CN1168314A - Blow-molded multi-layer article of polyacetal resin and process for producing the same - Google Patents
Blow-molded multi-layer article of polyacetal resin and process for producing the same Download PDFInfo
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- CN1168314A CN1168314A CN 97110050 CN97110050A CN1168314A CN 1168314 A CN1168314 A CN 1168314A CN 97110050 CN97110050 CN 97110050 CN 97110050 A CN97110050 A CN 97110050A CN 1168314 A CN1168314 A CN 1168314A
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- alkene
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- blow moulded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2059/00—Use of polyacetals, e.g. POM, i.e. polyoxymethylene or derivatives thereof, as moulding material
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Provides a multilayered blow molded product which has excellent performance in heat resistance, surface smoothness, impact resistance, creep resistance and chemical resistance. A adhesive resin layer consisting of a modified olefinic polymer C is disposed between a polyacetal resin A and other thermoplastic resin B.
Description
The present invention relates to a kind of multi-layer product that has good hear resistance, impact resistance, surface smoothness, creep resistance and chemical resistance and contain the blow moulded shaping of at least one strata acetal resin resin bed.
The blow moulded molded article is widely used in automobile.In OA equipment, field of food and the various industrial circle.A large amount of up to now resins for universal use is used for blow molding always, and engineering plastics only account for very little ratio therein.But, along with the expansion of the application of blow molding, require higher levels of performance in recent years, utilize engineering plastics just among consider.
Polyacetal resin---it also is a kind of engineering plastics---also developed energetically in case fullest utilize its hear resistance, impact resistance, surface smoothness, creep resistance and chemical resistance.Yet the blow moulded molded article that contains polyacetal resin can not satisfy steam permeability and the requirement of impact resistance in some cases.In addition, compare with resins for universal use, it is great and cost of material is high to contain the ratio of blow moulded molded article of polyacetal resin.
In order to compensate the characteristic that these shortcomings make full use of above-mentioned polyacetal resin simultaneously, attempted for example forming sandwich construction, i.e. multilayer blow moulding mould-forming with the alkene resin that is resins for universal use with other thermoplastic resin.Thereby, this mould-forming goods can not obtain good blow moulded molded article but causing the separation between polyacetal resin layer and polyalkenes layer always.
In order to address the above problem, the inventor makes great efforts to study to obtain the having multi-layer product that good hear resistance, impact resistance, surface smoothness, creep resistance and chemical resistance and steam permeability and not only cheap but also light blow moulded are shaped always.Result as research, they have found a kind of bonds well resin that achieves the above object, by carrying out the multilayer blow moulding mould-forming with such method with other thermoplastic resin, this method is compensated the shortcoming of polyacetal resin, the feature of this resin is showed, thereby they have realized the present invention.
The present invention is the multi-layer product that a kind of blow moulded is shaped, and it contains:
One deck contains the resin bed of a kind of polyacetal resin (A),
One deck contain another kind of thermoplastic resin (B) resin bed and
One deck be placed on (A) and (B) between contain the binding resin layer of modification alkene (being total to) polymers (C).
To describe the present invention in detail hereinafter.
Polyacetal resin used in the present invention (A) can have any straight chain, side chain and crosslinked structure.
The straight chain polyacetal resin can the homopolymerization by formaldehyde Huo trioxane obtain, or to obtain as the formaldehyde Huo trioxane of principal monomer and a kind of cyclic ethers or cyclic formal copolymerisation as comonomer.There is the polyacetal resin of side chain or cross-linked structure the homopolymerization by formaldehyde Huo trioxane to obtain, or for example carries out the copolymerization acquisition in the presence of the polyfunctional compound of hydroxyl, amino, carboxyl and epoxy radicals with in molecule, have three functional groups at least as a kind of cyclic ethers of comonomer or cyclic formal as the formaldehyde Huo trioxane of principal monomer.
