) of inorganic filler (C) is only with the addition of in ionomer 1 is also
The degree slightly increased.On the other hand, the reality of amines (B) and inorganic filler (C) is with the addition of in ionomer 1
Apply in example 2 (oxygen index (OI) 28.0), oxygen index (OI) is significantly increased.
Similarly, also it is able to confirm that and is gathered using ionomer 2, ionomer by table 1 (especially oxygen index (OI))
Compound 3 or EMAA1 improve effect as anti-flammability when resin component (A).
In addition, improving effect for the anti-flammability obtained by using resin component (A) as resin component, also can
Confirmed by embodiment 1~13 and comparative example 10~13.
For example, adding both amines (B) and inorganic filler (C) in EEA1 (being not belonging to resin component (A))
(comparative example 12), with only added in EEA1 certain one in amines (B) and inorganic filler (C) situation (comparative example 10,
11) compare, oxygen index (OI) does not also almost increase.
(embodiment 14)
Using as the ionomer 3 of resin component (85.5 mass parts) and PE (9.5 mass parts), be used as amine compounds
The Aceto (5 mass parts) of thing and as inorganic filler calcium carbonate (50 mass parts) and meanwhile under 200 DEG C of resin temperature melt
Mixing 10 minutes, has obtained resin combination.
Using obtained resin combination, similarly to Example 13, the making and evaluation of formed body are carried out.As a result, oxygen
Index is 25.5, without dripping off.
(embodiment 15)
As the ionomer 1 of resin component (95 mass parts) and the 4 of amines, 4 '-diaminourea will be used as
Diphenyl methane (and Wako Pure Chemical Industries (strain) system, 91 DEG C of fusing point, 5 mass parts) melting mixing 15 under 200 DEG C of resin temperature
Minute, using obtained mixture (100 mass parts) and it is used as the CaCO of inorganic filler3The resin temperature of (50 mass parts) at 200 DEG C
The lower melting mixing of degree 10 minutes, has obtained resin combination.
Using obtained resin combination, the making and evaluation of formed body are carried out similarly to Example 1.As a result, oxygen refers to
Number is 26.0, without dripping off.
(comparative example 24)
As the ionomer 1 of resin component (95 mass parts) and ethylenediamine (and the light of amines will be used as
Industrial (strain) system of pure medicine, 9 DEG C of fusing point, 5 mass parts) melting mixing 15 minutes under 200 DEG C of resin temperature, by obtained mixing
Thing (100 mass parts) and it is used as the CaCO of inorganic filler3(50 mass parts) 10 points of melting mixing under 200 DEG C of resin temperature
Clock, has obtained resin combination.
Using obtained resin combination, the making and evaluation of formed body are carried out similarly to Example 1.As a result, oxygen refers to
Number is 24.0, without dripping off.
(embodiment 16~19, comparative example 25~30)
Using the resin combination shown in table 2 below, the making and evaluation of formed body are carried out similarly to Example 1.Will
Evaluation result is shown in table 2 below.
The details of compounding process " 1 " and " 2 " in table 2 below is as follows.
- compounding process-
" 1 " is the compounding process in embodiment 13.That is, by whole compositions while under 200 DEG C of resin temperature
The melting mixing method of 10 minutes.
" 2 " are the compounding process in embodiment 1.I.e., first, by resin component and amines at 275 DEG C
Melting mixing 15 minutes, are made mixture under resin temperature, next, the resin by the mixture and inorganic filler at 200 DEG C
At a temperature of the melting mixing method of 10 minutes.
(making of formed body and the evaluation of wearability)
In above-described embodiment 16~19 and comparative example 25~30, the evaluation of wearability is carried out as further described below.
Resin combination under 180 DEG C of resin temperature obtained by hot pressing, obtains the thick 2mm experiment (shaping of sheet material 2
Body).
From obtained above-mentioned experiment sheet material 2, diameter 107mm, thickness 2mm discoid test film are cut out.For obtaining
Discoid test film, with reference to JIS K7204-1999, in the environment of 23 DEG C of 55%RH, use Taber abrasiometers
(Toyo Co., Ltd.'s essence mechanism makees made Rotating Cutter test instrument (Rotary Abrasion Tester) (model T)), uses
CS17 takes turns as abrasion, is that 1kg, rotary speed are that 60rpm, revolution are under conditions of 1000 turns, to carry out Taber abrasion in load
Experiment.
Subtracted from the quality of the discoid test film before above-mentioned Taber abrasion tests after above-mentioned Taber abrasion tests
The quality of discoid test film, thus obtains Taber abrasion loss (mg).The value of the Taber abrasion loss (mg) is smaller, represents wear-resisting
Property is more excellent.
Taber abrasion loss (mg) is shown in table 2 below.
[table 2]
As shown in table 2, in embodiment 16~19, anti-flammability and excellent in abrasion resistance.
The Japanese patent application 2012-247484 filed an application on November 9th, 2012 complete disclosure is passed through
Reference is incorporated in this specification.
All documents, patent application and technical standard described in this specification, by referring to being merged in this specification,
Each document, patent application and technical standard are by referring to the degree that is merged in and the degree phase of situation that is specific and respectively recording
Together.
Claims (10)
1. a kind of resin combination, it contains：
Resin component A, the resin component A are comprising the construction unit and the structure as derived from unsaturated carboxylic acid as ethylene derivative
At least one party in the copolymer and its ionomer of unit, containing resin component total amount in, the resin
Ratio shared by composition A is more than 80 mass %；
Amines, the amines has more than 2 amino in an intramolecular, and fusing point is more than 30 DEG C；With
Inorganic filler, the content of the inorganic filler is the mass % of 10 mass %~50 relative to resin combination total amount.
