CN1223633C - Polyacetal resin composition - Google Patents
Polyacetal resin composition Download PDFInfo
- Publication number
- CN1223633C CN1223633C CN 02123271 CN02123271A CN1223633C CN 1223633 C CN1223633 C CN 1223633C CN 02123271 CN02123271 CN 02123271 CN 02123271 A CN02123271 A CN 02123271A CN 1223633 C CN1223633 C CN 1223633C
- Authority
- CN
- China
- Prior art keywords
- acid
- hydroxy
- polyacetal resin
- glass
- category
- 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.)
- Expired - Lifetime
Links
Abstract
The invention provides a polyacetal resin composition compounded with a glass filler improved in mechanical characteristics. This polyacetal resin composition contains (A) a polyacetal resin in an amount of 100 pts.wt., (B) the glass filler in an amount of 3-200 pts.wt., and (C) a hydroxycarboxylic acid compound having a carboxy group and an alcoholic hydroxyl group in its molecule in an amount of 0.001-3 pts.wt.
Description
Technical field:
The present invention relates to a kind of polyacetal resin composite with good mechanical properties.
Background technology:
Well known, for the mechanical characteristics that improves polyacetal resin for example intensity and rigidity, can add category of glass inorganic filling material etc. as its strengthening material.But, because the chemical property torpescence of polyacetal resin, and the category of glass inorganic filling material also lacks chemically reactive, even dissolve and mix so add the category of glass inorganic filling material to polyacetal resin, also do not have good reinforcing effect, its physical strength is also lower than the polyacetal resin of not strengthening sometimes on the contrary.
In order to improve this point, also can adopt through epoxy compounds, silane compound, titanate ester compound surface-treated category of glass inorganic filling material improves its mechanical characteristics thus.
But,, require to have higher mechanical characteristics in recent years under many circumstances, and the present method of understanding can not satisfy corresponding requirements well with the expansion of polyacetal resin Application Areas.
Summary of the invention:
In view of more than, present inventors etc. confirm that through wholwe-hearted research inorganic filling material with specific compound and polyacetal resin and category of glass dissolves the composition of preparing after mixing jointly, can obviously improve the mechanical characteristics of polyacetal resin composite, thereby finish the present invention.
Promptly the present invention relates to a kind of (A) in the polyacetal resin of per 100 weight parts, add (B) 3-200 weight part the category of glass inorganic filling material and, (C) have the hydroxy carboxylic acid compound of carboxyl and alcoholic extract hydroxyl group in each molecule of 0.001-3 weight part and the polyacetal resin composite that forms.Promptly contain above-mentioned A, the composition of B and C.
Below the present invention will be described in detail.
The polyacetal resin that uses among the present invention (A) is with oxygen methylene radical (CH
2O-) macromolecular compound of the main component units of conduct, in fact, also can use with the oxygen methylene radical is to repeat also to contain outside unitary polyacetal homopolymer, the deoxygenation methylene radical any in the Copolyacetal (comprising segmented copolymer) of a small amount of other component units and the terpolymer etc.And their molecular structure can be a wire, also can be a chain or a crosslinked shape.In addition, also can select for use in the above-mentioned polyacetal resin two or more as blend simultaneously.
In above-mentioned polyacetal resin of the present invention, preferred Copolyacetal, for example: the Copolyacetal that the polymer monomers of copolymerization 0.1-30 weight % obtains, the preferably Copolyacetal that obtains of the polymer monomers of copolymerization 0.5-5 weight %.Can keep various characteristics such as plasticity, thermostability, mechanical characteristics etc. simultaneously thus.
The monomer component for preparing this type of Copolyacetal is had no particular limits, generally use compound with following formula.
(the R in the formula
1, R
2, R
3And R
4Represent hydrogen atom or alkyl, they can be identical groups, can be different groups also, are generally hydrogen atom.R
5Methylene radical that representative is replaced by methylene radical, oxygen methylene radical, oxygen methylene radical or oxygen methylene radical (p represents the integer of 0-3 here) or with formula-(CH
2)
q-OCH
2-or-(O-CH
2-CH
2)
q-OCH
2The divalent group (p represents the integer of 1-4 here) of-expression.