In addition, the used polyacetal resin (A) of the present invention can with for example various elastomers of various anti-impact modifiers mutually blending so that improve blow moulded formability and its impact resistance.One of them preferred embodiment contains core-shell polymer (core-shell polymer).Here said core-shell polymer is meant a kind of organic compound that contains an elastomeric polymer core and contain a nature of glass polymer shell.It can prepare with known method, the product that maybe can use market to sell.Its typical example comprises Rohm﹠amp; HaasCo., Ltd. product A cryloid KM 330 and KM 653 (trade mark), Kureha Chemical Ind.Co., Ltd. product B alaloid KCAS-102 and KCA-301 (trade mark), TakedaPharmaceutical Ind.Co., Ltd. product P O-0270 and PO-0143 (trade mark), Kanegafuchi Chemical Ind.Co., Ltd. product K ane Ace FM (trade mark), and Mitsibishi Rayon Co., product Metapren C-102, E-901, W-800 and the S-2001 of Ltd..
In this case, be 1～100 weight portion in the blending amount of per 100 these core-shell polymers of weight portion polyacetal resin weight, 10～40 weight portions preferably.
Equally, polyacetal resin (A) and a kind of thermoplastic polyurethane resin and---if necessary---and a kind of isocyanate compound blending can be used as a preferred embodiment.In this case, in per 100 weight portion polyacetal resin weight, the blending amount of thermoplastic polyurethane is 1～100 weight portion, 10～50 weight portions preferably, isocyanate compound blending amount is 0.1～10 weight portion, preferably the 0.3-5 weight portion.
Can in polyacetal resin of the present invention, suitably add the known substance that joins usually in the synthetic resin according to desired performance, i.e. stabilizing agent such as antioxidant and UV absorbent, antistatic additive, fire retardant, the colouring agent such as dyestuff and pigment, lubricant.Antitack agent.In addition, as long as the performance of not very big degree ground infringement polyacetal resin also can add other resin.
In the present invention, the melting viscosity of polyacetal resin has no particular limits.Extrude decline index (drawdown index) with another kind of thermoplastic resin forms the multi-layered type embryo, preferably 2.5 or bigger, particularly preferably be 3.0 or bigger.The decline index determines with following method:
Port mould diameter/core diameter=50 (mm)/46 (mm), extrusion capacity=24kg/ hour
Have again, any resin, as long as in a single day it after the fusion, can form the multi-layered type embryo with polyacetal resin at 160～250 ℃ extrusion temperatures in extruder, just can be used as the thermoplastic resin (B) that carries out the multilayer blow moulding mould-forming with polyacetal resin.Extrusion temperature is lower than 160 ℃ and causes that polyacetal resin solidifies, and greatly increases and extrudes load, makes the mould-forming difficulty.Simultaneously, extrusion temperature surpasses 250 ℃ and causes the polyacetal resin thermal decomposition, and it is impossible that mould-forming is become.
The special case of above-mentioned thermoplastic resin has, for example such as high density polyethylene (HDPE), low density polyethylene (LDPE) and polyacrylic vistanex; The polyamide of nylon 6 and nylon 66 for example; Mylar such as polybutylene terephthalate and PET; Polystyrene; Merlon and modified poly ethylene.
The invention is characterized in provides one deck resin bed conduct that contains a kind of modification alkene (being total to) polymer (C) at the above-mentioned binding resin layer that contains in resin (A) and the multilayer blow moulding moulding article (B).
In the present invention, modification alkene (being total to) polymer (C) that uses as the binding resin layer is a kind of by introducing alkene (being total to) polymer (C) of a modified with polar.The example of this polar group comprises, carboxyl, glycidyl, NCO, hydroxyl, amino and the group of deriving from them.Wherein, by introducing carboxyl, glycidyl and being preferred from group modified alkene (being total to) polymer (C) that they are derived.
