CN1280145A - Polyolefine resin composition - Google Patents
Polyolefine resin composition Download PDFInfo
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- CN1280145A CN1280145A CN00120230A CN00120230A CN1280145A CN 1280145 A CN1280145 A CN 1280145A CN 00120230 A CN00120230 A CN 00120230A CN 00120230 A CN00120230 A CN 00120230A CN 1280145 A CN1280145 A CN 1280145A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- 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
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
A polyolefin resin composition having excellent transparency and high impact resistance at low temperature, each of the compositions containing a specific amount of a nucleating agent together with at least one of low-density polyethylene resins or linear low-density polyethylene resins.
Description
The present invention relates to polyolefine resin composition.More particularly, relate to polypropylene resin composite with good transparency, and have good transparency and have the polyethylene resin composition of high-impact at low temperatures, every kind of resin combination all contain the specified quantitative nucleator and contain ldpe resin or type low density polyethylene resin at least a.
Propylene-ethylene block copolymer is because its excellent in resistance impact has been widely used in the every field that injection moulding and blow moulding are produced moulded product, and these moulded products for example are auto parts, electrical equipment, industrial part, daily necessities and food packaging article.
High-density polyethylene resin is because its excellent low temperature shock-resistance also has been widely used in injection moulding production moulded product, and these moulded products for example are motorcycle parts, electrical equipment, industrial part, and daily necessities.
Recently, much having the moulded product (molding) that transparent appearance is called " matrix type " produces in thermoplastic product field.Yet though its shock-resistance of product that is made by propylene-ethylene block copolymer is good, the transparency is poor.In addition, though the shock-resistance under its low temperature of product that is made by high-density polyethylene resin is good, the transparency is also poor.
The inventor has furtherd investigate to address the above problem, and finally find, by with the nucleator of specified quantitative and will comprise that at least a resin in new LDPE (film grade) and the LLDPE adds to the polyolefine resin composition that makes among propylene-ethylene block copolymer or the high density polyethylene(HDPE), desirable performance above obtaining.
An object of the present invention is to provide a kind of polypropylene resin composite, when it is used as moulding material, show excellent in impact resistance and transparency based on propylene-ethylene block copolymer.
Another object of the present invention provides a kind of polyethylene resin composition based on high-density polyethylene resin, demonstrates excellent low temperature shock-resistance and excellent transparency when it is used as moulding material.
The present invention relates to a kind of polypropylene resin composite, it comprises 100 weight part propylene-ethylene block copolymers, 0.1-0.6 weight part nucleator, and at least a in 20-100 weight part new LDPE (film grade)s and the LLDPE.
The invention still further relates to polypropylene resin composite, it also comprises one or more superoxide of 0.001-0.1 weight part, and these superoxide are selected from 1,3-two (t-butyl peroxy sec.-propyl) benzene and 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane.
In an embodiment of polypropylene resin composite, (230 ℃ is 0.5-100 grams/10 minutes 21.18N) to the melt flow rate (MFR) of propylene-ethylene block copolymer, and density is 0.895-0.910g/cm
3, ethylene content is 3-15% weight, random copolymers content is 6-30% weight.
In an embodiment of polypropylene resin composite, (190 ℃ is 5-70 grams/10 minutes 21.18N) to the melt flow rate (MFR) of low density ethylene resin, and density is 0.915-0.925g/cm
3, (190 ℃ is 0.5-5 grams/10 minutes 21.18N) to the melt flow rate (MFR) of type low density polyethylene resin, and density is 0.920-0.930g/cm
3
In another embodiment of polypropylene resin composite, nucleator is to be selected from the following compounds one or more: 1,3: 2,4-Sorbitol dibenzal, 1,3: 2,4-two (right-the methyl benzylidene) sorbyl alcohols, 1,3-right-chlorine benzylidene-2,4-to methyl benzylidene sorbitol, 1,3: 2,4-two (right-the ethyl benzylidene) sorbyl alcohols, and two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt.
The invention still further relates to polyethylene resin composition, it comprises 100 weight part high-density polyethylene resins, 0.1-0.6 weight part nucleator, and at least a resin in 20-100 weight part ldpe resins and the LLDPE.
In an embodiment of polyethylene resin composition, (190 ℃ is 1-50 grams/10 minutes 21.18N) to the melt flow rate (MFR) of high-density polyethylene resin, and density is 0.941-0.965g/cm
3
In an embodiment of polyethylene resin composition, (190 ℃ is 5-70 grams/10 minutes 21.18N) to the melt flow rate (MFR) of ldpe resin, and density is 0.915-0.925g/cm
3, and the melt flow rate (MFR) of type low density polyethylene resin (190 ℃, 21.18N) be 0.5-5 grams/10 minutes, density is 0.920-0.930g/cm
3
In the another embodiment of polyethylene resin composition, nucleator is to be selected from the following compounds one or more: 1,3: 2,4-Sorbitol dibenzal, 1,3: 2,4-two (right-the methyl benzylidene) sorbyl alcohols, 1,3-right-chlorine benzylidene-2,4-to the methyl benzylidene sorbitol, 1,3: 2,4-two (right-the ethyl benzylidene) sorbyl alcohols, and two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt.
Being used for propylene-ethylene block copolymer of the present invention is the block polymer that contains the propene polymer part and 5-40% ethene polymers part of 60-95% weight, described propene polymer part mainly contains the propylene (the following PP part that is called sometimes) that is generated by the polyreaction fs, and described ethene polymers partly contains the ethene (the following RC part that is called sometimes) that is generated by the polyreaction subordinate phase quite in a large number.(230 ℃, (0 gram/10 minutes, density is 0.895-0.910g/cm to the melt flow rate (MFR) of this segmented copolymer 21.18N) to be 0.5-1
3, ethylene content (with respect to the ratio of whole segmented copolymers) is 3-15% weight.The PP of this segmented copolymer partly is alfon or contains 95% weight or more propylene and 5% weight or the random copolymers of ethene still less; This RC partly is the random copolymers that contains 60-95% weight acrylamide and 5-40% weight ethene.
