CN1214051C - Coating material comprising linear, isotactic polymers - Google Patents

Coating material comprising linear, isotactic polymers Download PDF

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Publication number
CN1214051C
CN1214051C CNB008140502A CN00814050A CN1214051C CN 1214051 C CN1214051 C CN 1214051C CN B008140502 A CNB008140502 A CN B008140502A CN 00814050 A CN00814050 A CN 00814050A CN 1214051 C CN1214051 C CN 1214051C
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CN
China
Prior art keywords
coating
present
goods
better
polymer
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Expired - Fee Related
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CNB008140502A
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Chinese (zh)
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CN1378565A (en
Inventor
V·A·达特罗夫
B·汉克
B·里格
M·奥洛斯
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Abstract

The present invention relates to articles comprising elements at least partially coated with polymeric material wherein the structure of the polymeric material contains elastic amorphous areas of nano-scale-size reinforced with self arranged crystalline domains of nano-crystals. An article, comprising an element and a polymeric coating material covering at least portion of the surface of said element characterized in that said coating material comprises a polyolefinic homopolymer having an isotacticity of less than 60 % of mmmm pentad concentration, is claimed.

Description

The coating that contains linear, isotactic polymers
Invention field
The present invention relates to for example to be used to insulate, the coating of shock absorption, buffering, packing.The present invention is specifically related to elastic coating.
The background of invention
Coated article particularly contains the coating of olefin polymer, is well-known in the art, and has obtained widespread use industrial.The common Application Areas of this coating comprises hygienic articles, particularly disposable absorbent article, wrapping material.
The coating that is made by polyolefine (as PP, PE, PS, PIB) commonly used has many useful performances.They are physiologically acceptable, food compatible, chemically stable, inertia, non-toxic materials.Yet the major part of these materials is inflexible, and bad mechanical property comprises low intensity/resistance to tearing, low stretchiness and elasticity etc.
Several these polymer coating rubber-like methods that make have now been proposed in the prior art.The most frequently used method is based on by introduce hinge type tie point/part in main polymer chain and changes the chemical structure of this polymkeric substance.These hinges (hing) provide bigger flexibility to main polymer chain, thereby prevent polymer crystallization, reduces the elasticity of its second-order transition temperature (Tg) and raising gained material.Usually, these hinge groups contain to insert in main chain or the bulky side group provides flexible heteroatoms, as oxygen, nitrogen or chlorine.Another kind method is to plasticate by polymkeric substance is mixed with special softening agent.Yet these two kinds of methods all need be introduced heteroatoms in the molecule of coating or body.
Making the third method of polymer coating rubber-like in the prior art is to form the heterogeneous of enhancing bulk material by forming the physical mesh thing.This method and of the present invention more approaching.In order to reach this purpose, carry out block copolymerization with the different monomers that is no less than two kinds, produce the main polymer chain that contains block with different glass transition temperature.Make like this and microphase-separated takes place in the body, form the flexible chain interconnective enhancing crystallization microcell of a kind of multipolymer simultaneously by second kind of multipolymer.
In fact, Chang Gui polymer coating has many intrinsic shortcomings.These shortcomings include, but are not limited to low intensity/resistance to tearing, low stretchiness/elasticity, bio-incompatibility, food uncompatibility, produce poisonous resistates etc. owing to contain the heteroatoms of chlorine and so on when burning.
The purpose of this invention is to provide the coating that can overcome existing coating shortcoming.
Another object of the present invention provides the goods that contain elastic coating.
The 3rd purpose of the present invention provides the manufacture method of coated article of the present invention.
Summary of the invention
The invention provides a kind of coating composition that is used for covering with polymer coating at least a portion element surface, its characteristics are that above-mentioned coating composition contains the olefin homo of [mmmm] five unit group concentration less than the degree of isotacticity of 60% (pentadconcentration).
The present invention also provides a kind of goods, and it comprises element and covers the above-mentioned polymer coating at least a portion said elements surface.
The present invention also provides the method for the above-mentioned polymer coating application element of a kind of usefulness.This method comprises and is selected from dip-coating, spraying, emulsion coating or their bonded steps.
The detailed description of invention
The invention provides the coating that contains olefin homo.
The used term " olefin homo " of the application is meant and only contains the polyolefine that all molecules all have the molecule phase of similar three-dimensional chemical configuration.For example, when using this term, do not comprise the blend of own polymeric nonstereospecific polymer simultaneously of two-phase and isotactic polymer.Term " homopolymer " comprises that all molecules all have the multipolymer of similar three-dimensional chemical configuration.