As alkene (being total to) polymer (C) of this class modification or produce their method known have various, not to they special restrictions.Component utilized (C) contains a kind of resin by the glycerol polymerization of a kind of unsaturated carboxylic acid or derivatives thereof is generated on the main chain of the copolymer of the copolymer that contains a kind of alkene homopolymers, two kinds or multiple alkene or a kind of alkene and another kind of unsaturated monomer in the present invention; With contain a kind of by the glycerol polymerization of a kind of unsaturated carboxylic acid or derivatives thereof to containing the resin that the copolymer chain of a kind of alkene with the unsaturated monomer of the another kind of group that a carboxyl, glycidyl is arranged or derive from them generates.The resin that generates on the main chain of especially preferred a kind of copolymer by but the unsaturated monomer of one or more copolymerization or the polymer graft that contains one or more unsaturated monomers being aggregated to the copolymer that contains a kind of alkene homopolymers, two kinds or multiple alkene or a kind of alkene and another kind of unsaturated monomer.
For example, by be exactly a kind of resin that obtains with a kind of unsaturated carboxylic acid such as maleic anhydride-modified processing such as poly a kind of alkene polymers preferred a kind of in the polymer.
In the present invention, according to as the form of the binding resin layer of above-mentioned component (C) the binding resin layer is provided is effective, especially a kind of alkene (being total to) polymers with sour modification of the wide or bigger adhesion strength of 0.8kgf/15mm does not produce lamination when extruding.In order to obtain higher adhesion strength, preferably use low (being total to) polymers of a kind of degree of crystallinity as component (C).
Multilayer blow moulding mould-forming of the present invention can be undertaken by the multilayer blow moulding mould-forming of thermoplastic resin multilayer blow moulding mould-forming equipment commonly used by traditional method.Be above-mentioned polyacetal resin (A), another kind of thermoplastic resin (B) and as the composition (C) of binding resin in extruder by plasticizing, extrude or inject, form a fusion or softening multi-layered type embryo intermediate by an annular die.The multi-layered type indusium that makes is like this put into a metal pattern die, gas is blown into it is expanded so that consistent with metal pattern die.Then, obtain the moulding article of consistent hollow shape by cooling curing.
With regard to the condition of used in the present invention polyacetal resin multilayer blow moulding mould-forming, extrusion temperature is preferably in 170～250 ℃ scope.The extrusion temperature (not causing under this temperature that component descends) that particularly preferably is as the attached fat of thermoplasticity of main resin in the multilayer component is in above-mentioned scope.Gas as in being blown into into can use air, nitrogen or other gas arbitrarily.From the viewpoint of economy, use air usually.The pressure of its blowing is 4～10kg/cm preferably
2This mould-forming also can carry out by means of the special blow moulded forming machine such as the tri-dimensional blow moulding molding machine.
The invention is characterized in the shortcoming of compensation polyacetal resin, by polyacetal resin and another kind of thermalplastic resin multi-layer blow moulded shaping fullest utilize its feature.If necessary, blow moulded goods of the present invention can Unitarily molded shaping or with the parts clinkering that an injection molding is shaped, perhaps can be used as embedded component/externally inlaid part that injection moulding uses and use.
The present invention will be described in more detail below with reference to embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1～3 and comparative example 1～4
Following polyacetal resin A, thermoplastic resin B1 or B2 and binding resin C1 and C2 make the extrusion type embryo of three kinds, three layers and 40mm diameter (wall thickness 2.5mm) 200～220 ℃ of resin temperatures with one three kinds and three layers of blow moulded forming machine (Placor Co., three layers of tri-dimensional blow moulding molding machine of 3-XY that Ltd makes).Then air at 6kg/cm
2Low pressure under in matched moulds (60～80 ℃ of mold temperatures), be blown into air, form the hydrostatic column (capacity 500ml) that the blow moulded of three kinds and three layers is shaped.Measure the character of mould-forming goods then.
