CN1772804A - Ptef aqueous dispersion liquid composition, polytetrafluoroethylene film and roof materials - Google Patents
Ptef aqueous dispersion liquid composition, polytetrafluoroethylene film and roof materials Download PDFInfo
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- CN1772804A CN1772804A CN 200510105741 CN200510105741A CN1772804A CN 1772804 A CN1772804 A CN 1772804A CN 200510105741 CN200510105741 CN 200510105741 CN 200510105741 A CN200510105741 A CN 200510105741A CN 1772804 A CN1772804 A CN 1772804A
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Abstract
To provide a polytetrafluoroethylene aqueous dispersion composition suitable as a material for a membranous material, to provide the polytetrafluoroethylene membranous material having excellent light transmittance and to provide a roofing material composed of the polytetrafluoroethylene membranous material. The polytetrafluoroethylene aqueous dispersion composition is obtained by dispersing fluoropolymer particles composed of tetrafluoroethylene homopolymer and/or a modified polytetrafluoroethylene in an aqueous medium. The polytetrafluoroethylene aqueous dispersion composition is characterized in that [alpha] calculated from formula (Ia) [alpha]=10/ln(I<SB>0</SB>/I) is >=260 when the intensity of the incident light for the polytetrafluoroethylene membranous material without containing a substrate is I<SB>0</SB>; the intensity of transmitted light is I and the thickness of the membranous material is 10 [mu]m.
Description
Technical field
The present invention relates to aqueous polytetrafluoroethyldispersion dispersion composition, the membranaceous thing of tetrafluoroethylene and contain the roof Material of the membranaceous thing of this tetrafluoroethylene.
Background technology
Because the polytetrafluoroethylene (PTFE) film has outstanding thermotolerance and weathering resistance etc., past is used as the roof Material, high frequency printed base plate, carry strap, liner of membrane structure buildings etc.
When being used for the roof Material of membrane structure buildings, need higher light transmission, therefore proposed to use the technology (for example, with reference to patent documentation 1 and patent documentation 2) of PTFE at the roof Material of membrane structure buildings.But, the technology of putting down in writing in these patent documentations has provided water-repellancy and hydrophilic technology respectively.
As the PTFE of the roof Material that is used for the membrane structure buildings, also disclose to improving the PTFE layer (for example, with reference to patent documentation 3) that light transmission is provided with.Yet only this PTFE layer makes it to produce light transmission by containing granulated glass sphere, its objective is the antifouling property of raising as roof Material integral body.
As using PTFE, proposed fluorine resins such as PTFE be impregnated in the technology (for example, with reference to patent documentation 4 and patent documentation 5) of specific base material with the roof Material of light transmission as the membrane structure buildings of purpose.Yet, be to use the base material of ad hoc structure on these technological essences, so that PTFE does not fill the space of base material is inaccessible, there is the limited problem of range of choice of the base material that can use in these technology.
[patent documentation 1] spy opens flat 7-290660 communique
[patent documentation 2] spy opens flat 10-193528 communique
[patent documentation 3] spy opens flat 9-207289 communique
[patent documentation 4] spy opens flat 4-300363 communique
[patent documentation 5] spy opens flat 9-256277 communique
Summary of the invention
In view of stating present situation, the objective of the invention is to, the good membranaceous thing of tetrafluoroethylene of suitable aqueous polytetrafluoroethyldispersion dispersion composition, the light transmission of making the membranoid substance material is provided and contains the roof Material of the membranaceous thing of described tetrafluoroethylene.
The present invention relates to aqueous polytetrafluoroethyldispersion dispersion composition, it is the aqueous polytetrafluoroethyldispersion dispersion composition that the fluoropolymer particles that contains proplast and/or modified Teflon is scattered in aqueous medium; It is characterized in that make and do not contain the membranaceous thing of tetrafluoroethylene of base material at using described aqueous polytetrafluoroethyldispersion dispersion composition, establishing its incident light intensity is I
0, the transmission light intensity is I, the thickness of membranoid substance is 10 μ m, then according to following formula (Ia): α=10/ln (I
o/ the α that I) calculates is more than or equal to 260.
The present invention relates to the membranaceous thing of tetrafluoroethylene, it is characterized by, have impregnated body and reach by described aqueous polytetrafluoroethyldispersion dispersion composition being immersed in the tunicle that obtains on the described impregnated body.
The present invention relates to the membranaceous thing of tetrafluoroethylene, it is the membranaceous thing of tetrafluoroethylene that contains the modified Teflon that tetrafluoroethylene and comonomer copolymerization are obtained; It is characterized in that the comonomer unit that described comonomer forms accounts at least 0.05 quality % of described modified Teflon.
The present invention relates to roof Material, it is the roof Material in the membrane structure buildings; It is characterized in that described roof Material contains the membranaceous thing of described tetrafluoroethylene.
Embodiment
Below the present invention is described in detail.
Polytetrafluoroethylene (PTFE) aqueous dispersion composition of the present invention is the aqueous polytetrafluoroethyldispersion dispersion composition that the fluoropolymer particles that contains proplast and/or modified Teflon is scattered in aqueous medium, uses the polytetrafluoroethylene (PTFE) membranoid substance that this aqueous polytetrafluoroethyldispersion dispersion composition makes and has the feature of hereinafter describing.