The high rigidity propylene-ethylene block copolymer of also preferred use, contain 60-95% weight PP part (this part generates in the polyreaction the first step of using two or more polyphone polymerization reactors) and 5-40% weight RC part, wherein the maximum value of the melt flow rate (MFR) of resulting polymers in each reactor of polyreaction fs (below be called MFR (h)) and melt flow minimum value (below be called MFR (l)) have following relationship:
0.1 the melt flow rate (MFR) of the melt flow rate (MFR) of≤log (MFR (h)/MFR (l))≤1 and PP part (below be called MFR (p)) and RC part (below be called MFR (r)) has following relation:
3≤log(MFR(p)／MFR(r))≤7。
The high rigidity propylene-ethylene block copolymer of this class can be produced with the described method of JP-A-859766, the polymkeric substance that wherein mainly contains propylene generated in the polyreaction fs of using two or more tandem reactors, the polymkeric substance that contains quite a large amount of ethene then generates in the polyreaction subordinate phase subsequently, in subordinate phase, use is by containing titanium tetrachloride, the solid catalyst component of magnesiumcarbonate and n-butyl phthalate, prepared catalyst system combines with triethyl aluminum and diisopropyl dimethoxy silane.In the fs and the subordinate phase of polyreaction, the melt flow rate (MFR) of PP part and RC part by adopting known molecular weight regulator, as hydrogen etc., and is adjusted to desired level respectively.
Being used for high-density polyethylene resin of the present invention is Alathon, or by at least a multipolymer of forming in 95% weight or more ethene and 5% weight or propylene still less or the butylene-1, (190 ℃ of melt flow rate (MFR)s, 21.18N) be 1-50 grams/10 minutes, density is 0.945-0.965g/cm
3
Be used for ldpe resin of the present invention melt flow rate (MFR) (190 ℃, 21.18N) be preferably 5-70 the gram/10 minutes, density is 0.915-0.925g/cm
3, and can be selected from commercially available new LDPE (film grade) suitably, as the Petrothen 202,248,249 and 342 of Tosoh Ltd. manufacturing.The add-on of new LDPE (film grade) with for used propylene-ethylene block copolymer of 100 weight parts or high-density polyethylene resin, adds 20-100 weight parts.When the polyethylene that adds was less than 20 weight parts, it is not enough that the transparency of gained moulded product becomes; And when surpassing 100 weight account polyethylenes, though transparency is enough, the rigidity of moulded product is much lower sometimes.
Be used for type low density polyethylene resin of the present invention melt flow rate (MFR) (190 ℃, 21.18N) be 0.5-5 the gram/10 minutes, density is 0.920-0.930g/cm
3, can be selected from commercially available LLDPE suitably, as the LF 2408 of the made Suntec-LL of Asahi Chemical Industry Co..The add-on of LLDPE with for used propylene-ethylene block copolymer of 100 weight parts or high density polyethylene(HDPE), adds 20-100 weight parts.When this polyethylene that adds was less than 20 weight parts, it is not enough that the transparency of gained moulded product becomes; And when surpassing 100 weight account polyethylenes, though transparency is enough, the rigidity of moulded product is much lower sometimes.
Be used for nucleator of the present invention and be being selected from one or more of following compounds: 1,3: 2,4-Sorbitol dibenzal, 1,3: 2,4-two (right-the methyl benzylidene) sorbyl alcohols, 1,3-right-chlorine benzylidene-2,4-to methyl benzylidene sorbitol, 1,3: 2,4-two (right-the ethyl benzylidene) sorbyl alcohols, and two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt.
The add-on of these nucleators, with respect to 100 weight parts used propylene-ethylene block copolymer or high-density polyethylene resin, its ratio is 0.1-0.6 weight part, is preferably 0.2-0.4 weight part.When add-on is less than 0.1 weight part, the improvement deficiency of transparency, then impracticable when more than 0.6 weight part, do not improve because how many transparencies do not have, so its economical efficiency has reduced.
In addition, except propylene-ethylene block copolymer or high-density polyethylene resin, nucleator, and from least a resin in new LDPE (film grade) and the LLDPE, also can be with superoxide, for example 1,3-two (t-butyl peroxy sec.-propyl) benzene and 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, be added in the polypropylene resin composite of the present invention as properties-correcting agent, to improve transparency.These properties-correcting agent can use separately, but also two or more use together.
The additional proportion of properties-correcting agent contains propylene-ethylene block copolymer, nucleator and from least a acrylic resin polymkeric substance in new LDPE (film grade) or the LLDPE, can be 0.001-0.1 weight part with respect to 100 weight parts.When add-on was less than 0.001 weight part, transparency can not get improving, and when more than 0.1 weight part, can not effectively improve its transparency, so economical efficiency is bad and impracticable.
High density polyethylene(HDPE), ethene-acrylic rubber, vinylbenzene-divinyl rubber, polyvinyl acetate (PVA) or its partial hydrolysate, and the polymkeric substance of ethene-vinyl acetate copolymer or its partial hydrolysate and so on, except that effect of the present invention is had the detrimentally affect person, all can join in the polypropylene resin composite of the present invention.
Polypropylene, ethene-acrylic rubber, vinylbenzene-divinyl rubber, polyvinyl acetate (PVA) or its partial hydrolysate, and the polymkeric substance of ethene-vinyl acetate copolymer or its partial hydrolysate and so on, except that effect of the present invention is had the detrimentally affect person, all can join in the polyethylene resin composition of the present invention.
Also can be with mineral filler, talcum for example, mica, glass fibre, wollastonite, zeolite, lime carbonate and magnesium hydroxide and pigment or the like except that the present invention is had the detrimentally affect person, all can join in polypropylene of the present invention and the polyethylene resin composition.
In addition, in polypropylene of the present invention and the polyethylene composition, can add polyolefine various additives commonly used, stablizer for example, neutralizing agent, properties-correcting agent, anti-caking agent, static inhibitor, or nucleator are so that improve its rigidity by generating polyolefinic microlitic structure.
Stablizer comprises inferior phosphorus antioxidant, phenol antioxidant and photostabilizer; Neutralizing agent comprises the calcium salt of higher fatty acid; Properties-correcting agent comprises that radical produces agent and various silane coupling agent, metatitanic acid salt, boron class and aluminate class; And nucleator comprises 2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, two-(to tert-butyl-phenyl) sodium phosphate and p-tert-butyl benzoic acid aluminium or the like.Each of these additives can add with the ratio with respect to 100 weight part polypropylene resin composite or polyethylene resin composition 0.01-2.0 weight parts.
Polypropylene resin composite of the present invention or polyethylene resin composition can be by sending the said components of specified quantitative into mixing machine commonly used, as Henschel mixing machine (trade(brand)name), super mixing machine, ribbon mixer, mixing machine mixes and makes in tumbler mixer and the spot cloth.Then with the mixture of gained with single screw rod or twin screw extruder or roller at 150-300 ℃, preferred 180-250 ℃ fusion is kneaded and is extruded under the temperature, to obtain the granulous composition.
Polypropylene resin composite can be used any moulding method, as injection moulding, injection moulding blow moulding or the like and molding becomes moulded work.The molding temperature scope is 180-300 ℃, be preferably 200-260 ℃, and the die temperature scope is 0-80 ℃, is preferably 20-60 ℃.