The resin material that uses and method of testing as follows: (resin material)
A: polyacetal resin
B1: high density polyethylene (HDPE)
B2: nylon 6
C1: binding resin (maleic anhydride-modified polyethylene; Peracid-modification degree)
C2: binding resin (maleic anhydride-modified polyethylene; Low acid-modification degree)
(test of blow moulded molded article) 1) adhesion strength:
Downcut the bar shaped test sample of long 150mm and wide 15mm to measure its adhesion strength from the be shaped hydrostatic column of the average wall thickness 1.5mm make of blow moulded.
Tear speed: shock-testing 300mm/min (T-peels off) 2):
Use the rupture strength of a kind of DYNATUP shock machine (General Research Corp.) test with the average thickness 1.5mm hydrostatic column of blow moulded shaping manufacturing.
Weight: the 5.86kg that drops hammer, height of the fall: 86cm3) gasoline permeability:
The normal benzine that market is sold pours into average wall thickness 1.5mm and is shaped in the hydrostatic column made from blow moulded, to 10% of total measurement (volume).Seal this container and be placed in 60 ℃ the environment to measure the gasoline permeability.
Table 1
| Embodiment | The comparative example | ||||||
| ??1?????????????2???????????3 | ????1???????????2???????????3??????????4 | ||||||
| The layer structural outside layers tack coat internal layer of moulding article | ??B1 ??C1 ??A | ????B1 ????C2 ????A | ????B2 ????C2 ????A | ????A ????- ????- | ????B1 ????- ????- | ????B1 ????- ????A | ????B2 ????A |
| Tearing strength kgf/15mm width | ??3.0 | ????1.2 | ????1.6 | ????- | ????- | ????0 | ????0 |
| Impact strength kN/mm | ??1.8 | ????1.8 | ????2.1 | ????0.4 | ????1.8 | ????1.0 | ????1.4 |
| Gasoline permeability g.mm/m 2.24H | ??1.5 | ????1.5 | ????1.5 | ????1.5 | ????250 | ????1.5 | ????1.5 |
Polyacetal resin blow moulded shaping multi-layer product according to the present invention is characterised in that the shortcoming of compensation polyacetal resin, utilize simultaneously its maximum feature, polyacetal resin blow moulded multilevel shaping goods according to the present invention that good hear resistance, impact resistance, table are arranged fullest and slickness, creep resistance and chemical resistance,
Claims (8)
1. the multi-layer product that is shaped of a blow moulded, it contains:
One deck contains the resin bed of a kind of polyacetal resin (A),
One deck contain another kind of thermoplastic resin (B) resin bed and
One deck be placed on (A) and (B) between the binding resin layer that contains modification alkene (being total to) polymers (C).
2. the multi-layer product that blow moulded as claimed in claim 1 is shaped, wherein the alkene of modification (being total to) polymers (C) has a carboxyl, a glycidyl or a group of deriving from them.
3. the multi-layer product that blow moulded as claimed in claim 1 is shaped, wherein the alkene of modification (being total to) polymers (C) is by the glycerol polymerization of a kind of unsaturated carboxylic acid or derivatives thereof is generated on the main chain of the copolymer of the copolymer that contains a kind of alkene homopolymers, two kinds or multiple alkene or a kind of alkene and another kind of unsaturated monomer.
4. the multi-layer product that blow moulded as claimed in claim 1 is shaped, wherein the alkene of modification (being total to) polymers (C) is by the glycerol polymerization of a kind of unsaturated carboxylic acid or derivatives thereof is being contained a kind of alkene and having a carboxyl.The main chain of the copolymer of the unsaturated monomer of the group that glycidyl or derive from such group generates.
5. the multi-layer product that blow moulded as claimed in claim 3 is shaped, wherein alkene (be total to) polymer (C) but be by one or more and contain a kind of homopolymers, one two kinds of alkene and the unsaturated monomer of the main chain copolymerization of the copolymer of the copolymer of multiple alkene or a kind of alkene and another kind of unsaturated monomer or a kind of polymer graft that contains one or more unsaturated monomers is aggregated on the main chain generates.
