CN104769032A - Resin composition and molded article - Google Patents
Resin composition and molded article Download PDFInfo
- Publication number
- CN104769032A CN104769032A CN201380056904.XA CN201380056904A CN104769032A CN 104769032 A CN104769032 A CN 104769032A CN 201380056904 A CN201380056904 A CN 201380056904A CN 104769032 A CN104769032 A CN 104769032A
- Authority
- CN
- China
- Prior art keywords
- resin combination
- resinous principle
- amine compound
- quality
- mass parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention provides a resin composition containing a resin component (A) that is a copolymer containing a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid and/or an ionomer thereof, an amine compound (B) having a melting point of 30 DEG C or higher and having two or more amino groups per molecule, and inorganic filler (C).
Description
Technical field
The present invention relates to resin combination and formed body.
Background technology
All the time, the research of the flame retardant resistance improving the resin such as thermoplastic resin, thermosetting resin is carried out.
Such as, as the flame retardant resin composition that can suppress mold deposits (mold deposit), ooze out (bleed out), the appearance characteristics of products formed can be improved, the known flame retardant resin composition (for example, see Japanese Unexamined Patent Publication 2004-203846 publication) containing specific guanamines compound or its salt and resin.
In addition, as can improve polyacetal resin thermostability, especially forming process time the resin combination of melt stability, known by polyacetal resin, ionomer resin be selected from the polyacetal resin composite (for example, see Japanese Unexamined Patent Publication 2000-239485 publication) that at least one inhibitor in urea or derivatives thereof and amidine derivative forms.
In addition, about the compound that the fire retardant as organic materialss such as acrylic resin, urethane resin, polystyrene, polyolefine, vinyl chloride resin, polyphenylene oxide is useful, two guanamines (diguanamine) compound (for example, see Japanese Unexamined Patent Publication 5-202007 publication) of known ad hoc structure.
Summary of the invention
But, only in resin, add above-mentioned guanidine amine compound, amidine derivative etc., sometimes cannot obtain sufficient flame retardant resistance.
The present invention completes in view of the foregoing.In above-mentioned situation, require the resin combination that flame retardant resistance is significantly excellent and formed body.
The present inventor finds: the resin combination of the combination containing following composition is compared with the resin combination lacking in these compositions at least a kind, the flame retardant resistance that display is extremely excellent, described composition is: comprise at least one party in the multipolymer of the structural unit by ethylene derivative and the structural unit by unsaturated carboxylic acid derivative and ionomer thereof; Amine compound (have more than 2 amino in a part, fusing point is more than 30 DEG C); And mineral filler.The present invention is completed based on above-mentioned discovery.
That is, the concrete means for solving above-mentioned problem are as follows.
< 1 > resin combination, it contains:
Resinous principle (A) comprises at least one party in the multipolymer of the structural unit by ethylene derivative and the structural unit by unsaturated carboxylic acid derivative and ionomer thereof;
Amine compound (B), in a part, have more than 2 amino, fusing point is more than 30 DEG C; With
Mineral filler (C).
The resin combination of < 2 > as described in < 1 >, wherein, in the total amount of the resinous principle contained, the ratio shared by above-mentioned resinous principle (A) is more than 80 quality %.
The resin combination of < 3 > as described in < 1 > or < 2 >, wherein, in the total amount of the resinous principle contained, the ratio shared by above-mentioned resinous principle (A) is more than 90 quality %.
The resin combination of < 4 > according to any one of < 1 > ~ < 3 >, wherein, when being 100 mass parts with the total amount of above-mentioned resinous principle (A) and above-mentioned amine compound (B), the amount of above-mentioned resinous principle (A) is 99 mass parts ~ 80 mass parts, and the amount of above-mentioned amine compound (B) is 1 mass parts ~ 20 mass parts.
The resin combination of < 5 > according to any one of < 1 > ~ < 4 >, wherein, when being 100 mass parts with the total amount of above-mentioned resinous principle (A) and above-mentioned amine compound (B), the amount of mineral filler (C) is 20 mass parts ~ 100 mass parts.
The resin combination of < 6 > according to any one of < 1 > ~ < 5 >, wherein, the fusing point of above-mentioned amine compound (B) is more than 200 DEG C.
The resin combination of < 7 > according to any one of < 1 > ~ < 6 >, wherein, above-mentioned amine compound (B) has guanidine amine structure.
The resin combination of < 8 > according to any one of < 1 > ~ < 7 >, wherein, above-mentioned mineral filler (C) comprises at least a kind that is selected from calcium carbonate, clay, talcum and silicon-dioxide.
The resin combination of < 9 > according to any one of < 1 > ~ < 8 >, wherein, above-mentioned resinous principle (A) comprises above-mentioned ionomer.
The resin combination of < 10 > according to any one of < 1 > ~ < 9 >, wherein, above-mentioned mineral filler (C) comprises calcium carbonate.
< 11 > formed body, it comprises the resin combination according to any one of < 1 > ~ < 10 >.
By the present invention, resin combination and formed body that flame retardant resistance is significantly excellent can be provided.
Embodiment
" resin combination "
Resin combination of the present invention contains: resinous principle (A), and it comprises at least one party (hereinafter also referred to as " resinous principle (A) ") in the multipolymer of the structural unit by ethylene derivative and the structural unit by unsaturated carboxylic acid derivative and ionomer thereof; Amine compound (B), it has more than 2 amino in a part, and fusing point is more than 30 DEG C (hereinafter also referred to as " amine compound (B) "); With mineral filler (C).
Resin combination of the present invention, by the combination of resinous principle (A) and amine compound (B) and mineral filler (C), thus the flame retardant resistance that display is significantly excellent.
Be still not clear about the reason obtaining above-mentioned flame resistance effect, but be presumed as follows.
Namely, think by resin combination of the present invention except containing except resinous principle (A) and amine compound (B) also containing mineral filler (C), following state can be formed, that is, the state that the carboxyl contained in resinous principle (A) or its salt are crosslinked by the part amino (1 in more than 2 amino contained in a part of such as amine compound (B)) contained in amine compound (B).Think and do not use the whole amino contained in amine compound (B) in this is crosslinked, but it is amino to only used a part.Think and suppress crosslinked degree to a certain extent thus, so can maintain the mobility of resin combination to a certain extent, result, resinous principle (A) and amine compound (B) are mixed with having good uniformity.