This polymer monomers can be oxyethane, epoxy chloropropane, 1,3-dioxolane, glycol ether methylal, 1,4-butyleneglycol methylal, 1,3-dioxane, propylene oxide etc.
The category of glass inorganic filling material of (B) composition of Shi Yonging can be the mixture of packing material, hollow form (glass balloon) or these materials of fibrous (glass fibre), powdery (grinding (ミ Le De) fiber), granular (granulated glass sphere), tabular (glass flake) as required in the present invention.
These category of glass inorganic filling materials can use not have treatedly, but preferably select for use titanate ester or silicane coupler to carry out the inorganic filling material of handling.
The titanate ester surface treatment agent can be titanium-isopropoxy octyne ethyl glycolate, four-titanium n-butoxide, four (2-ethyl hexyl oxy) titanium etc.
The silicane coupler can be vinyl alkoxy silane, oxirane TMOS, aminoalkoxy silane, sulfydryl organoalkoxysilane, allyl group organoalkoxysilane etc.
Vinyl alkoxy silane can be vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane etc.
The oxirane TMOS can be γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl-triethoxysilicane etc.
Aminoalkoxy silane can be enumerated as gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane etc.
The sulfydryl organoalkoxysilane can be enumerated as γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane etc.
The allyl group organoalkoxysilane can be enumerated as γ-diallyl TSL 8330, γ-allyl amino propyl trimethoxy silicane, γ-allyl sulfide for propyl trimethoxy silicane etc.
Use any in these surface treatment agents all to produce effect, but consider the surface treatment agent that aminoalkoxy silane is best suited for from purpose of the present invention.
Corresponding to the inorganic filling material of per 100 weight parts, the surface treatment agent consumption is advisable with the 0.01-20 weight part, preferred 0.05-10 weight part, most preferably 0.05-5 weight part.
For the present invention, corresponding per 100 weight part polyacetal resins (A), the use level of category of glass inorganic filling material (B) is advisable with the 3-200 weight part, wherein preferred 5-150 weight part, most preferably 10-100 weight part.The improvement of mechanical property is not fairly obvious when being less than 3 weight parts, has the problem of forming process difficulty when surpassing 200 weight parts.
Polyacetal resin composite feature of the present invention is the hydroxy carboxylic acid compound (C) that has carboxyl and alcoholic extract hydroxyl group when cooperating category of glass inorganic filling material (B) in polyacetal resin (A) in further with 1 molecule as necessary components matching in wherein.
As (C) composition among the present invention, the hydroxy carboxylic acid compound who has carboxyl and alcoholic extract hydroxyl group in 1 molecule can be exemplified as aliphatic acid, alicyclic alkyd, aromatic series alkyd etc.Preferred aliphat alkyd wherein.
Concrete aliphatics alkyd is monohydroxy monoprotic acid, monohydroxy diprotic acid, monohydroxy triprotic acid, dihydroxyl monoprotic acid, dihydroxyl diprotic acid, dihydroxyl triprotic acid, trihydroxy monobasic acid, trihydroxy tribasic acid, trihydroxy tribasic acid etc.Enumerate concrete compound below.