6. the multi-layer product that is shaped as the described blow moulded of arbitrary claim among the claim 1-5, wherein at the resin bed that contains polyacetal resin (A) with to contain another kind of thermoplastic resin be that 0.8kgf/15mm is wide or higher to the adhesion strength between the resin bed of fat (B), be owing to contain the existence generation of the binding resin layer of modification alkene (be total to) polymers (C).
7. as the multi-layer product of the described blow moulded shaping of arbitrary claim among the claim 1-6, the resin bed of wherein another kind of thermoplastic resin (B) is a kind of alkene (being total to) polymers that can contain modification alkene (being total to) polymers (C).
8. the method for the multi-layer product that is shaped as arbitrary claim defined production blow moulded among the claim 1-7, wherein, be included in obtain the decline index be 2.5 or higher such condition under form multi-layered type embryo and blow moulded this type embryo that is shaped.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59302/96 | 1996-03-15 | ||
| JP5930296A JPH09248851A (en) | 1996-03-15 | 1996-03-15 | Multilayered blow molded product of polyacetal resin and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1168314A true CN1168314A (en) | 1997-12-24 |
Family
ID=13109450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97110050 Pending CN1168314A (en) | 1996-03-15 | 1997-03-15 | Blow-molded multi-layer article of polyacetal resin and process for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH09248851A (en) |
| CN (1) | CN1168314A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952104A (en) * | 2008-01-09 | 2011-01-19 | 嘉士伯酿酒有限公司 | A method of stretch-blow-moulding a beverage container |
| WO2016206080A1 (en) * | 2015-06-26 | 2016-12-29 | The Procter & Gamble Company | Glossy container |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19932383A1 (en) * | 1999-07-14 | 2001-01-18 | Ticona Gmbh | Electrically conductive molded plastic parts |
| DE19951670A1 (en) * | 1999-10-27 | 2001-05-03 | Ticona Gmbh | Weldable components made of polyacetal |
| DE10061767B4 (en) | 1999-12-17 | 2009-10-15 | Asahi Kasei Kabushiki Kaisha | polyacetal resin |
| DE10104565A1 (en) | 2000-02-02 | 2001-10-31 | Asahi Chemical Ind | Integrated structural parts made of thermoplastic resins |
| JP4731022B2 (en) * | 2000-02-02 | 2011-07-20 | 旭化成ケミカルズ株式会社 | Thermoplastic resin bonded structure |
| DE10251333A1 (en) * | 2002-11-05 | 2004-05-19 | Ticona Gmbh | Composite including polyacetal and polyolefin shaped parts useful for preparation of structural parts contacting fuels, especially fuel-feed units, valves, tanks, or tank filler caps, gear wheels, guide rollers, drive parts |
| US20050173433A1 (en) * | 2004-02-11 | 2005-08-11 | Spahr Timothy A. | Fuel container having contiguous unbonded polyacetal/polyolefin layers |
-
1996
- 1996-03-15 JP JP5930296A patent/JPH09248851A/en active Pending
-
1997
- 1997-03-15 CN CN 97110050 patent/CN1168314A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952104A (en) * | 2008-01-09 | 2011-01-19 | 嘉士伯酿酒有限公司 | A method of stretch-blow-moulding a beverage container |
| CN101952104B (en) * | 2008-01-09 | 2014-06-25 | 嘉士伯酿酒有限公司 | A method of stretch-blow-moulding a beverage container |
| WO2016206080A1 (en) * | 2015-06-26 | 2016-12-29 | The Procter & Gamble Company | Glossy container |
| US10987848B2 (en) | 2015-06-26 | 2021-04-27 | The Procter & Gamble Company | Article with different textured surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09248851A (en) | 1997-09-22 |
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