And think, even if when applying heat wanting to make resin composition burns of the present invention, the major part of the heat applied due to remaining (untapped in crosslinked) that contain in amine compound (B) amino with the uncrosslinked carboxyl in resinous principle (A) or the crosslinking reaction of its salt and being consumed, result, become and not easily reach burning (that is, flame retardant resistance uprises).
Inferred by above content, resin combination of the present invention, by the combination of resinous principle (A) and amine compound (B) and mineral filler (C), present significantly excellent flame retardant resistance.
In resin combination of the present invention, when above-mentioned resinous principle (A) being replaced to other resinous principles (such as the ethylene unsaturated carboxylic acid's ester copolymer) beyond above-mentioned resinous principle (A), flame retardant resistance reduces.
In addition, in resin combination of the present invention, when amine compound (B) is replaced to fusing point lower than 30 DEG C and there is more than 2 amino amine compound in a part time, flame retardant resistance reduces.About its reason, although indefinite, following reason can be thought, when amine compound lower than 30 DEG C of melting mixing resinous principle (A) and fusing point, both poor compatibility; Fusing point volatilizees lower than the amine compound of 30 DEG C; Etc..
It should be noted that, in the present invention, " melting mixing " refers to, by be in molten state resinous principle (A), mix with other compositions (such as amine compound (B), mineral filler (C) etc.).Now, although resinous principle (A) becomes molten state, other compositions must not become molten state.
The optimal way of the melting mixing in the present invention is melting mixing.
In addition, in resin combination of the present invention, when being used as the normally used metal hydroxides of the fire retardant of resin (magnesium hydroxide, aluminium hydroxide etc.) to replace amine compound (B), there is following tendency: the mobility of resin combination significantly reduces, resinous principle (A) and metal hydroxides mixing itself are become difficulty.
In addition, in resin combination of the present invention, when not containing mineral filler (C), flame retardant resistance reduces.
In addition, according to resin combination of the present invention, by the combination of resinous principle (A) and amine compound (B) and mineral filler (C), flame retardant resistance improves, and wear resistance also improves.
About the reason obtaining above-mentioned wear resistance effect, although indefinite, be presumed as follows.
Namely, in resin combination of the present invention, as mentioned above, with the state that the carboxyl contained in following state, i.e. resinous principle (A) or its salt are crosslinked by the part amino contained in amine compound (B), resinous principle (A) is mixed with amine compound (B) with having good uniformity, and thinks that this contributes to improving wear resistance.
In resin combination of the present invention, when above-mentioned resinous principle (A) being replaced with other resinous principles (such as the ethylene unsaturated carboxylic acid's ester copolymer) beyond above-mentioned resinous principle (A), wear resistance reduces.
In addition, in resin combination of the present invention, when amine compound (B) is replaced with fusing point lower than 30 DEG C and there is more than 2 amino amine compound in a part time, wear resistance reduces.
In addition, in resin combination of the present invention, when not containing mineral filler (C), wear resistance reduces.
Next, the preferred scope containing ratio of the resinous principle (A) in resin combination of the present invention, amine compound (B) and mineral filler (C) is described, but the invention is not restricted to following preferable range.
In resin combination of the present invention, when being 100 mass parts with the total amount of resinous principle (A) and amine compound (B), the amount of preferred resin composition (A) is 99.9 mass parts ~ 60 mass parts, the amount of amine compound (B) is 0.1 mass parts ~ 40 mass parts, more preferably the amount of resinous principle (A) is 99 mass parts ~ 80 mass parts, and the amount of amine compound (B) is 1 mass parts ~ 20 mass parts.
When the amount of amine compound (B) is more than 0.1 mass parts, flame retardant resistance improves further.In addition, from the viewpoint of performance in practical use and economy, the amount of amine compound (B) is that below 40 mass parts are just enough.
In addition, in resin combination of the present invention, when being 100 mass parts with the total amount of above-mentioned resinous principle (A) and above-mentioned amine compound (B), the amount of mineral filler (C) is preferably 10 mass parts ~ 200 mass parts, is more preferably 20 mass parts ~ 100 mass parts.
When the amount of mineral filler (C) is more than 10 mass parts, flame retardant resistance improves further.
When the amount of mineral filler (C) is below 200 mass parts, formability and resin characteristics become better.
Below, each composition contained is described in resin combination of the present invention.
< resinous principle (A) >
Resin combination of the present invention contains resinous principle (A), and described resinous principle (A) at least comprises at least one party in the multipolymer (hereinafter also referred to " ethylene unsaturated carboxylic acid's multipolymer ") of the structural unit by ethylene derivative and the structural unit by unsaturated carboxylic acid derivative and ionomer thereof.
Above-mentioned ethylene unsaturated carboxylic acid's multipolymer carries out the multipolymer of copolymerization to major general's ethene and unsaturated carboxylic acid as copolymer composition.
As multipolymer, random copolymers, segmented copolymer etc. can be enumerated, preferred random copolymers.
As above-mentioned unsaturated carboxylic acid, unsaturated carboxylic acid or half ester that the carbonatomss such as such as vinylformic acid, methacrylic acid, ethylacrylic acid, methylene-succinic acid, itaconic anhydride, fumaric acid, β-crotonic acid, toxilic acid, maleic anhydride, maleic mono-ester (monomethyl maleate, ethyl maleate etc.), maleic anhydride monoesters (maleic anhydride mono-methyl, maleic anhydride monoethylester etc.) are 3 ~ 8 can be enumerated.
Wherein preferred vinylformic acid, methacrylic acid.
In above-mentioned ethylene unsaturated carboxylic acid's multipolymer, for the content of the structural unit by unsaturated carboxylic acid derivative, when considering the easiness of industry acquisition, relative to the total amount of multipolymer, be preferably 2 quality % ~ 40 quality %, be more preferably 2 quality % ~ 40 quality %, be particularly preferably 5 quality % ~ 25 quality %.