Monohydroxy monoprotic acid can be enumerated oxyacetic acid, lactic acid, Alpha-hydroxy-butanic acid, Alpha-hydroxy isobutyric acid, Alpha-hydroxy-positive valeric acid, the Alpha-hydroxy isovaleric acid, 2-hydroxy-2-methyl butyric acid, Alpha-hydroxy-n-caproic acid, the Alpha-hydroxy isocaproic acid, 2-ethyl-2-hydroxybutyric acid, 2-ethyl-3, the 3-acid dimethyl, 2-hydroxy-2-methyl valeric acid, 2-hydroxy-2-methyl caproic acid, 2-hydroxyl-2,4-dimethyl valeric acid, 2-hydroxyl docosoic acid, 2-hydroxyl tetracosanoic acid, 2-hydroxyl hydroxyhexacosanoic acid, hydroxyl acrylic, beta-hydroxy-butanoic acid, the beta-hydroxy isopropylformic acid, beta-hydroxy-positive valeric acid, beta-hydroxy-isovaleric acid, α-ethyl hydroxy-propionic acid, the hydroxyl trimethylacetic acid, 3-hydroxy-2-methyl valeric acid, 3-hydroxyl-2-tetradecyl stearic acid, the 11-hydroxy tetradecanoic acid, the 11-hydroxy-palmitic acid, the 14-hydroxy-palmitic acid, the 12-hydroxylauric acid, the 12-oxystearic acid, the 16-hydroxy-palmitic acid, 22-hydroxyl docosoic acid, Alpha-hydroxy vinylformic acid, vinylglycollic acid, the propenyl oxyacetic acid, 3-hydroxy-2-methyl butyric acid, 3-hydroxyl-2-tetradecyl-11-octadecenic acid, ricinoleic acid, 9-hydroxyl-12-octadecenic acid, 18-hydroxyl-9,11, the 13-punicic acid, 8-hydroxyl-11-octadecylene-9-acetylenic acid, 12-hydroxyl-stearolic acid, 13-hydroxyl-10-19 acetylenic acids etc.
The monohydroxy diprotic acid can be enumerated tartronic acid, different oxysuccinic acid, 1-hydroxy propane-1, the 1-dicarboxylic acid, 1-hydroxyl butane-1, the 1-dicarboxylic acid, 1-hydroxy-2-methyl propane-1, the 1-dicarboxylic acid, 2-hydroxyl ethane-1, the 1-dicarboxylic acid, 2-hydroxy-3-methyl propane-1, the 1-dicarboxylic acid, 1-(hydroxyethyl) propane-1, the 1-dicarboxylic acid, oxysuccinic acid, the Alpha-Methyl oxysuccinic acid, Alpha-hydroxy-α '-methylsuccinic acid, Alpha-hydroxy-α ', α '-dimethyl succinate, Alpha-hydroxy-α, α '-dimethyl succinate, Alpha-hydroxy-α '-ethyl succsinic acid, Alpha-hydroxy-α '-methyl-α-ethyl succsinic acid, the trimethylammonium oxysuccinic acid, the alpha-hydroxypentyl diacid, the beta-hydroxy pentanedioic acid, beta-hydroxy-Beta-methyl pentanedioic acid, beta-hydroxy-α, the alpha-alpha-dimethyl pentanedioic acid, beta-hydroxy-α, alpha, gamma-trimethylammonium pentanedioic acid, the Alpha-hydroxy suberic acid, the Alpha-hydroxy sebacic acid, 2-hydroxyl-2-octyl group sebacic acid, 2-hydroxyl-2-octyl group tetradecane diacid etc.
The monohydroxy triprotic acid can be enumerated citric acid, isocitric acid, 2-hydroxyl heptadecane-1,2,3-tricarboxylic acid, 2-hydroxyl nonadecane-1,2,3-tricarboxylic acid etc.
Dihydroxyl monoprotic acid can be R-Glyceric acid, 2,3-dihydroxyl butyric acid, 2,3-dihydroxyl-2 Methylpropionic acid, 3-hydroxyl-2-hydroxymethyl propionic acid, 3,4-dihydroxyl butyric acid, 2,4-dihydroxyl-3,3-acid dimethyl, 2,3-dihydroxyl-2-(1 '-methylethyl) butyric acid, 3,11-ipurolic acid, 15,16-ustilic acid A, 9,10-dihydroxyl octadecanoic acid, 9,14-dihydroxyl-10,12-octadecane diolefinic acid, 12,13-dihydroxyl-9-octadecenoic acid etc.