The moulded product of making by polypropylene resin composite can enumerate following these: auto parts, as battery container, mirror lid and cylindrical member, electrical equipment, as the dry cabinet of tableware, humidifier body and mix cover; Industrial part is as container and spare parts kit; Daily necessities, as suitcase, instrument cases, bathhouse article, hose rack, kitchen tackle, sanitary product and spray gun; The lid of makeup, washing composition, medicine, oil and drinking water container; Ice cream is as the container of ice-creams and shaving cream; Food is as the container of pudding, juice and tap water.They can be widely used as each the field articles for use that needs transparency.
Polyethylene resin composition also can be molded as moulded product with various moulding method.When injection moulding, the molding temperature scope is 150-300 ℃, is preferably 180-260 ℃, and the die temperature scope is 0-80 ℃, is preferably 20-60 ℃.Under above-mentioned condition of moulding, can obtain motorcycle parts, cover as protective shield; Various electrical equipment; Industrial part is as container and spare parts kit; Daily necessities, as snow cave shovel, sled, work box, bathhouse article, kitchen tackle and sanitary product; The container cover of fuel, makeup, washing composition, medicine, oil and tap water; Ice cream is as the container of ice-creams and shaving cream; Food is as the container of pudding, juice and tap water.They can be widely used as the article of the various occasions that need transparency.
Polypropylene resin composite of the present invention can make by the nucleator of adding specified quantitative and a kind of resin in new LDPE (film grade) and the LLDPE in propylene-ethylene block copolymer, can make the moulded parts with excellent in resistance impact and transparency thus.This class moulded product can be widely used in each side, comprises auto parts, as store battery, and Jing Gai and pillar; Electrical equipment, as the dry cabinet of tableware, humidifier body and mixing cover; Industrial part is as container and spare parts kit; Daily necessities are as suitcase, work box, bathhouse article, hose rack, kitchen tackle, sanitary product and spray gun; The container cover of makeup, washing thorn, medicine and tap water; Ice cream is as the container of ice-creams and shaving cream; Food is as the container of pudding, juice and tap water.
Polyethylene resin composition of the present invention can make by a kind of resin that adds in specified quantitative nucleator and new LDPE (film grade) and the LLDPE in the high-density polyethylene resin, can make moulded parts thus with excellent in resistance impact and transparency, this class moulded product can be widely used in each side, comprise motorcycle parts, cover as protective shield; Various electrical equipment; Industrial part is as container and spare parts kit; Daily necessities are as snow cave shovel, sled, work box, bathhouse article, kitchen tackle and sanitary product; The container cover of fuel, makeup, washing composition, medicine, oil and tap water; Ice cream is as the container of ice-creams and shaving cream; Food is as the container of pudding, juice and tap water.
The present invention describes with the following example and comparing embodiment, and these embodiment never limit the scope of the invention.The Evaluation Method that is adopted among these embodiment is based on following method:
(1) according to JIS K 6758 (230 ℃ 21.18N) are measured the melt flow rate (MFR) of propylene-ethylene block copolymer.
(2) according to JIS K 6760 (190 ℃ 21.18N) are measured the melt flow rate (MFR) of high-density polyethylene resin.
(3) according to JIS K 6760 (190 ℃ 21.18N) are measured the melt flow rate (MFR) of ldpe resin.
(4) according to JIS K 6760 (190 ℃ 21.18N) are measured the melt flow rate (MFR) of type low density polyethylene resin.
(5) measure optical haze degree (unit: %) according to " optical haze test method " described in the ASTM D 1003.To carry out granulation at 230 ℃ of resin combinations that under nitrogen atmosphere, melt extrude and make of temperature with single screw extrusion machine.At resin temperature is 250 ℃, and initial injection pressure is 1000kg/cm
2, die temperature is 50 ℃, and cycling time be under 25 seconds the condition, particle to be carried out molding, generate the test film of wide 25 * 50mm, thick 1.0mm.Room temperature be controlled at regulate 48 hours in 23 ± 2 ℃ the isothermal chamber after, the optical haze degree of experiment with measuring sheet.
(6) measure modulus in flexure (unit: MPa) according to " bend test method " described in the JIS K 7203.To carry out granulation at the knead resin combination of gained of 230 ℃ of following fusions of temperature.At initial injection pressure is 1000kg/cm
2, die temperature be 50 ℃ and cycling time be under 25 seconds the condition with the particle injection moulding, generate test film.Room temperature be controlled at regulate 48 hours in 23 ± 2 ℃ the isothermal chamber after, the modulus in flexure of experiment with measuring sheet.
(7) measure cantilever-type impact strength (unit: KJ/m according to " shock test method " described in the JIS K 7110
2).The resin combination granulation that to knead gained 230 ℃ of following fusions.At initial injection pressure is 1000kg/cm
2, die temperature is 50 ℃ and cycling time to be following particle injection moulding of condition of 25 seconds, generates test film.Room temperature be controlled at regulate 48 hours in 23 ± 2 ℃ the isothermal chamber after, the cantilever-type impact strength of experiment with measuring sheet.
Embodiment 1-23
In the polyethylene resin composition that contains propylene-ethylene block copolymer, nucleator and ldpe resin or type low density polyethylene resin, the calcium salt (neutralizing agent) that adds inferior phosphorus antioxidant, phenol antioxidant and higher fatty acid, their ratio is mixed them 2 minutes with Henschel mixing machine (trade(brand)name) then as described in the following table 1-4.The mixture diameter of gained is that the single screw extrusion machine of 40mm carries out fusion and kneads under 230 ℃ of temperature, and is extruded as particle.The particle molding of gained among each embodiment is become the test film of aforementioned shapes, and these test films are used for aforesaid test method(s) and assess it and comprise physicalies such as optical haze degree, modulus in flexure and cantilever-type impact strength.The results are shown in the table 1-4.