When being more than 2 quality % by the content of the structural unit of unsaturated carboxylic acid derivative, flame retardant resistance improves further.
In addition, in above-mentioned ethylene unsaturated carboxylic acid's multipolymer, for the content of the structural unit by ethylene derivative, relative to the total amount of multipolymer, be preferably 40 quality % ~ 98 quality %, be more preferably 60 quality % ~ 98 quality %, be particularly preferably 70 quality % ~ 95 quality %.
Above-mentioned ethylene unsaturated carboxylic acid's multipolymer also can comprise the structural unit derived by esters of unsaturated carboxylic acids.
As above-mentioned esters of unsaturated carboxylic acids, the alkyl ester of above-mentioned unsaturated carboxylic acid can be enumerated, the carbonatoms being preferably above-mentioned unsaturated carboxylic acid is the alkyl ester of 2 ~ 5, and more preferably the carbonatoms of above-mentioned unsaturated carboxylic acid is the alkyl ester (isobutyl ester, positive butyl ester etc.) of 4.
As above-mentioned esters of unsaturated carboxylic acids, specifically, methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Propenoic acid, 2-methyl, isobutyl ester, n-BMA, Isooctyl methacrylate, dimethyl maleate etc. can be enumerated.Wherein, the alkyl ester of the acrylic or methacrylic acid such as preferred methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Propenoic acid, 2-methyl, isobutyl ester, n-BMA, Isooctyl methacrylate, the lower alkyl esters (carbonatoms is the alkyl ester of 2 ~ 5) of more preferably acrylic or methacrylic acid.
The carbonatoms of preferably acrylic or methacrylic acid is the alkyl ester of 4 further, and wherein further preferred acrylic acid carbonatoms is the alkyl ester (particularly preferably isobutyl ester) of 4.
When above-mentioned ethylene unsaturated carboxylic acid's multipolymer comprises the structural unit derived by esters of unsaturated carboxylic acids, for the content of the structural unit derived by esters of unsaturated carboxylic acids, relative to the total amount of multipolymer, be preferably 3 quality % ~ 20 quality %, be more preferably 5 quality % ~ 20 quality %.
In above-mentioned ethylene unsaturated carboxylic acid's multipolymer, relative to the structural unit by ethylene derivative, the structural unit by unsaturated carboxylic acid derivative and the total 100 quality % of structural unit that derived by esters of unsaturated carboxylic acids, can containing be greater than 0 quality % and be below 30 quality %, be preferably greater than 0 quality % and be the structural unit derived by other co-polymerized monomers of below 25 quality %.
As other co-polymerized monomers above-mentioned, unsaturated ester (such as the vinyl ester such as vinyl-acetic ester and propionate), carbon monoxide, sulfurous gas etc. can be enumerated.
Ionomer in the present invention forms following structure, that is, the structure that the carboxyl contained in polymkeric substance (base polymer), this base polymer based on aforesaid ethylene unsaturated carboxylic acid's multipolymer is neutralized by metal ion.
Kind for above-mentioned metal ion is not particularly limited, such as, can enumerate the polyvalent metal ions etc. such as the alkalimetal ions such as lithium (Li) ion, potassium (K) ion, sodium (Na) ion, calcium (Ca) ion, magnesium (Mg) ion, zinc (Zn) ion, aluminium (Al) ion.Especially, from the viewpoint of the easiness of the reaction with amine compound (B), preferred polyvalent metal ion, wherein, particularly preferably zine ion.
The degree of neutralization of above-mentioned ionomer is preferably 10% ~ 90%, is more preferably 20% ~ 80%.
For the resinous principle (A) in the present invention, consider processibility and physical strength, according to JIS K7210-1999,190 DEG C, the melt flow rate (MFR) (MFR) that records under the condition of 2160g load is preferably 0.01 ~ 1000g/10 minute, is more preferably 0.1 ~ 100g/10 minute.
Resin combination of the present invention only can comprise a kind of resinous principle (A), also can comprise two or more.
In the total amount of the resinous principle contained by resin combination of the present invention, the ratio shared by resinous principle (A) is preferably more than 40 quality %.
The ratio of resinous principle (A) is that more than 40 quality % refer to, the major part in the resinous principle contained by resin combination of the present invention is resinous principle (A).Thus, flame retardant resistance improves further.
The ratio of above-mentioned resinous principle (A) is more preferably more than 60 quality %, more preferably more than 80 quality %, more preferably more than 90 quality %, more preferably more than 95 quality %, more preferably more than 98 quality %, most preferably be 100 quality % (that is, the mode that the resinous principle contained by resin combination of the present invention is only made up of above-mentioned resinous principle (A)).
Resin combination of the present invention can comprise other resinous principles beyond at least a kind of resinous principle (A).
As other resinous principles, be not particularly limited, such as polyethylene, ethylene unsaturated carboxylic acid's ester copolymer, ethylene vinyl acetate copolymer etc. can be enumerated.As other resinous principles, preferably polyethylene.
As polyethylene, high density polyethylene(HDPE) (HDPE), high-pressure process low-density polyethylene (LDPE), straight-chain Low Density Polyethylene (LLDPE) etc. can be enumerated.HDPE, LDPE and LLDPE can be used alone a kind, also can use with the form of mixture of more than two kinds.
In addition, from the viewpoint of improving flame retardant resistance and wear resistance further, resinous principle (A) preferably comprises above-mentioned ionomer.
When resinous principle (A) comprises above-mentioned ionomer, relative to the total amount of resinous principle (A), the ratio of above-mentioned ionomer is preferably more than 40 quality %, be more preferably more than 60 quality %, more preferably more than 80 quality %, more preferably more than 90 quality %, most preferably are 100 quality % (mode that above-mentioned resinous principle (A) is only made up of above-mentioned ionomer).
When the ratio of the ionomer in above-mentioned resinous principle (A) is more than 40 quality %, flame retardant resistance improves further.Although its reason is indefinite, infer it is following reason: resinous principle (A) improves with the reactivity of amine compound (B), flame retardant resistance improves.