The dihydroxyl diprotic acid can be enumerated tartrate, methyl tartrate, dimethyl tartrate, α, the beta-dihydroxyl pentanedioic acid, α, γ-dihydroxyl pentanedioic acid, α, γ-dihydroxyl-Beta-methyl pentanedioic acid, α, γ-dihydroxyl-β-ethyl-Beta-methyl pentanedioic acid, α, γ-dihydroxyl-α, the γ dimethylated pentanedioic acid, α, δ-dihydroxyl hexanodioic acid, β, γ-dihydroxyl hexanodioic acid, 2,5-dihydroxyl-5-sec.-propyl-2-methyl hexanodioic acid, 6,7-dihydroxyl dodecanedioic acid, 7,8-dihydroxyl Thapsic acid, 9,10-dihydroxyl octadecane diacid, Dihydroxyfumaric acid, dihydroxymaleic acid etc.
The dihydroxyl triprotic acid can enumerate 1,2-dihydroxyl ethane-1,2,2-tricarboxylic acid, 1,2-dihydroxypropane-1,2,3-tricarboxylic acid, 1,3-dihydroxypropane-1,1,3-tricarboxylic acid etc.
Trihydroxy monobasic acid can be enumerated trihydroxy-butyric acid, trihydroxy-isopropylformic acid, 3,4,5-trihydroxy caproic acid, 9,10,16-aleuritic acid, 2,15,16-aleuritic acid, 9,10,12-trihydroxy-stearic acid, 9,10,16-trihydroxy-stearic acid etc.Trihydroxy tribasic acid can be enumerated trihydroxy glutaric acid.
Wherein preferred alcohol acid, lactic acid, Alpha-hydroxy isobutyric acid, beta-hydroxy isopropylformic acid, hydroxyl trimethylacetic acid, 12-oxystearic acid, oxysuccinic acid, citric acid, tartrate etc.These can use separately, also can use two or more mixtures.
The present invention, the polyacetal resin (A) of corresponding per 100 weight parts, hydroxy carboxylic acid compound's (C) dosage is the 0.001-3 weight part, is preferably the 0.01-2 weight part, most preferably the 0.03-1 weight part.The improvement of mechanical property and insufficient when being less than 0.01 weight part can cause the decomposition and the foaming of polyacetal resin when surpassing 3 weight parts, reduced stability.
Can add various additives commonly used again in the polyacetal resin composite in the present invention, as various tinting materials, remover, nuclear agent, antistatic agent, other tensio-active agent, various polymkeric substance etc.And, only otherwise cause the reduction significantly of moulding resistance of the present invention, also can select one or more non-glass class packing materials commonly used such as fibrous, tabular, the powder granulous weighting agent of inorganic, organic and metal etc. for use, be mixed in wherein.This class weighting agent can be materials such as talcum, mica, wollastonite, carbon fiber, is limited to these but have more than.
Have no particular limits for the preparation of compositions method among the present invention, easily prepare according to the equipment and the method for the preparation resin combination that generally adopts up to now.Such as i) mix after each composition, the extruding of rubbing by extrusion machine earlier is prepared into coccoid, and then the method for moulding, ii) different beads of forming (pellet) of preparation earlier, amount is mixed bead (pellet) in shaping in accordance with regulations again, obtains the moulding product that target is formed after the moulding.Iii) directly pack in the shaper one or more composition, any can the use in the aforesaid method.In addition, a part of resinous principle being made that fine powder and other component be mixed together is the Perfected process of each component of uniform mixing.
Also have, the resin combination that the present invention relates to can moulding with any methods such as extrusion moulding, ejection formation, compressed moulding, vacuum forming, blow molding, foamings.
Embodiment
Embodiment
Below demonstrate the present invention, but the present invention has more than and is limited to these embodiment.
Example 1-26, comparative example 1-13
Cooperating various category of glass inorganic filling materials (B) and hydroxy carboxylic acid compound (C) in the ratio shown in table 1～2 in 100 weight part polyacetal resins (Polyplastics Co., Ltd. (JP) 30, Azuchimachi 2-chome, Higashi-ku, Osaka-shi, Osak make, trade(brand)name " ジ ユ ラ コ Application M90 "), is that melting mixing obtains coccoid shape composition in 200 ℃ the forcing machine at cylinder temperature.Then, obtain test film, and measured following rerum natura with the above-mentioned coccoid shape composition of Jet forming machine moulding.It the results are shown in Table 1～2.Evaluation method is as follows
Tensile strength and extension
According to the ISO3167 standard, the tension test sheet at 23 ℃, is placed after 48 hours according to the ISO527 standard test under 50% humidity.