Olefin homo of the present invention can comprise having one or several C 3-C 20Olefinic monomer structure, [mmmm] five unit group concentration are less than 60%, better less than 55%, better less than 50%, preferably less than 45% degree of isotacticity and [mmmm] five unit group concentration greater than 15%, better greater than 20%, better greater than 25%, more preferably greater than the linear, isotactic polymers of degree of isotacticity.Olefin homo of the present invention better is a polypropylene.
Because the statistical distribution of polymer chain neutral body error (stereoscopic error), the degree of isotacticity of these homopolymer is lower than the degree of isotacticity of existing isotactic polyprophlene.Term " three-dimensional error " is meant the three-dimensional sequences that usefulness [mrrm] five unit groups characterize.In this case, center monomer have with this Unit five group in all the other four steric configurations that monomer is opposite.Therefore, [mrrm] five unit group concentration are higher than statistical probability p in this polymkeric substance 2(1-p) 2, p=[m in the formula], 1-p=[r], and p 4=[mmmm].Five unit group concentration better are at least [p (1-p] qP (1-p), q is 0.8 in the formula, is preferably 0.6, more preferably 0.4, better is 0.2, is preferably 0.1.
In some embodiments of homopolymer, particularly, proved that now the atactic sequence of low levels helps the performance of coating of the present invention reducing in the embodiment of degree of crystallinity with single three-dimensional error (single stereoerror).[rmrm] five unit group concentration should be lower than 6%, better are lower than 5%, better are lower than 4%, are lower than 3% better, are preferably lower than 2.5%.
In some embodiments of homopolymer, particularly, proved that now the syndiotactic sequence of low levels helps the performance of coating of the present invention reducing in the embodiment of degree of crystallinity with single three-dimensional error.[rrrr] five unit group concentration should be lower than 6%, better are lower than 5%, better are lower than 4%, are lower than 3% better, are preferably lower than 2.5%.
Perhaps, homopolymer of the present invention can comprise the sequence of atactic and isotactic polymer blocks.
The average molecular weight Mw of this polymkeric substance is preferably more than the 100000 gram/moles, is preferably more than the 200000 gram/moles, and is more preferably more than the 250000 gram/moles, better greater than 300000 gram/moles, more preferably greater than 350000 gram/moles.
Glass transition temperature Tg is between-50 ℃ to+30 ℃.This second-order transition temperature should be lower than 10 ℃, better is lower than 5 ℃, better is lower than 0 ℃, is preferably lower than-6 ℃.This sample is heated to 150 ℃, then this polymkeric substance is cooled to-50 ℃ after, obtain the melt temperature of this polymkeric substance.
Though do not want to be subjected to the constraint of this theory, these olefin polymers have the hypocrystalline structure.This structure contains useful from the nano level crystalline crystallization microcell enhanced nano level elasticity amorphous areas of arranging.In this main polymer chain, introduce defective, can be by this polymer formation fragility macrocrystalline material.The isolated cell unit that will have opposite steric configuration is as this defective, as single three-dimensional error.
The manufacture method of suitable polymers and these polymkeric substance is documented among the PCT patent application EP99/02379.This patent application is with reference to being incorporated among the present invention.Be applicable to that the catalyst composition of making these polymkeric substance is documented among the PCT patent application EP99/02378.This patent application is with reference to being incorporated among the present invention.Method described in the PCT patent application EP99/02378 should be lower than 30 ℃, better is lower than 25 ℃, better is lower than 20 ℃, is preferably lower than under 15 ℃ the temperature to carry out, to improve the molecular weight of resulting polymers.In order to improve molecular weight, polyreaction should be carried out in the liquid monomer of propylene liquid and so on.In order to improve molecular weight, this catalyzer should be used in combination with the boron activator described in the PCT patent application EP99/02378.
The manufacture method of other suitable polymers and these polymkeric substance is documented among the WO 99/20664.This patent application is with reference to being incorporated among the present invention.
The preferred homopolymer that uses in the coating of the present invention is because can significantly reduce the mutability of each batch than polymerization heterogenetic multiphase polymer in the single reaction in the manufacturing processed of homopolymer.
The polymkeric substance that is used to make coating of the present invention should have distinctive rubber-resilient planar district on tensile strength curve.
The polymkeric substance that is used for coating of the present invention is biocompatible, can burn, and not have toxic residue, because their not chloride and so on heteroatomss.They also do not contain toxicity monomer residue thing.
Have now found that coating of the present invention can have excellent flexibility.The A level Shore hardness of coating of the present invention should be less than 30, and is better less than 15 better less than 20 better less than 25, preferably less than 10.Reduce degree of isotacticity ([mmmm] five unit group concentration) when making coating of the present invention, can improve the flexibility of coating of the present invention.