Table 1
Annotate):
| Embodiment | ||||||
| ????l | ????2 | ????3 | ????4 | ????5 | ||
| PP Resin A (PW) | ??100 | ??100 | ??100 | ??100 | ??100 | |
| PE Resin A (PW) | ??43 | ??43 | ??43 | ??43 | ??43 | |
| Nucleator A (PW) | ?0．30 | ??- | ??- | ??- | ??- | |
| Nucleator B (PW) | ??- | 0．30 | ??- | ??- | ??- | |
| Nucleator C (PW) | ??- | ??- | ?0．30 | ??- | ??- | |
| Nucleator D (PW) | ??- | ??- | ??- | ?0．30 | ??- | |
| Nucleator E (PW) | ??- | ??- | ??- | ??- | ?0．30 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ??33 | ??28 | ??32 | ??33 | ??33 | |
| Modulus in flexure (MPa) | ??820 | ??850 | ??820 | ??840 | ??880 | |
| Cantilever-type impact strength (kJ/m 2) | ??20 | ??20 | ??12 | ??11 | ??12 | |
PW: weight part
The PP Resin A: propylene-ethylene block copolymer, its MFR are 30 (restraining/10 minutes), and PP/RC is 86/14, and ethylene content is 7.0% weight (ethylene content is 48% weight in the RC part), and density is 0.902g/cm
3
The PE Resin A: (commodity are called Petrothen to the new LDPE (film grade) of Tosoh Ltd. system; The rank name is called 248), its MFR is 58 (restraining/10 minutes), density is 0.917g/cm
3
Nucleator A:1,3:2,4-Sorbitol dibenzal
Nucleator B:1,3:2, two (right-the methyl benzylidene) sorbyl alcohols of 4-
Nucleator C:1,3-are to chlorine benzylidene-2, and 4-is to the methyl benzylidene sorbitol
Nucleator D:1, two (right-the ethyl benzylidene) sorbyl alcohols of 3:2.4-
Nucleator E: two (2,4,8, and 10-tetra-tert-6-hydroxyl-12H-dibenzo [d, gl|1,3,2 ︱, two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt
Inferior phosphorus antioxidant: tricresyl phosphite (2, the 4-di-tert-butyl) ester
Phenol antioxidant: four ︱ methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic acid ︱ methane
Neutralizing agent: calcium stearate
Table 2
Annotate):
| Embodiment | |||||
| ????6 | ????7 | ????8 | ????9 | ????10 | |
| PP resin B (PW) | ????100 | ???- | ????- | ????- | ?????- |
| PP resin C (PW) | ????- | ????100 | ????- | ????- | ?????- |
| PP resin D (PW) | ????- | ???- | 100 | ????- | ?????- |
| PP resin E (PW) | ????- | ???- | ????- | ????100 | ?????- |
| PP resin F (PW) | ????- | ???- | ????- | ????- | ????100 |
| PE Resin A (PW) | ????43 | ????43 | ????43 | ????43 | ????43 |
| Nucleator B (PW) | ?0.30 | ?0.30 | ?0.30 | ?0.30 | ??0.30 |
| Inferior phosphorus antioxidant (PW) | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ??0.05 |
| Phenol antioxidant (PW) | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ??0.05 |
| Neutralizing agent (PW) | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ??0.10 |
| Optical haze degree (%) | ????29 | ????28 | ????27 | ????45 | ????26 |
| Modulus in flexure (MPa) | ????820 | ????820 | ????900 | ????780 | ????1000 |
| Cantilever-type impact strength (kJ/m 2) | ????40 | ????15 | ????7 | ????40 | ????7 |
The PP resin B: propylene-ethylene block copolymer, MFR are 1 (restraining/10 minutes), and PP/RC (weight ratio) is 86/14, and ethylene content is 7.0% weight (ethylene content is 48% weight in the RC part), and density is 0.902 g/cm
3
PP resin C: propylene-ethylene block copolymer, MFR are 60 (restraining/10 minutes), and PP/RC is 86/14 (weight ratio), and ethylene content is 7.0% weight (ethylene content is 48% weight in the RC part), and density is 0.902g/cm
3
PP resin D: propylene-ethylene block copolymer, MFR are 30 (restraining/10 minutes), and PP/RC is 92/8 (weight ratio), and ethylene content is 4.0% weight (ethylene content is 48% weight in the RC part), and density is 0.902g/cm
3
PP resin E: propylene-ethylene block copolymer, MFR are 30 (restraining/10 minutes), and PP/RC is 81/19 (weight ratio), and ethylene content is 11.0% weight (ethylene content is 58% weight in the RC part), and density is 0.902g/cm
3
PP resin F: high rigidity propylene-ethylene block copolymer, MFR is 30 (restraining/10 minutes), PP/RC is 88/12 (weight ratio), ethylene content is 4.5% weight (ethylene content is 54% weight in the RC part), log[MFR (h)/MFR (l)]=0.29, and log[MFR (p)/MFR (r)]=4.2.
Table 3
Annotate):
| Embodiment | |||||||||
| ??11 | ?12 | ?13 | ?14 | ?15 | ?16 | ?17 | ?18 | ||
| PP Resin A (PW) | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | |
| PE Resin A (PW) | ?43 | ?43 | ?20 | ?100 | ??- | ??- | ??- | ??- | |
| PE resin B (PW) | ??- | ??- | ??- | ??- | ??43 | ??- | ??- | ??- | |
| PE resin C (PW) | ??- | ??- | ??- | ??- | ??- | ??43 | ??- | ??- | |
| PE resin D (PW) | ??- | ??- | ??- | ??- | ??- | ??- | ??43 | ??- | |
| PE resin E (PW) | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??43 | |
| Nucleator B (PW) | ?0．20 | ?0．50 | ?0．30 | ?0．30 | ?0．30 | ?0．30 | ?0．30 | ?0．30 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?O．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ?30 | ?27 | ?35 | ?23 | ?29 | ?31 | ?33 | ?31 | |
| Modulus in flexure (MPa) | ?810 | ?840 | ?900 | ?750 | ?810 | ?810 | ?820 | ?830 | |
| Cantilever-type impact strength (kJ/m 2) | ?20 | ?20 | ?15 | ?40 | ?22 | ?20 | ?20 | ?40 | |
The PE resin B: the ldpe resin of Tosoh Ltd. system (commodity are called Petrothen, rank by name 342), MFR is 8 (restraining/10 minutes), density is 0.919g/cm
3
The ldpe resin of PE resin C:Tosoh Ltd. system (commodity are called Petrothen, rank by name 202), MFR is 23 (restraining/10 minutes), density is 0.918g/cm
3
The ldpe resin of PE resin D:Tosoh Ltd. system (commodity are called Petrothen, rank by name 249), MFR is 70 (restraining/10 minutes), density is 0.916g/cm
3
The type low density polyethylene resin of PE resin E:Asahi Chemical Co. system (commodity are called Suntec-LL, and rank is called LF 2408), MFR is 0.8 (restraining/10 minutes), density is 0.924 g/cm
3
Table 4
Annotate)
| Embodiment | |||||
| ????19 | ????20 | ????21 | ????22 | ????23 | |
| PP Resin A (PW) | ???100 | ???100 | ?100 | ?100 | ?100 |
| PE Resin A (PW) | ????43 | ????43 | ??43 | ??43 | ??43 |
| Nucleator B (PW) | ??0.30 | ???0.30 | ?0.30 | ?0.30 | ?0.30 |
| Rigidity nucleator A (PW) | ??0.20 | ?????- | ???- | ???- | ???- |
| ????B(PW) | ???- | ????0.20 | ???- | ???- | ???- |
| ????C(PW) | ???- | ?????- | ?0.20 | ???- | ???- |
| Superoxide A (PW) | ???- | ?????- | ???- | ?0.01 | ???- |
| ????B?(PW) | ???- | ?????- | ???- | ???- | ?0.01 |
| Inferior phosphorus antioxidant (PW) | ??0.05 | ??0.05 | ??0.05 | ?0.05 | ?0.05 |
| Phenol antioxidant (PW) | ??0.05 | ??0.05 | ??0.05 | ?0.05 | ?0.05 |
| Neutralizing agent (PW) | ??0.10 | ??0.10 | ??0.10 | ?0.10 | ?0.10 |
| Optical haze degree (%) | ????29 | ????29 | ????29 | ??25 | ??25 |
| Modulus in flexure (MPa) | ??1000 | ????950 | ???900 | ?810 | ?810 |
| Cantilever-type impact strength (kJ/m 2) | ????18 | ????18 | ????19 | ??15 | ??15 |
The rigidity nucleator:
A: phosphoric acid 2,2 '-methylene radical-two-(4, the 6-di-tert-butyl) ester sodium salt
B: two (to the tert.-butylbenzene) ester sodium salts of phosphoric acid
C: p-tert-butyl benzoic acid aluminium
Superoxide A:1,3-two (t-butyl peroxy sec.-propyl) benzene
Superoxide B:2.5-dimethyl-2.5-two (t-butyl peroxy) hexane
Comparing embodiment 1-25
In various propylene-ethylene block copolymers, add ldpe resin or type low density polyethylene resin, nucleator, inferior phosphorus antioxidant, phenol antioxidant and neutralizing agent, its ratio is mixed its then and is extruded as the particle similar to embodiment 1-23 described in following table 5-9.The particle of gained is molded as the test film of above-mentioned shape in each comparing embodiment.These test films are used for above-mentioned test method and assess its physical properties.Gained the results are shown in the table 5-9.