Table 1
| Resin is formed | Evaluation result | ||||||
| (A) polyacetal resin (weight part) | (B) category of glass packing material | (C) hydroxycarboxylic acid | Tensile strength (MPa) | Unit elongation (%) | |||
| Kind | Weight part | Kind | Weight part | ||||
| Embodiment 1 | 100 | B-1 | 35 | C-1 | 0.03 | 60 | 11 |
| Embodiment 2 | 100 | B-2 | 35 | C-1 | 0.01 | 54 | 10 |
| Embodiment 3 | 100 | B-2 | 35 | C-1 | 0.005 | 52 | 10 |
| Embodiment 4 | 100 | B-2 | 35 | C-1 | 0.03 | 63 | 16 |
| Embodiment 5 | 100 | B-2 | 35 | C-1 | 0.05 | 65 | 15 |
| Embodiment 6 | 100 | B-2 | 10 | C-1 | 0.03 | 57 | 14 |
| Embodiment 7 | 100 | B-2 | 70 | C-1 | 0.03 | 53 | 8 |
| Embodiment 8 | 100 | B-2 | 35 | C-2 | 0.03 | 62 | 14 |
| Embodiment 9 | 100 | B-2 | 35 | C-3 | 0.03 | 60 | 13 |
| Embodiment 10 | 100 | B-2 | 35 | C-4 | 0.03 | 61 | 12 |
| Embodiment 11 | 100 | B-2 | 35 | C-5 | 0.03 | 62 | 12 |
| Embodiment 12 | 100 | B-2 | 35 | C-6 | 0.03 | 60 | 11 |
| Embodiment 13 | 100 | B-2 | 35 | C-7 | 0.03 | 59 | 10 |
| Embodiment 14 | 100 | B-2 | 35 | C-8 | 0.03 | 60 | 11 |
| Embodiment 15 | 100 | B-2 | 35 | C-9 | 0.03 | 59 | 13 |
| Embodiment 16 | 100 | B-3 | 35 | C-1 | 0.03 | 63 | 15 |
| Embodiment 17 | 100 | B-4 | 35 | C-1 | 0.03 | 62 | 16 |
| Embodiment 18 | 100 | B-5 | 35 | C-1 | 0.03 | 63 | 15 |
| Comparative example 1 | 100 | B-1 | 35 | 46 | 12 | ||
| Comparative example 2 | 100 | B-2 | 35 | 48 | 15 | ||
| Comparative example 3 | 100 | B-2 | 10 | 49 | 17 | ||
| Comparative example 4 | 100 | B-2 | 70 | 38 | 4 | ||
| Comparative example 5 | 100 | B-3 | 35 | 47 | 14 | ||
| Comparative example 6 | 100 | B-4 | 35 | 48 | 12 | ||
| Comparative example 7 | 100 | B-5 | 35 | 47 | 14 | ||
Table 2
| Resin is formed | Evaluation result | ||||||
| (A) polyacetal resin (weight part) | (B) category of glass packing material | (C) hydroxycarboxylic acid | Tensile strength (MPa) | Unit elongation (%) | |||
| Kind | Weight part | Kind | Weight part | ||||
| Embodiment 19 | 100 | B-6 | 35 | C-1 | 0.03 | 145 | 2.7 |
| Embodiment 20 | 100 | B-6 | 35 | C-1 | 0.005 | 128 | 2.4 |
| Embodiment 21 | 100 | B-6 | 35 | C-1 | 0.01 | 133 | 2.5 |
| Embodiment 22 | 100 | B-6 | 10 | C-1 | 0.03 | 102 | 4.1 |
| Embodiment 23 | 100 | B-7 | 35 | C-1 | 0.03 | 142 | 2.8 |
| Comparative example 8 | 100 | B-6 | 35 | 120 | 2.2 | ||
| Comparative example 9 | 100 | B-6 | 10 | 82 | 3.3 | ||