In addition, when the ratio of the ionomer in above-mentioned resinous principle (A) is more than 40 quality %, wear resistance also improves further.
In addition, content for the resinous principle (A) in resin combination of the present invention is not particularly limited, and relative to resin combination total amount, is preferably 20 quality % ~ 99.9 quality %, be more preferably 40 quality % ~ 90 quality %, be particularly preferably 50 quality % ~ 80 quality %.
< amine compound (B) >
Resin combination of the present invention contains amine compound (B), and described amine compound (B) has more than 2 amino in a part, and fusing point is more than 30 DEG C.
From the viewpoint of improving flame retardant resistance further, the fusing point of amine compound (B) is preferably more than 200 DEG C, is more preferably more than 250 DEG C.
When the fusing point of amine compound (B) is more than 200 DEG C, when with resinous principle (A) melting mixing, dissolving or the decomposition of amine compound (B) can be suppressed, therefore, it is possible to homogeneity mixes with the above-mentioned resinous principle (A) being in molten state better.Thus, flame retardant resistance when forming resin combination improves further.
As amine compound (B), be not particularly limited, such as guanamines (another name: 2,4-diamino-1,3,5-triazines) (fusing point more than 300 DEG C can be enumerated, molecular weight 111.11), CTU guanamines (two [2-(3,5-diamino-2,4,6-triazinyl) ethyl]-2,4,8,10-tetra-oxaspiro [5.5] undecanes of another name: 3,9-) (fusing point 270 DEG C, molecular weight 434.46), acetylguanamine (another name: 2,4-diamino-6-methyl isophthalic acid, 3,5-triazine) (fusing point 274 DEG C ~ 276 DEG C, molecular weight 125.13), benzoguanamine (another name: 2,4-diamino-6-phenyl-1,3,5-triazines) (fusing point 219 DEG C ~ 221 DEG C, molecular weight 187.2), hexamethylene-diamine (fusing point 39 DEG C ~ 42 DEG C, molecular weight 116.20), 2,4 di amino toluene (fusing point 99 DEG C, molecular weight 122.17), 4,4 '-diaminodiphenyl-methane (another name: 4,4 '-methylene dianiline (MDA)) (fusing point 91 DEG C, molecular weight 198.26), 4,4 '-diamino-diphenyl ethane (fusing point 136 DEG C ~ 138 DEG C, molecular weight 212.29) etc.
In addition, as amine compound (B), also can enumerate fusing point in the two guanidine amine compound recorded in urea, the derivative of urea and the amidine derivative and Japanese Unexamined Patent Publication 5-202007 publication recorded in the guanidine amine compound recorded in Japanese Unexamined Patent Publication 2004-203846 publication and salt thereof, Japanese Unexamined Patent Publication 2000-239485 publication and be more than 30 DEG C and there are more than 2 amino compounds in a part.
As amine compound (B), preferably there is the compound of triazine structure, be more preferably the compound with guanidine amine structure.
Herein, as the compound with triazine structure, as long as have at least 1 triazine structure in a part, be not particularly limited.In addition, as the compound with guanidine amine structure, as long as have at least 1 guanidine amine structure in a part, be not particularly limited.
Herein, guanidine amine 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 guanidine amine structure, guanamines, CTU guanamines, acetylguanamine, benzoguanamine can be enumerated.
In the compound with guanidine amine structure, particularly preferably fusing point is the compound of more than 200 DEG C (preferably more than 250 DEG C).As such compound, guanamines, CTU guanamines, acetylguanamine, benzoguanamine can be enumerated, preferred guanamines, CTU guanamines, acetylguanamine.
Molecular weight for amine compound (B) is not particularly limited, and from the viewpoint of more effectively playing effect of the present invention, being preferably less than more than 100 1000, being more preferably less than more than 200 600, being particularly preferably less than more than 400 500.
Resin combination of the present invention only can comprise a kind of amine compound (B), also can comprise two or more.
In addition, content for the amine compound (B) in resin combination of the present invention is not particularly limited, relative to resin combination total amount, be preferably 0.05 quality % ~ 40 quality %, be more preferably 0.1 quality % ~ 40 quality %, more preferably 0.5 quality % ~ 20 quality %, more preferably 1 quality % ~ 20 quality %, be particularly preferably 1 quality % ~ 10 quality %.
< mineral filler (C) >
Resin combination of the present invention contains mineral filler (C).
Resin combination of the present invention only can comprise a kind of mineral filler (C), also can comprise two or more.
As mineral filler (C), be not particularly limited, known mineral filler can be used.
As mineral filler (C), specifically, calcium carbonate, clay, talcum, silicon-dioxide, fortifying fibre (glass fibre, carbon fiber etc.), sheet glass (glass flake), mica etc. can be enumerated.As mineral filler (C), the mineral filler of synthesis can be used, also can use commercially available product.
From the viewpoint of improving flame retardant resistance further, mineral filler (C) preferably comprises at least a kind that is selected from calcium carbonate, clay, talcum and silicon-dioxide, preferably comprise at least a kind that is selected from calcium carbonate, clay and talcum, more preferably comprise calcium carbonate.
In addition, by making mineral filler (C) comprise to be selected from least a kind in calcium carbonate, clay, talcum and silicon-dioxide (be more preferably selected from least a kind in calcium carbonate, clay and talcum, more preferably calcium carbonate), thus also improve wear resistance.
When mineral filler (C) comprises calcium carbonate, mineral filler (C) can be only wrap mineral filler calciferous, also can be the mineral filler comprising calcium carbonate and other mineral fillers (being such as selected from least a kind in clay, talcum and silicon-dioxide).
When mineral filler (C) comprises calcium carbonate, relative to mineral filler (C) total amount, the ratio of the amount of calcium carbonate is preferably more than 50 quality %, be more preferably more than 80 quality %, more preferably more than 90 quality %, most preferably are 100 quality % (mode that above-mentioned mineral filler (C) is only made up of calcium carbonate).