Have now found that coating of the present invention has the temperature stability higher than existing coating.Some reasons are that coating of the present invention uses homopolymer, and partly cause is the high molecular of this homopolymer.The fusing point of coating of the present invention should be at least 100 ℃, better is at least 110 ℃, better is at least 120 ℃, preferably is at least 130 ℃.Sample is heated to 150 ℃, then polymkeric substance is cooled to-50 ℃, can record the melt temperature of this polymkeric substance.For example this homopolymer is mixed with conventional isotactic polymer (as polypropylene), can obtain higher fusing point.
Have now found that coating of the present invention is stretchable, and have elasticity.The tensility of this coating and elasticity thereof can be regulated by the tacticity of homopolymer of the present invention.Have now found that coating of the present invention can be stretched to 500% of former length at least, better be stretched to 1000% of former length at least, better be stretched to 1500% of former length at least, preferably be stretched to 2000% of former length at least, and can not tear.In addition, coating of the present invention be stretched to former length 500% and keep 1 minute after, should in 10 minutes, return to less than 300% of former length, better return to less than 200% of former length, preferably return to less than 150% of former length.Also have, have now found that coating of the present invention has low compressive set.Coating of the present invention is after being compressed to 50%1 minutes of original thickness, can in 10 minutes, return to 60% of original thickness at least, better return to 70% of original thickness at least, better 80% of the original thickness that returns at least, good more 90% of the original thickness that returns at least preferably returns to 95% of original thickness at least.The homopolymer that maybe will hang down tacticity by the tacticity that improves homopolymer mixes the compressibility of adjustable abridged edition invention coating with conventional isotactic polymer (as polypropylene).
Have now found that coating of the present invention can be coated with by lower ground mass, the ground mass of coating of the present invention should less than 50 the gram/square metre, better less than 40 the gram/square metre, better less than 30 the gram/square metre, better less than 20 the gram/square metre, preferably less than 10 the gram/square metre.
Existing oneself finds, coating of the present invention at room temperature has lower viscosity because the molecular weight of polymkeric substance is high.
Can add various additives in the homopolymer of the present invention, so that change polymer properties, performance as known in the art.
Another aspect of the present invention provides and comprises the goods of at least a portion surface with the element of coating coating of the present invention.
In the prior art, known many technology that is suitable for making coated article.These technology include, but are not limited to dip coating, spraying method, emulsion coating method and their combination.As long as the polymkeric substance in the coating can be fully bonding with ground, coating of the present invention is not limited to specific ground.Suitable ground includes, but are not limited to the object of various materials, as metal, polymkeric substance, timber, weave and non-woven fabric material, film etc.The known certain benefits of those of ordinary skill in all capable territory of the method for above-mentioned manufacturing coated article.Therefore, those skilled in the art can select to be applicable to the method for making coating of the present invention according to the specific requirement of coating various uses.
In order to make coating of the present invention have ventilation property, make with this coating that stretches before (before or after ground contact), this polymkeric substance can be mixed with the granular filler of lime carbonate and so on, so that when stretching coating, comprising the place generation micropore of filler.The moisture transmission of the ventilative thin-film material of the present invention (MVTR) should be at least/24 hours square metres of 1000 grams, better is at least/24 hours square metres of 2000 grams, better is at least/24 hours square metres of 3000 grams, preferably is at least/24 hours square metres of 4000 grams.The measuring method of moisture permeability is well known in the art, can directly use.
Coated article of the present invention can be a hygienic articles.Used term " hygienic articles " instigates the time spent to contact with human body or approaching goods among the application.These hygienic articles can be disposable, or can be repeatedly or life-time service.These hygienic articles include, but are not limited to unlined long gown, surgical operation curtain, body and are implanted into sheet, apparatus, bearing part, sheet, wound dressings, wound spray, hair spray etc.Considered to be used for the concrete advantage of polymkeric substance of goods of the present invention, how those skilled in the art know that the coating with polymer materials of the present invention is used for above-mentioned with similar hygienic articles.
Coating of the present invention also can be used as the structural element in the goods.Therefore, the function of coating of the present invention include, but are not limited to thermal insulation, electrical isolation, absorption impact, buffering, sound wave damping, protection goods other element, protection against corrosion, make other element can relative movement, anti-skidding etc.These goods include, but are not limited to toy, furniture, clothes, shoes, sports equipment, clip, complex construction such as buildings (flooring material, gap-filling glue, sealing agent, ridge/crack filler etc.), automobile, household electrical appliance etc.After having considered to be used for the concrete advantage of polymkeric substance of goods of the present invention, those skilled in the art how to know with coating of the present invention as and at random be improved to structural elements above-mentioned and similar goods.