| Comparative example 10 | 100 | B-7 | 35 | 121 | 2.0 | ||
| Embodiment 24 | 100 | B-8 | 30 | C-1 | 0.03 | 62 | 15 |
| Embodiment 25 | 100 | B-9 | 30 | C-1 | 0.03 | 60 | 16 |
| Comparative example 11 | 100 | B-8 | 30 | 47 | 10 | ||
| Comparative example 12 | 100 | B-9 | 30 | 46 | 13 | ||
| Embodiment 26 | 100 | B-10 | 35 | C-1 | 0.03 | 72 | 4.8 |
| Comparative example 13 | 100 | B-10 | 35 | 62 | 3.9 | ||
B-1: the granulated glass sphere that does not use surface treatment agent
B-2: with the granulated glass sphere after the γ-An Jibingjisanyiyangjiguiwan surface treatment
B-3: with the granulated glass sphere after the vinyltriethoxysilane surface treatment
B-4: with the granulated glass sphere after γ-glycidoxy propyl-triethoxysilicane surface treatment
B-5; With the granulated glass sphere after the octylene ethyl glycolate surface treatment of titanium-isopropoxy
B-6: with the glass fibre after the γ-An Jibingjisanyiyangjiguiwan surface treatment
B-7: with the glass fibre after titanium-I-propoxy-octyne ethyl glycolate processing
B-8: the milled glass fiber that does not use surface treatment agent
B-9: with the milled glass fiber after the γ-An Jibingjisanyiyangjiguiwan surface treatment
B-10: with the glass flake after the γ-An Jibingjisanyiyangjiguiwan surface treatment
C-1: oxyacetic acid
C-2: lactic acid
C-3: Alpha-hydroxy isobutyric acid
C-4: beta-hydroxy isopropylformic acid
C-5: the hydroxyl trimethylacetic acid,
C-6:1,2-hydroxystearic acid,
C-7: oxysuccinic acid,
C-8: citric acid,
C-9: tartrate
Claims (3)
1. polyacetal resin composite, it is characterized in that, it is with respect to (A) polyacetal resin 100 weight parts, add (B) category of glass inorganic filling material 10-100 weight part and (C) have the hydroxy carboxylic acid compound 0.005-1 weight part of carboxyl and alcoholic extract hydroxyl group in molecule and the polyacetal resin composite that forms, wherein this category of glass inorganic filling material (B) is selected from glass fibre, granulated glass sphere, milled fiber and glass flake, and hydroxy carboxylic acid compound (C) is selected from monohydroxy monoprotic acid, monohydroxy diprotic acid, monohydroxy triprotic acid, dihydroxyl diprotic acid.
2. composition as claimed in claim 1 is characterized in that this category of glass inorganic filling material (B) has carried out surface treatment with aminoalkoxy silane.