Content for the mineral filler (C) in resin combination of the present invention is not particularly limited, relative to resin combination total amount, be preferably 10 quality % ~ 70 quality %, be preferably 10 quality % ~ 60 quality %, be more preferably 10 quality % ~ 50 quality %.
Other compositions of < >
In the scope not damaging object of the present invention, resin combination of the present invention also can comprise other compositions beyond mentioned component.
As other compositions, antioxidant, protective agent, photostabilizer, thermo-stabilizer, UV light absorber, lubricant (Metallic stearates such as such as Zinic stearas), anti-hard caking agent, softening agent, tackiness agent, tinting material (pigment, dyestuff), fire retardant (such as metal hydroxides (magnesium hydroxide, aluminium hydroxide etc.)), flame retardant, whipping agent, frothing aid, dimeracid (or its metal-salt) etc. can be enumerated.
In addition, from the viewpoint of more effectively playing effect of the present invention, relative to resin combination total amount, the total amount of resinous principle (A), amine compound (B) and mineral filler (C) is preferably more than 80 quality %, be more preferably more than 85 quality %, be particularly preferably more than 90 quality %.
For resin combination of the present invention, according to JIS K7210-1999,230 DEG C, the melt flow rate (MFR) (MFR) that records under the condition of 10kg load is preferably 0.01 ~ 1000g/10 minute, is more preferably 0.1 ~ 100g/10 minute.
< manufacture method >
As manufacturing the method for resin combination of the present invention, as long as will at least method that mixes of resinous principle (A), amine compound (B) and mineral filler (C), be not particularly limited.
As the example of the method for manufacture resin combination of the present invention, can following methods be enumerated:
(method 1) is by the method for resinous principle (A), amine compound (B) and mineral filler (C) (and other compositions as required) melting mixing;
(method 2) first, by resinous principle (A) and amine compound (B) melting mixing, in the mixture obtained, add mineral filler (C) (and other compositions as required), carry out the method for melting mixing further; Etc..
Wherein, from the viewpoint of with better homogeneity, each composition is mixed, preferred method 2.
As the mode of the melting mixing in method 1 and method 2, preferred molten is mixing.
For the melting mixing in method 1 and method 2, known mixing device (kneading device such as such as single screw extrusion machine, twin screw extruder, Banbury mixer, kneader) can be used to carry out.
As resin temperature during melting mixing in aforesaid method 1, be preferably more than 150 DEG C less than 250 DEG C.
In aforesaid method 2, as by resin temperature when resinous principle (A) and amine compound (B) melting mixing, be preferably more than 200 DEG C less than 350 DEG C, be more preferably more than 200 DEG C less than 330 DEG C, be particularly preferably more than 250 DEG C less than 300 DEG C.
In aforesaid method 2, as by the resin temperature when mixture of resinous principle (A) and amine compound (B) and mineral filler (C) melting mixing, be preferably more than 150 DEG C less than 250 DEG C, further, be preferably than by temperature low for resin temperature when resinous principle (A) and amine compound (B) melting mixing.
" formed body "
Formed body of the present invention comprises resin combination of the present invention and forms, be utilize known method by shaping for resin combination of the present invention and formed.
As shaping method, the various methods such as hot-forming, extrusion moulding (melt extruding shaping), injection molding, blow molding, drawing and forming can be enumerated.
As described above, resin combination excellent in flame retardance of the present invention, therefore, by shaping for this resin combination and formed body that is that obtain can be widely used in the building such as ceiling materials, baseboard material, engineering materials; Trolley part; OA equipment; Electrical and electronic parts, household electrical appliances article component, solar cell component parts (such as back-sheet, sealing material etc.) or their keeping containing box; Stationery; The purposes such as daily necessities.
Embodiment
Next, in further detail the present invention is described by embodiment, but the present invention is not by any restriction of these examples.
Hereinafter, " part " represents mass parts.
In addition, as the resinous principle of raw material melt flow rate (MFR) (MFR) according to JISK7210-1999,190 DEG C, measure under the condition of 2160g load.
In addition, " ethylene content " refers to the structural unit that the derives from ethene content (quality %) (other the record about " content " too) relative to multipolymer entirety.
< raw material >
The raw material used in the present embodiment is as follows.
-resinous principle-
Ionomer 1:
The zinc ionomer (degree of neutralization=59%, MFR=0.9g/10 minute) of ethylene methacrylic acid copolymer (ethylene content=85 quality %, methacrylic acid content=15 quality %)
Ionomer 2:
The sodium ionomer (degree of neutralization=54%, MFR=0.9g/10 minute) of ethylene methacrylic acid copolymer (ethylene content=85 quality %, methacrylic acid content=15 quality %)
Ionomer 3:
The zinc ionomer (degree of neutralization=70%, MFR=1g/10 minute) of ethylene methacrylic acid isobutyl acrylate copolymer (ethylene content=80 quality %, methacrylic acid content=10 quality %, i-butyl ester content=10 quality %)
Ionomer 4:
The zinc ionomer (degree of neutralization=21%, MFR=16g/10 minute) of ethylene methacrylic acid copolymer (ethylene content=85 quality %, methacrylic acid content=15 quality %)
·EMAA1：
Ethylene methacrylic acid copolymer (ethylene content=85 quality %, methacrylic acid content=15 quality %, MFR=25g/10 minute)
·EMAA2：
Ethylene methacrylic acid isobutyl acrylate copolymer (ethylene content=80 quality %, methacrylic acid content=10 quality %, i-butyl ester content=10 quality %, MFR=35g/10 minute)
·EMAA3：
Ethylene methacrylic acid isobutyl acrylate copolymer (ethylene content=80 quality %, methacrylic acid content=10 quality %, i-butyl ester content=10 quality %, MFR=30g/10 minute)
·EEA1：
Ethylene ethyl acrylate copolymer (ethylene content=82 quality %, ethyl propenoate content=18 quality %, MFR=6g/10 minute)
·EEA2：
Ethylene ethyl acrylate copolymer (ethylene content=84 quality %, ethyl propenoate content=16 quality %, MFR=1g/10 minute)
·EVA1：
Ethylene vinyl acetate copolymer (ethylene content=81 quality %, vinyl acetate content=19 quality %, MFR=2.5g/10 minute)
·EVA2：
Ethylene vinyl acetate copolymer (ethylene content=83 quality %, vinyl acetate content=17 quality %, MFR=0.8g/10 minute)
·PE：
Straight-chain Low Density Polyethylene (LLDPE) (the EVOLUE SP0511 of (strain) Prime Polymer; Density=903kg/m
3, MFR=1.2g/10 minute)
In above-mentioned resinous principle, ionomer 1, ionomer 2, ionomer 3, ionomer 4, EMAA1, EMAA2 and EMAA3 belong to the resinous principle (A) in the present invention.