Table 5
| Comparing embodiment | |||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |
| PP Resin A (PW) | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| PE Resin A (PW) | ??- | ?20 | ?43 | ?100 | ???- | ???- | ???- |
| Nucleator B (PW) | ??- | ??- | ???- | ???- | ?0.10 | ?0.30 | ?0.60 |
| Inferior phosphorus antioxidant (PW) | 0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 |
| Phenol antioxidant (PW) | 0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 |
| Neutralizing agent (PW) | 0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 |
| Optical haze degree (%) | 90 | ?50 | ?40 | ?37 | ?90 | ?90 | ?89 |
| Modulus in flexure (MPa) | 980 | ?770 | ?700 | ?600 | ?1100 | ?1250 | ?1300 |
| Cantilever-type impact strength (k.J/m 2) | ????8 | ????9 | ????10 | ????15 | ????7 | ????7 | ????7 |
Table 6
| Comparing embodiment | |||||
| ????8 | ????9 | ????10 | ????11 | ||
| PP Resin A (PW) | ???100 | ???100 | ???100 | ???100 | |
| Nucleator A (PW) | ??0．30 | ??- | ??- | ??- | |
| ????C(PW) | ??- | ??0．30 | ??- | ??- | |
| ????D(PW) | ??- | ??- | ??0．30 | ??- | |
| ????E(PW) | ??- | ??- | ??- | ??0．30 | |
| The inferior anti-oxidant chaste tree of phosphorus (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Phenol antioxidant (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Neutralizing agent (PW) | ??0．10 | ??0．10 | ??0．10 | ??0．10 | |
| Optical haze degree (%) | ?89 | ?89 | ?89 | ?89 | |
| Modulus in flexure (MPa) | ?1200 | ?1200 | ?1200 | ?1300 | |
| Cantilever-type impact strength (kJ/m 2) | ????7 | ????7 | ????7 | ????7 | |
Table 7
| Comparing embodiment | |||||
| ??12 | ??13 | ??14 | ??15 | ??16 | |
| PP resin B (PW) | ??100 | ??- | ??- | ??- | ??- |
| PP resin C (PW) | ??- | ??100 | ??- | ??- | ??- |
| PP resin D (PW) | ??- | ??- | ??100 | ??- | ??- |
| PP resin E (PW) | ??- | ??- | ??- | ??100 | ??- |
| PP resin F (PW) | ??- | ??- | ??- | ??- | ??100 |
| PE Resin A (PW) | ??43 | ??43 | ??43 | ??43 | ??43 |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 |
| Optical haze degree (%) | ?40 | ?40 | ?40 | ?55 | ?39 |
| Modulus in flexure (MPa) | ?700 | ?700 | ?1000 | ?650 | ?900 |
| Cantilever-type impact strength (kJ/m 2) | ?25 | ?8 | ?7 | ?15 | ?9 |
Table 8
| Comparing embodiment | |||||
| ????17 | ????18 | ????19 | ????20 | ????21 | |
| PP resin B (PW) | ????100 | ??- | ??- | ??- | ??- |
| PP resin C (PW) | ??- | 100 | ??- | ??- | ??- |
| PP resin D (PW) | ??- | ??- | 100 | ??- | ??- |
| PP resin E (PW) | ??- | ??- | ??- | 100 | ??- |
| PP resin F (PW) | ??- | ??- | ??- | ??- | ????100 |
| Nucleator B (PW) | ?0．30 | ?0．30 | ?0．30 | ?0．30 | ?0．30 |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．053 | ?0．05 |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 |
| Optical haze degree (%) | ????90 | ????90 | ????89 | ????90 | ????90 |
| Modulus in flexure (MPa) | ?1200 | ?1250 | ?1300 | ?1000 | ?1300 |
| Cantilever-type impact strength (kJ/m 2) | ????20 | ????6 | ????6 | ????12 | ????7 |
Table 9
| Comparing embodiment | ||||
| ????22 | ????23 | ????24 | ????25 | |
| PP Resin A (PW) | ????100 | ????100 | ????100 | ????100 |
| PE resin B (PW) | ????43 | ?????- | ?????- | ?????- |
| PE resin C (PW) | ????- | ????43 | ?????- | ?????- |
| PE resin D (PW) | ????- | ????- | ????43 | ?????- |
| PE resin E (PW) | ????- | ????- | ?????- | ????43 |
| Inferior phosphorus antioxidant (PW) | ????0.05 | ????0.05 | ????0.05 | ???0.05 |
| Phenol antioxidant (PW) | ????0.05 | ????0.05 | ????0.05 | ???0.05 |
| Neutralizing agent (PW) | ????0.10 | ????0.10 | ????0.10 | ???0.10 |
| Optical haze degree (%) | ????40 | ????30 | ????39 | ????39 |
| Modulus in flexure (MPa) | ????700 | ????700 | ????700 | ????750 |
| Cantilever-type impact strength (kJ/m 2) | ????10 | ????9 | ????8 | ????11 |
Embodiment 24-44
Contain in the polyethylene resin composition of high density polyethylene(HDPE), nucleator and ldpe resin or type low density polyethylene resin, the calcium salt (neutralizing agent) that adds inferior phosphorus antioxidant, phenol antioxidant and higher fatty acid, described in its ratio such as the following table 10-13, then it was mixed 2 minutes with Henschel mixing machine (ProductName).The gained mixture carries out fusion with diameter 40mm single screw extrusion machine under 230 ℃ temperature kneads, and is extruded as granule.The granule of gained is molded as the test film of aforementioned shapes among each embodiment, and these test films are used for aforesaid test method(s) assessment and comprise physicalies such as optical haze degree, modulus in flexure and cantilever fine strain of millet formula shock strength.The results are shown in table 10-13.