2. resin combination as claimed in claim 1, wherein, containing resin component total amount in, the resin component A
Shared ratio is more than 90 mass %.
3. resin combination as claimed in claim 1 or 2, wherein, with the resin component A and the amines total amount
During for 100 mass parts, the amount of the resin component A is the mass parts of 99 mass parts~80, and the amount of the amines is 1 mass parts
~20 mass parts.
4. resin combination as claimed in claim 1 or 2, wherein, with the resin component A and the amines total amount
During for 100 mass parts, the amount of inorganic filler is the mass parts of 20 mass parts~100.
5. resin combination as claimed in claim 1 or 2, wherein, the fusing point of the amines is more than 200 DEG C.
6. resin combination as claimed in claim 1 or 2, wherein, the amines has guanamines structure.
7. resin combination as claimed in claim 1 or 2, wherein, the inorganic filler, which is included, is selected from calcium carbonate, clay, cunning
It is at least one kind of in stone and silica.
8. resin combination as claimed in claim 1 or 2, wherein, the resin component A includes the ionomeric
Thing.
9. resin combination as claimed in claim 1 or 2, wherein, the inorganic filler includes calcium carbonate.
10. a kind of formed body, it includes resin combination according to any one of claims 1 to 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012247484 | 2012-11-09 | ||
| JP2012-247484 | 2012-11-09 | ||
| PCT/JP2013/080309 WO2014073661A1 (en) | 2012-11-09 | 2013-11-08 | Resin composition and molded article |
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| CN104769032A CN104769032A (en) | 2015-07-08 |
| CN104769032B true CN104769032B (en) | 2017-08-04 |
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|---|---|
| JP (1) | JP6196630B2 (en) |
| KR (1) | KR101821277B1 (en) |
| CN (1) | CN104769032B (en) |
| WO (1) | WO2014073661A1 (en) |
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| US10325988B2 (en) | 2013-12-13 | 2019-06-18 | Power Integrations, Inc. | Vertical transistor device structure with cylindrically-shaped field plates |
| CN111683975B (en) * | 2018-02-15 | 2023-03-28 | 三井—陶氏聚合化学株式会社 | Modified resin for molded body and golf ball |
| US11708439B2 (en) | 2018-02-15 | 2023-07-25 | Dow-Mitsui Polychemicals Co., Ltd. | Modified resin for molded article and golf ball |
| BR112021018678A2 (en) * | 2019-03-20 | 2021-11-23 | Dow Mitsui Polychemicals Co Ltd | Resin composition for laminated glass interlayer, laminated glass interlayer, and laminated glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029154A (en) * | 2006-03-03 | 2007-09-05 | 日立电线株式会社 | Halogen free flame retardant resin composition and wire cable using same |
| CN102196909A (en) * | 2008-10-30 | 2011-09-21 | 三井-杜邦聚合化学株式会社 | Multilayer sheet, solar cell element sealing material and solar cell module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222841A (en) * | 1985-07-22 | 1987-01-31 | Du Pont Mitsui Polychem Co Ltd | Thermoplastic polymer composition having excellent rigidity |
| JP3597966B2 (en) * | 1997-02-18 | 2004-12-08 | 三井・デュポンポリケミカル株式会社 | Golf ball material and ionomer composition |
| JPH1129672A (en) * | 1997-07-08 | 1999-02-02 | Du Pont Mitsui Polychem Co Ltd | Ionomer composition |
| JP4690517B2 (en) * | 2000-03-22 | 2011-06-01 | 三井・デュポンポリケミカル株式会社 | Ethylene copolymer composition |
| JP2005220251A (en) * | 2004-02-06 | 2005-08-18 | Sumitomo Rubber Ind Ltd | Rubber composition for tire tread and pneumatic tire using the same |
| US8236880B2 (en) * | 2008-04-23 | 2012-08-07 | Taylor Made Golf Company, Inc. | Compositions comprising an amino triazine and ionomer or ionomer precursor |
-
2013
- 2013-11-08 KR KR1020157011952A patent/KR101821277B1/en active IP Right Grant
- 2013-11-08 CN CN201380056904.XA patent/CN104769032B/en active Active
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- 2013-11-08 WO PCT/JP2013/080309 patent/WO2014073661A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029154A (en) * | 2006-03-03 | 2007-09-05 | 日立电线株式会社 | Halogen free flame retardant resin composition and wire cable using same |
| CN102196909A (en) * | 2008-10-30 | 2011-09-21 | 三井-杜邦聚合化学株式会社 | Multilayer sheet, solar cell element sealing material and solar cell module |
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| Publication number | Publication date |
|---|---|
| CN104769032A (en) | 2015-07-08 |
| JPWO2014073661A1 (en) | 2016-09-08 |
| JP6196630B2 (en) | 2017-09-13 |
| WO2014073661A1 (en) | 2014-05-15 |
| KR20150067324A (en) | 2015-06-17 |
| KR101821277B1 (en) | 2018-01-23 |
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Address after: Tokyo, Japan, Japan Patentee after: Mitsui-Dow Polymerization Chemical Co., Ltd. Address before: Tokyo, Japan, Japan Patentee before: Mitsui Du Pont Polychemical |