-amine compound-
Aceto: acetylguanamine (fusing point 274 DEG C ~ 276 DEG C)
CTU:CTU guanamines (fusing point 270 DEG C)
4,4 '-diaminodiphenyl-methane (fusing point 91 DEG C)
The two aminomethyl cyclohexane (fusing point-70 DEG C) of 1,3-BAC:1,3-
Quadrol (fusing point 9 DEG C)
In above-mentioned amine compound, Aceto, CTU and 4,4 '-diaminodiphenyl-methane belongs to the amine compound (B) in the present invention.
-mineral filler-
Calcium carbonate (CaCO
3; Day, eastern efflorescence industry (strain) made (trade(brand)name; NCC#110))
Clay (Northeast chemistry (strain) system (trade(brand)name; KAOLIN))
Talcum (loose village industry (strain) system (trade(brand)name; HiFiller#5000PJ))
Silicon-dioxide (SiO
2; FUJI SILYSIA CHEMICAL LTD. system (trade(brand)name; SYLYSIA 450))
-other compositions-
Zinic stearas (pharmaceutical worker industry (strain) system pure with light)
Magnesium hydroxide (Mg (OH)
2; " KISUMA5A " that consonance chemical industry (strain) is made)
(embodiment 1)
The making > of < resin combination
Using the ionomer 1 (95 mass parts) as resinous principle and the Aceto (5 mass parts) as amine compound melting mixing 15 minutes under the resin temperature of 275 DEG C, using the mixing thing (100 mass parts) that obtains and the CaCO as mineral filler
3(50 mass parts) melting mixing 10 minutes under the resin temperature of 200 DEG C, obtains resin combination.
The making of < formed body and evaluation >
Under the resin temperature of 180 DEG C, hot pressing is carried out to the resin combination obtained, obtain the test sheet material 1 (formed body) of thick 3mm.
From the test sheet material 1 obtained, cut out the test film of 80mm × 6.5mm × thick 3mm, for this test film, the evaluation below having carried out is as the evaluation of flame retardant resistance.
Evaluation result is shown in following table 1.
(mensuration of oxygen index (O.I))
For above-mentioned test film, carry out combustion test according to JIS K7201-1995, determine oxygen index (O.I).
The value of the oxygen index recorded is larger, represents flame retardant resistance more excellent (namely flame retardant resistance is high).
(evaluation of drippage (drip))
When burning in above-mentioned combustion test, visual confirmation is with or without drippage.
Excellent in flame retardance (namely flame retardant resistance is high) is represented without drippage.
(embodiment 2 ~ 12)
In embodiment 1, change the kind of resinous principle and amount, the kind of amine compound and the kind of amount and mineral filler and amount as shown in table 1ly, in addition, make resin combination similarly to Example 1, carry out making and the evaluation of formed body similarly to Example 1.
Evaluation result is shown in following table 1.
(embodiment 13)
In example 4, by resinous principle and amine compound and mineral filler melting mixing 10 minutes under the resin temperature of 200 DEG C simultaneously, in addition, make resin combination similarly to Example 4, carry out making and the evaluation of formed body similarly to Example 4.
Evaluation result is shown in following table 1.
(comparative example 1)
In embodiment 1, do not use amine compound and mineral filler, be used as the ionomer 1 of resinous principle to make formed body, in addition, carry out making and the evaluation of formed body similarly to Example 1.
Evaluation result is shown in following table 1.
(comparative example 2,17 and 20)
In comparative example 1, change the kind of resinous principle as shown in table 1ly, in addition, carry out making and the evaluation of formed body in the same manner as comparative example 1.
Evaluation result is shown in following table 1.
(comparative example 3 ~ 13,15,16,18,19,21,22 and 23)
In embodiment 1, change the kind of resinous principle and amount, the kind of amine compound and the kind of amount and mineral filler and amount as shown in table 1ly, in addition, make resin combination similarly to Example 1, carry out making and the evaluation of formed body similarly to Example 1.
Herein, the amount of amine compound is made to be resin combination in the example (not using the example of amine compound) of 0 mass parts, by melting mixing under the resin temperature of 200 DEG C makes for 10 minutes by resinous principle and mineral filler.
In addition, the amount of mineral filler is made to be resin combination in the example (not using the example of mineral filler) of 0 mass parts, by melting mixing under the resin temperature of 275 DEG C makes for 15 minutes by resinous principle and amine compound.
Evaluation result is shown in following table 1.
(comparative example 14)
Using the ionomer 1 (95 mass parts) as resinous principle with as 1 of amine compound, 3-BAC (5 mass parts) melting mixing 15 minutes under the resin temperature of 200 DEG C, using the mixing thing (100 mass parts) that obtains and the CaCO as mineral filler
3(50 mass parts) melting mixing 10 minutes under the resin temperature of 200 DEG C, makes resin combination, carries out making and the evaluation of formed body similarly to Example 1.
Evaluation result is shown in following table 1.
[table 1]
-explanation of Biao 1-
The amount (part) of each composition is mass parts.
As shown in table 1, employ the embodiment 1 ~ 13 of resinous principle (A), amine compound (B) and mineral filler (C), compared with the comparative example 1 ~ 23 of at least a kind lacked in resinous principle (A), amine compound (B) and mineral filler (C), oxygen index is high, excellent in flame retardance.