Table 10
Annotate):
| Embodiment | ||||||
| ????24 | ????25 | ????26 | ????27 | ????28 | ||
| PE Resin A (PW) | ????100 | ??- | ??- | ??- | ??- | |
| PE resin M (PW) | ????43 | ????43 | ????43 | ????43 | ????43 | |
| Nucleator A (PW) | ??0．30 | ??- | ??- | ??- | ??- | |
| ????B(PW) | ??- | ??0．30 | ??- | ??- | ??- | |
| ????C(PW) | ??- | ??- | ???0．30 | ??- | ??- | |
| ????D(PW) | ??- | ??- | ??- | ??0．30 | ??- | |
| ????E(PW) | ??- | ??- | ??- | ??- | ??0．30 | |
| Inferior phosphorus antioxidant (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Phenol antioxidant (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Neutralizing agent (PW) | ??0．10 | ??0．10 | ??0．10 | ??0．10 | ??0．10 | |
| Optical haze degree (%) | ??67 | ??58 | ??67 | ???67 | ???70 | |
| Modulus in flexure (MPa) | ??740 | ??740 | ??740 | ???740 | ???740 | |
| Cantilever fine strain of millet formula shock strength (kJ/m 2) | ??6 | ??6 | ??6 | ??6 | ??6 | |
The PE Resin A: high density ethylene-propylene copolymer, MFR are 20 (restraining/10 minutes), and density is 0.960g/cm
3
The PE resin M: the ldpe resin of Tosoh Ltd. system, (commodity are called Petrothen, rank by name 248), and its MFR is 58 (restraining/10 minutes), density is 0.917g/cm
3
Nucleator A:1,3:2,4-Sorbitol dibenzal
Nucleator B:1,3:2,4-two (right-the methyl benzylidene) sorbyl alcohols
Nucleator C:1,3-to chlorine benzylidene-2,4-to the methyl benzylidene sorbitol
Nucleator D:1,3:2,4-two (to the ethyl benzylidene) sorbyl alcohols
Nucleator E: two (2,4,8.10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2], two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt
Inferior phosphorus antioxidant: tricresyl phosphite (2,4-di-tert-butyl) ester
Phenol antioxidant: four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic acid] methane
Neutralizing agent: calcium stearate
Table 11
Annotate):
| Embodiment | ||||||
| ????29 | ????30 | ????31 | ????32 | ????33 | ||
| PE resin B (PW) | ????100 | ??- | ??- | ??- | ??- | |
| PE resin C (PW) | ??- | ???100 | ??- | ??- | ??- | |
| PE resin D (PW) | ??- | ??- | ??100 | ??- | ??- | |
| PE resin E (PW) | ??- | ??- | ??- | ??100 | ??- | |
| PE resin F (PW) | ??- | ??- | ??- | ??- | ??100 | |
| PE resin M (PW) | ????43 | ????43 | ????43 | ????43 | ????43 | |
| Nucleator B (PW) | ?0．30 | ?0．30 | ?0．30 | ?0．30 | ?0．30 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ????60 | ????59 | ????58 | ????58 | ????59 | |
| Modulus in flexure (MPa) | ????740 | ????740 | ????780 | ????600 | ????600 | |
| Cantilever-type impact strength (kJ/m 2) | ???40 | ????4 | ???40 | ????6 | ????4 | |
The PE resin B: high density ethylene-propylene copolymer, MFR are 2.5 (restraining/10 minutes), and density is 0.960g/cm
3
PE resin C: high density ethylene-propylene copolymer, MFR are 40 (restraining/10 minutes), and density is 0.960 g/em
3
PE resin D: high density ethylene homopolymers, MFR are 5 (restraining/10 minutes), and density is 0.962 g/cm
3
PE resin E: high density ethylene-butylene copolymer, MFR are 20 (gram/l0 minutes), and density is 0.950 g/cm
3
PE resin F: high density ethylene-propylene copolymer, MFR are 20 (restraining/10 minutes), and density is 0.950 g/cm
3
Table 12
Annotate):
| Embodiment | ||||||||
| 34 | ?35 | ?36 | ?37 | ?38 | ?39 | ?40 | ?41 | |
| PE Resin A (PW) | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| PE resin M (PW) | 43 | ?43 | ?20 | ?100 | ??- | ???- | ???- | ???- |
| PE resin N (PW) | ??- | ??- | ??- | ??- | 43 | ???- | ???- | ???- |
| PE resin P (PW) | ??- | ??- | ??- | ??- | ??- | 43 | ???- | ???- |
| PE resin Q (PW) | ??- | ??- | ??- | ??- | ??- | ???- | 43 | ???- |
| PE resin R (PW) | ??- | ??- | ??- | ??- | ??- | ???- | ???- | 43 |
| Nucleator B (PW) | 0.20 | ?0.50 | ?0.30 | ?0.30 | ?0.30 | ?0.30 | ?0.30 | ?0.30 |
| Inferior phosphorus antioxidant (PW) | 0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 |
| Phenol antioxidant (PW) | 0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 | ?0.05 |
| Neutralizing agent (PW) | 0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.10 |
| Optical haze degree (%) | 65 | ?59 | ?65 | ?54 | ?60 | ?60 | ?61 | ?61 |
| Modulus in flexure (MPa) | 740 | ?750 | ?850 | ?550 | ?760 | ?760 | ?760 | ?760 |
| Cantilever-type impact strength (kJ/m 2) | ????6 | ????6 | ????5 | ????30 | ????6 | ????6 | ????6 | ????6 |
The ldpe resin of PE resin N:Tosoh Ltd. system (commodity are called Petrothen, rank by name 342), MFR is 8 (restraining/10 minutes), density is 0.919g/cm
3
The ldpe resin of PE resin P:Tosoh Ltd. system (commodity are called Petrothen, rank by name 202), MFR is 23 (restraining/10 minutes), density is 0.918g/cm
3
The ldpe resin of PE resin Q:Tosoh Ltd. system (commodity are called Petrothen, rank by name 249), MFR is 70 (restraining/10 minutes), density is 0.916g/cm
3
The type low density polyethylene resin of PE resin R:Asahi Chemical Co. system (commodity are called Suntec-LL, and rank is called LF 2408), MFR is 0.8 (restraining/10 minutes), density is 0.924g/cm
3
Table 13
Annotate):
| Embodiment | ||||
| ????42 | ????43 | ????44 | ||
| PE Resin A (PW) | ????100 | ????100 | ????100 | |
| PE resin M (PW) | ????43 | ????43 | ????43 | |
| Nucleator B (PW) | ????0．30 | ????0．30 | ????0．30 | |