3. composition as claimed in claim 1 or 2 is characterized in that this hydroxy carboxylic acid compound (C) is for being selected from one or more the mixture in oxyacetic acid, lactic acid, Alpha-hydroxy isobutyric acid, beta-hydroxy isopropylformic acid, hydroxyl trimethylacetic acid, 12-oxystearic acid, oxysuccinic acid, citric acid, the tartrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP181477/2001 | 2001-06-15 | ||
| JP181477/01 | 2001-06-15 | ||
| JP2001181477A JP4979857B2 (en) | 2001-06-15 | 2001-06-15 | Polyacetal resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392195A CN1392195A (en) | 2003-01-22 |
| CN1223633C true CN1223633C (en) | 2005-10-19 |
Family
ID=19021741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02123271 Expired - Lifetime CN1223633C (en) | 2001-06-15 | 2002-06-17 | Polyacetal resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4979857B2 (en) |
| CN (1) | CN1223633C (en) |
| MY (1) | MY129911A (en) |
| TW (1) | TWI294897B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5005159B2 (en) * | 2003-06-04 | 2012-08-22 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP2005029714A (en) * | 2003-07-08 | 2005-02-03 | Polyplastics Co | Polyacetal resin composition |
| JP5028758B2 (en) * | 2004-07-27 | 2012-09-19 | 東レ株式会社 | Polyacetal resin composition and method for producing the same |
| JP4549784B2 (en) * | 2004-09-03 | 2010-09-22 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP5336710B2 (en) * | 2007-06-29 | 2013-11-06 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP5406173B2 (en) * | 2010-12-28 | 2014-02-05 | ポリプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6835650B2 (en) * | 2017-03-30 | 2021-02-24 | ポリプラスチックス株式会社 | Polyacetal resin composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3667023B2 (en) * | 1997-02-25 | 2005-07-06 | 旭化成ケミカルズ株式会社 | Method for producing polyoxymethylene resin composition |
| JP2000239484A (en) * | 1998-12-22 | 2000-09-05 | Polyplastics Co | Polyacetal resin composition and molded article |
| JP3835964B2 (en) * | 1998-12-24 | 2006-10-18 | ポリプラスチックス株式会社 | Flame retardant resin composition |
| JP4260284B2 (en) * | 1999-05-19 | 2009-04-30 | ポリプラスチックス株式会社 | Flame retardant and flame retardant resin composition |
| CN1267498C (en) * | 2000-09-21 | 2006-08-02 | 汎塑料株式会社 | Polyacetal resin composition and process for its production |
-
2001
- 2001-06-15 JP JP2001181477A patent/JP4979857B2/en not_active Expired - Fee Related
-
2002
- 2002-06-07 TW TW91112304A patent/TWI294897B/zh not_active IP Right Cessation
- 2002-06-12 MY MYPI20022207 patent/MY129911A/en unknown
- 2002-06-17 CN CN 02123271 patent/CN1223633C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| TWI294897B (en) | 2008-03-21 |
| JP4979857B2 (en) | 2012-07-18 |
| JP2002371168A (en) | 2002-12-26 |
| CN1392195A (en) | 2003-01-22 |
| MY129911A (en) | 2007-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1120184C (en) | Vinyl alcohol polymer and its composition | |
| KR101281834B1 (en) | Biodegradable polymer composite | |
| CN1576313A (en) | Polyacetal resin composition | |
| CN1946750A (en) | Vinyl chloride resin composition and method for preparation thereof | |
| CN1223633C (en) | Polyacetal resin composition | |
| JP2003026941A (en) | Composition for composite lumber and composite lumber | |
| CN1158348A (en) | Aqueous coating compositions | |
| CN101077925A (en) | Modified formulation for high surface hardness PC-ABS resin | |
| CN1475526A (en) | Composite material of polyolefin resin and filling and moulded product made thereof | |
| CN1576314A (en) | Polyacetal resin composition | |
| CN1244633C (en) | Toughened, high-modulus polyacetals | |
| MX2008013442A (en) | Stabilizers for improved open time of aqueous coatings. | |
| CN1305957C (en) | Glass fiber filled thermoplastic compositions with good surface appearance | |
| CN1596281A (en) | Molding compositions having improved properties | |
| CN1693396A (en) | Vacuum plating film coating | |
| CN1039024C (en) | Polyoxymethylene resin composition | |
| AU2002363006A1 (en) | Molding compositions having improved properties | |
| CN1765990A (en) | Nylon 6 composition useable for car engine hood and its preparation method | |
| CN1038041C (en) | Polyarylene sulfide resin composition | |
| CN1281006A (en) | Composition with thermoplastic methacrylic acid (co) polymers as main component and shaping product obtained from said composition | |
| JP2007119609A (en) | Polyalkylene carbonate resin composition and molded form thereof | |
| KR101476502B1 (en) | Thermoplastic Resin Compositions Having Good Paintability | |
| CN1643056A (en) | Filled weatherable compositions having a good surface appearance | |
| WO2001048084A1 (en) | Polyoxymethylene resin composition | |
| CN101061178A (en) | High density polyoxymethylene compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051019 |