In detail, for using ionomer 1 to improve effect as flame retardant resistance when resinous principle (A), such as, can 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 19.0) being used alone ionomer 1, only with the addition of in ionomer 1 in the comparative example 7 (oxygen index 19.0) of amine compound (B), oxygen index does not increase.In addition, compared with this comparative example 1, in ionomer 1, only with the addition of oxygen index in the comparative example 3 (oxygen index 21.5) of mineral filler (C) is also the degree slightly increased.On the other hand, with the addition of in ionomer 1 in the embodiment 2 (oxygen index 28.0) of amine compound (B) and mineral filler (C), oxygen index enlarges markedly.
Similarly, also can confirm use ionomer 2, ionomer 3 or EMAA1 by table 1 (especially oxygen index) and improve effect as flame retardant resistance time resinous principle (A).
In addition, effect being improved for the flame retardant resistance by using resinous principle (A) to obtain as resinous principle, also can be confirmed by embodiment 1 ~ 13 and comparative example 10 ~ 13.
Such as, even if add amine compound (B) and mineral filler (C) both (comparative examples 12) in EEA1 (not belonging to resinous principle (A)), compared with the situation (comparative example 10,11) of only adding certain one in amine compound (B) and mineral filler (C) in EEA1, oxygen index does not also almost increase.
(embodiment 14)
Using as the ionomer 3 (85.5 mass parts) of resinous principle and PE (9.5 mass parts), the Aceto (5 mass parts) as amine compound and the calcium carbonate (50 mass parts) as mineral filler melting mixing 10 minutes under the resin temperature of 200 DEG C simultaneously, obtain resin combination.
Use the resin combination obtained, similarly to Example 13, carry out making and the evaluation of formed body.As a result, oxygen index is 25.5, without drippage.
(embodiment 15)
Using the ionomer 1 (95 mass parts) as resinous principle with as 4 of amine compound, 4 '-diaminodiphenyl-methane (with pure pharmaceutical worker's industry (strain) system of light, fusing point 91 DEG C, 5 mass parts) melting mixing 15 minutes under the resin temperature of 200 DEG C, using the mixing thing (100 mass parts) that obtains and the CaCO as mineral filler
3(50 mass parts) melting mixing 10 minutes under the resin temperature of 200 DEG C, obtains resin combination.
Use the resin combination obtained, carry out making and the evaluation of formed body similarly to Example 1.As a result, oxygen index is 26.0, without drippage.
(comparative example 24)
Using the ionomer 1 (95 mass parts) as resinous principle and the quadrol as amine compound (with pure pharmaceutical worker's industry (strain) system of light, fusing point 9 DEG C, 5 mass parts) melting mixing 15 minutes under the resin temperature of 200 DEG C, using the mixing thing (100 mass parts) that obtains and the CaCO as mineral filler
3(50 mass parts) melting mixing 10 minutes under the resin temperature of 200 DEG C, obtains resin combination.
Use the resin combination obtained, carry out making and the evaluation of formed body similarly to Example 1.As a result, oxygen index is 24.0, without drippage.
(embodiment 16 ~ 19, comparative example 25 ~ 30)
Use the resin combination shown in following table 2, carry out making and the evaluation of formed body similarly to Example 1.Evaluation result is shown in following table 2.
Compounding process " 1 " in following table 2 and the details of " 2 " as follows.
-compounding process-
" 1 " is the compounding process in embodiment 13.That is, by whole composition melting mixing method of 10 minutes under the resin temperature of 200 DEG C simultaneously.
" 2 " are the compounding process in embodiment 1.That is, first, by resinous principle and amine compound melting mixing 15 minutes under the resin temperature of 275 DEG C, mixing thing is made, next, the melting mixing method of 10 minutes under the resin temperature of 200 DEG C by this mixing thing and mineral filler.
(making of formed body and the evaluation of wear resistance)
In above-described embodiment 16 ~ 19 and comparative example 25 ~ 30, carry out the evaluation of wear resistance further as described below.
The resin combination of hot pressing gained under the resin temperature of 180 DEG C, obtains the test sheet material 2 (formed body) of thick 2mm.
From the above-mentioned test sheet material 2 obtained, cut out the discoid test film of diameter 107mm, thick 2mm.For the discoid test film obtained, with reference to JIS K7204-1999, under the environment of 23 DEG C of 55%RH, use Taber wear testing machine (Toyo Co., Ltd.'s essence mechanism makes made Rotating Cutter tester (Rotary Abrasion Tester) (model T)), use CS17 as abrasion wheel, be 1kg at load, under speed of rotation is 60rpm, revolution is the condition of 1000 turns, carry out Taber wear test.
From the quality of the discoid test film before above-mentioned Taber wear test, deduct the quality of the discoid test film after above-mentioned Taber wear test, obtain Taber wear loss (mg) thus.The value of this Taber wear loss (mg) is less, represents that wear resistance is more excellent.
Taber wear loss (mg) is shown in following table 2.
[table 2]
As shown in table 2, in embodiment 16 ~ 19, flame retardant resistance and excellent in abrasion resistance.
By whole disclosures of Japanese patent application 2012-247484 of filing an application on November 9th, 2012 by referring to being incorporated in this specification sheets.
The all documents recorded in this specification sheets, patent application and technological standard, by referring to being merged in this specification sheets, each document, patent application and technological standard by referring to be merged in degree with specifically and the degree of situation about recording respectively is identical.
Claims (11)
1. a resin combination, it contains:
Resinous principle (A), described resinous principle (A) comprises at least one party in the multipolymer of the structural unit by ethylene derivative and the structural unit by unsaturated carboxylic acid derivative and ionomer thereof;
Amine compound (B), described amine compound (B) has more than 2 amino in a part, and fusing point is more than 30 DEG C; With
Mineral filler (C).
2. resin combination as claimed in claim 1, wherein, in the total amount of the resinous principle contained, the ratio shared by described resinous principle (A) is more than 80 quality %.
3. resin combination as claimed in claim 1 or 2, wherein, in the total amount of the resinous principle contained, the ratio shared by described resinous principle (A) is more than 90 quality %.