| Rigidity nucleator A (PW) | ????0．20 | ??- | ??- | |
| Rigidity nucleator B (PW) | ??- | ????0．20 | ??- | |
| Rigidity nucleator C (PW) | ??- | ??- | ????0．20 | |
| Inferior phosphorus antioxidant (PW) | ????0．05 | ????0．05 | ????0．05 | |
| Phenol antioxidant (PW) | ????0．05 | ????0．05 | ????0．05 | |
| Neutralizing agent (PW) | ????0．10 | ????0．10 | ????0．10 | |
| Optical haze degree (%) | ????59 | ????59 | ????59 | |
| Modulus in flexure (MPa) | ????750 | ????750 | ????750 | |
| Cantilever-type impact strength (kJ/m 2) | ????6 | ????6 | ????6 | |
The rigidity nucleator:
A: phosphoric acid 2,2 '-methylene radical-two (4,6-di-tert-butyl) ester sodium salt
B: two (to the tert.-butylbenzene) ester sodium salts of phosphoric acid
C: p-tert-butyl benzoic acid aluminium
Comparing embodiment 26-50
Add ldpe resin or type low density polyethylene resin, nucleator, inferior phosphorus antioxidant in the various high density polyethylene(HDPE)s, phenol antioxidant and neutralizing agent, its ratio is listed in the following table 14-18, then its is mixed and extrudes, and becomes the particle similar to embodiment 24-44.Each comparing embodiment gained particle molding is become the test film of aforementioned shapes.These test films are used for the afore-mentioned test method and assess its physicals.The results are shown in the table 14-18.
Table 14
| Comparing embodiment | |||||||
| ????26 | ???27 | ???28 | ???29 | ???30 | ???31 | ???32 | |
| PE Resin A (PW) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| PE resin M (PW) | ??- | ??20 | ???43 | ??100 | ??- | ??- | ??- |
| Nucleator B (PW) | ??- | ??- | ??- | ??- | 0．10 | ?0．30 | ?0．60 |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 |
| Optical haze degree (%) | ????91 | ?91 | ?90 | ?90 | ?85 | ?75 | ?75 |
| Modulus in flexure (MPa) | 1070 | ?900 | ?670 | ?500 | ?1070 | ?1080 | ?1100 |
| Cantilever fine strain of millet formula shock strength (kJ/m 2) | ?3 | ?3 | ?6 | ?30 | ?3 | ?3 | ?3 |
Table 15
| Comparing embodiment | |||||
| ????33 | ????34 | ????35 | ????36 | ||
| PE Resin A (PW) | ???100 | ???100 | ???100 | ???100 | |
| Nucleator A (PW) | ???0．30 | ??- | ??- | ??- | |
| Nucleator C (PW) | ??- | ??0．30 | ??- | ??- | |
| Nucleator D (PW) | ??- | ??- | ??0．30 | ??- | |
| Nucleator E (PW) | ??- | ??- | ??- | ??0．30 | |
| Inferior phosphorus antioxidant (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Phenol antioxidant (PW) | ??0．05 | ??0．05 | ??0．05 | ??0．05 | |
| Neutralizing agent (PW) | ??0．10 | ??0．10 | ??0．10 | ??0．10 | |
| Optical haze degree (%) | ????83 | ????83 | ????85 | ????85 | |
| Modulus in flexure (MPa) | ???1080 | ???1080 | ???1080 | ???1080 | |
| Cantilever-type impact strength (kJ/m 2) | ????3 | ????3 | ????3 | ????3 | |
Table 16
| Comparing embodiment | ||||||
| ????37 | ????38 | ????39 | ????40 | ????41 | ||
| PE resin B (PW) | ???100 | ??- | ??- | ??- | ??- | |
| PE resin C (PE) | ??- | ??100 | ??- | ??- | ??- | |
| PE resin D (PW) | ??- | ??- | ??- | ??- | ??- | |
| PE resin E (PW) | ??- | ??- | ??- | ??100 | ??- | |
| PE resin F (PW) | ??- | ??- | ??- | ??- | ???100 | |
| PE resin M (PW) | ????43 | ????43 | ????43 | ????43 | ????43 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ????91 | ????91 | ????91 | ????91 | ????91 | |
| Modulus in flexure (MPa) | ???670 | ???670 | ???700 | ???500 | ???500 | |
| Cantilever-type impact strength (kJ/m 2) | ????40 | ????5 | ????40 | ????6 | ????6 | |
Table 17
| Comparing embodiment | ||||||
| ????42 | ????43 | ????44 | ????45 | ????46 | ||
| PE resin B (PW) | ????100 | ??- | ??- | ??- | ??- | |
| PE resin C (PE) | ??- | ????100 | ??- | ??- | ??- | |
| PE resin D (PW) | ??- | ??- | ????100 | ??- | ??- | |
| PE resin E (PW) | ??- | ??- | ??- | ????100 | ??- | |
| PE resin F (PW) | ??- | ??- | ??- | ??- | ???100 | |
| Nucleator B (PW) | ?0．30 | ?0．30 | ?0．30 | ?0．30 | ?0．30 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ????77 | ????76 | ????75 | ????75 | ????76 | |
| Modulus in flexure (MPa) | ??1080 | ??1080 | ??1200 | ???900 | ???900 | |
| Cantilever-type impact strength (kJ/m 2) | ????25 | ????3 | ????9 | ????3 | ????3 | |
Table 18
| Comparing embodiment | |||||
| ????47 | ????48 | ????49 | ????50 | ||
| PE Resin A (PW) | ????100 | ????100 | ????100 | ????100 | |
| PE resin N (PE) | ????43 | ??- | ??- | ??- | |
| PE resin P (PW) | ??- | ????43 | ??- | ??- | |
| PE resin Q (PW) | ??- | ??- | ????43 | ??- | |
| PE resin R (PW) | ??- | ??- | ??- | ????43 | |
| Inferior phosphorus antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Phenol antioxidant (PW) | ?0．05 | ?0．05 | ?0．05 | ?0．05 | |
| Neutralizing agent (PW) | ?0．10 | ?0．10 | ?0．10 | ?0．10 | |
| Optical haze degree (%) | ????90 | ????90 | ????91 | ????91 | |
| Modulus in flexure (MPa) | ????750 | ????670 | ????750 | ????800 | |
| Cantilever fine strain of millet formula shock strength (kJ/m 2) | ????7 | ????6 | ????7 | ????20 | |
Be used for the below that the acrylic resin of embodiment and comparing embodiment, various polyvinyl resin and additive are described in table 1-4 and table 10-13 respectively.The add-on of each component is to represent with respect to the weight part of 100 weight part acrylic resins or high-density polyethylene resin.