Claims (6)

1. goods, it comprises element and covers the polymer coating of the described element surface of at least a portion, it is characterized in that described coating contain [mmmm] five unit group concentration less than 60%, [rmrm] five unit group concentration be lower than 3% and [rrrr] five unit group concentration be lower than the olefin homo of 6% degree of isotacticity, and described olefin homo contains the molecule phase that all molecules all have similar three-dimensional chemical configuration.
2. goods as claimed in claim 1 is characterized in that described coating is stretchable.
3. goods as claimed in claim 2, but it is characterized in that described coating is elastic expansion.
4. goods as claimed in claim 1 is characterized in that described homopolymer is a polypropylene.
5. goods as claimed in claim 1 is characterized in that described goods are hygienic articles.
6. goods as claimed in claim 1 is characterized in that described polymer coating is the structural element of described goods.
CNB008140502A 1999-10-08 2000-10-02 Coating material comprising linear, isotactic polymers Expired - Fee Related CN1214051C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99120173 1999-10-08
EP99120173.2 1999-10-08

Publications (2)

Publication Number Publication Date
CN1378565A CN1378565A (en) 2002-11-06
CN1214051C true CN1214051C (en) 2005-08-10

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Country Status (9)

Country Link
EP (1) EP1237956A1 (en)
JP (1) JP2003511525A (en)
KR (1) KR100497592B1 (en)
CN (1) CN1214051C (en)
AU (1) AU780540B2 (en)
BR (1) BR0014600A (en)
CA (1) CA2386901A1 (en)
MX (1) MXPA02003512A (en)
WO (1) WO2001027170A1 (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2830160A1 (en) * 1977-07-12 1979-01-25 Du Pont FRACTIONABLE ELASTIC POLYPROPYLENE AND THE METHOD FOR MANUFACTURING IT
US4522982A (en) * 1983-06-06 1985-06-11 Exxon Research & Engineering Co. Isotactic-stereoblock polymers of alpha-olefins and process for producing the same
USH1583H (en) * 1993-06-01 1996-08-06 Shell Oil Company Elastomeric polybutylene polymer
US5594080A (en) * 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor
JP3824325B2 (en) * 1994-12-20 2006-09-20 モンテル テクノロジー カンパニー ビーブイ Reactant blend polypropylene, process for its production and process for the production of metallocene ligands
WO1996026967A1 (en) * 1995-03-01 1996-09-06 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borate complexes and catalysts derived therefrom
IT1275408B (en) * 1995-05-30 1997-08-05 Spherilene Spa BIS-INDENYL METALLOCENIC COMPOUNDS PONTANTS PROCEDURE FOR THEIR PREPARATION AND THEIR USE IN CATALYSTS FOR THE POLYMERIZATION OF OLEFINS
DE19709486A1 (en) * 1997-03-07 1998-09-10 Studiengesellschaft Kohle Mbh Processes and catalysts for the stereospecific polymerization of olefins with chiral half-sandwich metallocene catalysts
US6265512B1 (en) * 1997-10-23 2001-07-24 3M Innovative Company Elastic polypropylenes and catalysts for their manufacture
DE19816154A1 (en) * 1998-04-09 1999-10-21 Bernhard Rieger Linear isotactic polymers, processes for their production and their use and a catalyst combination

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Publication number Publication date
CA2386901A1 (en) 2001-04-19
BR0014600A (en) 2002-06-11
KR100497592B1 (en) 2005-07-01
AU780540B2 (en) 2005-03-24
WO2001027170A1 (en) 2001-04-19
AU7846800A (en) 2001-04-23
KR20020040842A (en) 2002-05-30
CN1378565A (en) 2002-11-06
EP1237956A1 (en) 2002-09-11
MXPA02003512A (en) 2002-08-20
JP2003511525A (en) 2003-03-25

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