4. the resin combination according to any one of claims 1 to 3, wherein, when being 100 mass parts with the total amount of described resinous principle (A) and described amine compound (B), the amount of described resinous principle (A) is 99 mass parts ~ 80 mass parts, and the amount of described amine compound (B) is 1 mass parts ~ 20 mass parts.
5. the resin combination according to any one of Claims 1 to 4, wherein, when being 100 mass parts with the total amount of described resinous principle (A) and described amine compound (B), the amount of mineral filler (C) is 20 mass parts ~ 100 mass parts.
6. the resin combination according to any one of Claims 1 to 5, wherein, the fusing point of described amine compound (B) is more than 200 DEG C.
7. the resin combination according to any one of claim 1 ~ 6, wherein, described amine compound (B) has guanidine amine structure.
8. the resin combination according to any one of claim 1 ~ 7, wherein, described mineral filler (C) comprises at least a kind that is selected from calcium carbonate, clay, talcum and silicon-dioxide.
9. the resin combination according to any one of claim 1 ~ 8, wherein, described resinous principle (A) comprises described ionomer.
10. the resin combination according to any one of claim 1 ~ 9, wherein, described mineral filler (C) comprises calcium carbonate.
11. 1 kinds of formed bodys, it comprises the resin combination according to any one of claim 1 ~ 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-247484 | 2012-11-09 | ||
| JP2012247484 | 2012-11-09 | ||
| PCT/JP2013/080309 WO2014073661A1 (en) | 2012-11-09 | 2013-11-08 | Resin composition and molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104769032A true CN104769032A (en) | 2015-07-08 |
| CN104769032B CN104769032B (en) | 2017-08-04 |
Family
ID=50684752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380056904.XA Active CN104769032B (en) | 2012-11-09 | 2013-11-08 | Resin combination and formed body |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6196630B2 (en) |
| KR (1) | KR101821277B1 (en) |
| CN (1) | CN104769032B (en) |
| WO (1) | WO2014073661A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111683975A (en) * | 2018-02-15 | 2020-09-18 | 三井—陶氏聚合化学株式会社 | Modified resin for molded body and golf ball |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10325988B2 (en) | 2013-12-13 | 2019-06-18 | Power Integrations, Inc. | Vertical transistor device structure with cylindrically-shaped field plates |
| JP7265521B2 (en) * | 2018-02-15 | 2023-04-26 | 三井・ダウポリケミカル株式会社 | Modified resin for molding and golf ball |
| KR102618416B1 (en) * | 2019-03-20 | 2023-12-28 | 미츠이·다우 폴리케미칼 가부시키가이샤 | Resin composition for laminated glass interlayer, laminated glass interlayer and laminated glass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231400A (en) * | 1997-02-18 | 1998-09-02 | Du Pont Mitsui Polychem Co Ltd | Golf ball material and ionomer composition |
| 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 |
Family Cites Families (5)
| 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 |
| 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 JP JP2014545779A patent/JP6196630B2/en active Active
- 2013-11-08 WO PCT/JP2013/080309 patent/WO2014073661A1/en active Application Filing
- 2013-11-08 CN CN201380056904.XA patent/CN104769032B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231400A (en) * | 1997-02-18 | 1998-09-02 | Du Pont Mitsui Polychem Co Ltd | Golf ball material and ionomer composition |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111683975A (en) * | 2018-02-15 | 2020-09-18 | 三井—陶氏聚合化学株式会社 | Modified resin for molded body and golf ball |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6196630B2 (en) | 2017-09-13 |
| KR20150067324A (en) | 2015-06-17 |
| WO2014073661A1 (en) | 2014-05-15 |
| CN104769032B (en) | 2017-08-04 |
| KR101821277B1 (en) | 2018-01-23 |
| JPWO2014073661A1 (en) | 2016-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101175821B (en) | Flame retardant polyamide composition | |
| TW483915B (en) | Flame retardant resin composition | |
| CN103554637B (en) | High-elasticity wear-resistant low-smoke halogen-free flame-retardant injection molding material and preparation method thereof | |
| CN104769032A (en) | Resin composition and molded article | |
| CN103421309A (en) | Cold-resistant super-tough reinforced nylon 6 material for automobiles and preparation method thereof | |
| CN101790550A (en) | Graft copolymer, thermoplastic resin composition, and molded object | |
| CN104371143A (en) | Additive for plastic and application of additive, and flame-retardant polymer molding composition formed by additive | |
| KR20080040758A (en) | Flame-retardant resin composition | |
| JP2016531982A (en) | Flexible flame retardant thermoplastic composition with high thermomechanical strength, especially for electrical cables | |
| TWI468458B (en) | Methacrylic resin composition and compact | |
| JP2021533216A (en) | Ionomer of ethylenic acid copolymer with improved creep resistance | |
| JP2021532224A (en) | Ionomer of ethylenic acid copolymer with improved creep resistance | |
| CN104592509A (en) | Low-pH value polyamide molding composition | |
| KR101097185B1 (en) | Composition containing styrene resin, and molded article | |
| JP2011032327A (en) | Thermoplastic resin composition | |
| JP6420995B2 (en) | Flame-retardant polyamide resin composition and molded article thereof | |
| JP5144886B2 (en) | Resin composition | |
| CN111748153A (en) | Novel environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| JP2001031803A (en) | Flame-retardant resin composition | |
| JP7374984B2 (en) | ionomer composition | |
| JP4749524B2 (en) | Flame retardant resin composition | |
| JP5917968B2 (en) | POLYMER TYPE ANTISTATIC AGENT, POLYMER COMPOSITION, AND MOLDED ARTICLE | |
| JP2009298869A (en) | Cable housing | |
| CN116694067A (en) | Heat-conducting plastic-coated aluminum composition for lamp decoration, particles, preparation method of particles and lamp decoration piece | |
| JP6322435B2 (en) | Flame retardant resin composition and molded body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: Mitsui-Dow Polymerization Chemical Co., Ltd. Address before: Tokyo, Japan, Japan Patentee before: Mitsui Du Pont Polychemical |
|
| CP01 | Change in the name or title of a patent holder |