Claims (10)
1. polyolefine resin composition, contain the olefin polymer that 100 weight parts are selected from propylene-ethylene block copolymer and high density polyethylene(HDPE), 0.1-0.6 weight part nucleator, and at least a in 20-100 weight part new LDPE (film grade)s and the LLDPE.
2. the polyolefine resin composition of claim 1, wherein polyolefine is propylene-ethylene block copolymer.
3. the polyolefine resin composition of claim 2 also comprises one or more superoxide of 0.001-0.1 weight part, and described superoxide is selected from 1,3-two (t-butyl peroxy sec.-propyl) benzene and 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane.
4. the polyolefine resin composition of claim 2, wherein (230 ℃ is 0.5-100 grams/10 minutes 21.18N) to the melt flow rate (MFR) of propylene-ethylene block copolymer, and density is 0.895-0.910g/cm
3, ethylene content is 3-15% weight, random copolymers content is 6-30% weight.
5. the polyolefine resin composition of claim 2, wherein the melt flow rate (MFR) of ldpe resin (190 ℃ is 5-70 21.18N)) gram is/10 minutes, and density is 0.915-0.925g/cm
3, (190 ℃ is 0.5-5 grams/10 minutes 21.18N) to the melt flow rate (MFR) of type low density polyethylene resin, and density is 0.920-0.930g/cm
3
6. each polyolefine resin composition of claim 2-5, wherein nucleator is to be selected from the following compounds one or more: 1,3: 2,4-Sorbitol dibenzal, 1,3: 2,4-two (right-the methyl benzylidene) sorbyl alcohols, 1,3-right-chlorine benzylidene-2,4-to the methyl benzylidene sorbitol, 1,3: 2,4-two (right-the ethyl benzylidene) sorbyl alcohols, and two (2,4,8,11-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt.
7. the polyolefine resin composition of claim 1, wherein polyolefine is a high-density polyethylene resin.
8. the polyolefine resin composition of claim 7, wherein (190 ℃ is 1-50 grams/10 minutes 21.18N) to the melt flow rate (MFR) of high-density polyethylene resin, and density is 0.941-0.965g/cm
3
9. the polyolefine resin composition of claim 7, wherein (190 ℃ is 5-70 grams/10 minutes 21.18N) to the melt flow rate (MFR) of ldpe resin, and density is 0.915-0.925g/cm
3, and the melt flow rate (MFR) of type low density polyethylene resin (190 ℃, 21.18N) be 0.5-5 grams/10 minutes, density is 0.920-0.930g/cm
3
10. each polyolefine resin composition of claim 7-9, wherein nucleator is to be selected from the following compounds one or more: 1,3: 2,4-Sorbitol dibenzal, 1,3: 2,4-two (right-the methyl benzylidene) sorbyl alcohols, 1,3-right-chlorine benzylidene-2,4-to the methyl benzylidene sorbitol, 1,3: 2,4-two (right-the ethyl benzylidene) sorbyl alcohols, and two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phosphorus ring-6-oxide compounds) aluminium hydroxide salt.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19943199A JP4281157B2 (en) | 1999-07-13 | 1999-07-13 | Polypropylene resin composition |
| JP199431/1999 | 1999-07-13 | ||
| JP11215750A JP2001040151A (en) | 1999-07-29 | 1999-07-29 | Polyethylene resin composition |
| JP215750/1999 | 1999-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1280145A true CN1280145A (en) | 2001-01-17 |
Family
ID=26511532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00120230A Pending CN1280145A (en) | 1999-07-13 | 2000-07-12 | Polyolefine resin composition |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20010049764A (en) |
| CN (1) | CN1280145A (en) |
| TW (1) | TW524825B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101426880A (en) * | 2005-03-17 | 2009-05-06 | 陶氏环球技术公司 | Cap liners, closures and gaskets from multi-block polymers |
| CN101061173B (en) * | 2004-11-18 | 2010-05-12 | 博里利斯技术有限公司 | Novel propylene polymer compositions |
| CN104163984A (en) * | 2013-10-31 | 2014-11-26 | 中国石油化工股份有限公司 | Polyolefin resin composition and preparation method thereof |
| CN106025156A (en) * | 2016-05-19 | 2016-10-12 | 河南师范大学 | Nano plasticized porous polyethylene dry-stretched film for lithium ion batteries and preparation method thereof |
| CN111518330A (en) * | 2020-06-15 | 2020-08-11 | 康派新材料科技(扬州)有限公司 | Polyethylene composition for hazardous waste storage container |
-
2000
- 2000-07-05 TW TW089113290A patent/TW524825B/en active
- 2000-07-12 CN CN00120230A patent/CN1280145A/en active Pending
- 2000-07-12 KR KR1020000039880A patent/KR20010049764A/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061173B (en) * | 2004-11-18 | 2010-05-12 | 博里利斯技术有限公司 | Novel propylene polymer compositions |
| CN101426880A (en) * | 2005-03-17 | 2009-05-06 | 陶氏环球技术公司 | Cap liners, closures and gaskets from multi-block polymers |
| CN104163984A (en) * | 2013-10-31 | 2014-11-26 | 中国石油化工股份有限公司 | Polyolefin resin composition and preparation method thereof |
| CN104163984B (en) * | 2013-10-31 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of polyolefine resin composition and preparation method thereof |
| CN106025156A (en) * | 2016-05-19 | 2016-10-12 | 河南师范大学 | Nano plasticized porous polyethylene dry-stretched film for lithium ion batteries and preparation method thereof |
| CN106025156B (en) * | 2016-05-19 | 2019-05-14 | 河南师范大学 | A kind of lithium ion battery nanometer plasticizing porous polyethylene dry-stretched membrane and preparation method thereof |
| CN111518330A (en) * | 2020-06-15 | 2020-08-11 | 康派新材料科技(扬州)有限公司 | Polyethylene composition for hazardous waste storage container |
Also Published As
| Publication number | Publication date |
|---|---|
| TW524825B (en) | 2003-03-21 |
| KR20010049764A (en) | 2001-06-15 |
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