Relevant PTFE aqueous dispersion composition will hereinafter be described.
About described " feature that the PTFE membranoid substance is described hereinafter ", can be that PTFE aqueous dispersion composition of the present invention can form PTFE membranoid substance described later (1), but PTFE aqueous dispersion composition preferably of the present invention can form PTFE membranoid substance described later (2).PTFE aqueous dispersion composition of the present invention can be to form the composition that not only has the feature of PTFE membranoid substance (1) but also have the membranoid substance of PTFE membranoid substance (2) feature.In the PTFE membranoid substance (2) that described PTFE aqueous dispersion composition forms, preferred PTFE membranoid substance described later (2a).
The membranaceous thing of tetrafluoroethylene also is one of the present invention.
The membranaceous thing of tetrafluoroethylene of the present invention is the membranoid substance that contains fluoropolymer described later.In this manual, " membranoid substance " can be the object that is generally considered to be membranaceous, and normally thickness is the tabular object of 5 μ m～3000 μ m.
In this manual, for technical terms " the membranaceous thing of tetrafluoroethylene ", wherein used technology to be used for " tetrafluoroethylene " simply.But the fluoropolymer that constitutes the membranaceous thing of tetrafluoroethylene of the present invention is not only limited to tetrafluoroethylene (TFE) homopolymer, can be the modified Teflon (modified ptfe) that TFE and comonomer polymerization are obtained yet.
From the outstanding this point of light transmission of the PTFE membranoid substance that obtains, the modified Teflon (modified ptfe) of the fluoropolymer that preferably constitutes the membranaceous thing of tetrafluoroethylene of the present invention for TFE and comonomer polymerization are obtained.
Above-mentioned modified ptfe can be the material that the comonomer polymerization of TFE and other a kind or at least 2 kinds obtains.
There is not particular restriction for the comonomer in the described modified ptfe, so long as can get final product with the fluorochemicals of TFE copolymerization.Can exemplify into R 1216 (HFP), perfluor (alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), vinylidene (VdF) etc.
For described PAVE can exemplify into perfluor (ethylene methacrylic ether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) etc., wherein preferred PMVE and/or PPVE.
From the outstanding this point of light transmission of the tunicle that obtains, preferred described comonomer is PAVE and/or HFP, more preferably PAVE.
In above-mentioned modified Teflon, the comonomer unit that preferred comonomers forms accounts at least 0.05 quality % of described modified Teflon.
In described modified ptfe, if 0.05 quality % of the not enough described modified Teflon of described comonomer unit, the light transmission of the PTFE membranoid substance that then obtains sometimes is bad.Comonomer unit in the described modified ptfe can account for 1.0 quality % of this modified ptfe or be less than 1.0 quality % as long as within described scope.
From outstanding this point of light transmission of PTFE membranoid substance, the lower limit of comonomer unit described in the described modified ptfe is 0.1 quality % of this modified ptfe more preferably; From accessing this point of PTFE membranoid substance of PTFE character such as keeping thermotolerance, chemical resistant properties, preferred described comonomer unit is 0.5 quality % of this modified ptfe or is less than 0.5 quality %.
In this manual, described " comonomer unit " is the part on the modified ptfe molecular structure, is meant the part that is formed by comonomer.For example, when comonomer was PPVE, comonomer unit was to be formed by PPVE in the molecular structure of modified ptfe and with-[CF
2-CF (O-C
3F
7)]-expression part.
In this specification sheets, the containing ratio of the described comonomer unit in the described modified ptfe is meant, the PTFE powder that uses the PTFE aqueous dispersion to obtain through condensation, cleaning, drying, it is carried out the value that the infrared absorption chromatographic determination obtains, or with the remaining quantity in the gas chromatography assaying reaction system, according to calculating the value that consumption obtains with the relation of add-on.
In this manual, the fluoropolymer of membranoid substance " constitute PTFE " or identical therewith purpose " fluoropolymer " that use are the general names of TFE homopolymer and modified ptfe.
The modulator approach of relevant described fluoropolymer will hereinafter be described.
PTFE membranoid substance of the present invention both can be that membranoid substance (A) also can be a membranoid substance (B), can suitably select from described (A) and (B) according to purposes.Described membranoid substance (A) is the membranoid substance that contains base material and described fluoropolymer; Described membranoid substance (B) is the membranoid substance that only contains described fluoropolymer
As previously mentioned, in this manual, " membranoid substance (B) that only contains described fluoropolymer " is meant and " membranoid substance (A) that contains base material and described fluoropolymer " relative notion, represents that it does not comprise base material.For described " membranoid substance (B) that only contains described fluoropolymer ", remove the fluoropolymer beyond the region of objective existence, also can contain additives such as aftermentioned tensio-active agent, film forming modifying agent.
In this manual, so-called " tetrafluoroethylene [PTFE] membranoid substance that does not comprise base material " is not described " membranoid substance (A) that contains base material and described fluoropolymer ", be meant described " membranoid substance (B) that only contains described fluoropolymer ", promptly, it contains fluoropolymer, also can contain additives such as tensio-active agent described later, film forming modifying agent as required.
PTFE membranoid substance of the present invention contains the modified ptfe that TFE and described comonomer polymerization are obtained, and the comonomer unit that is formed by described comonomer accounts at least 0.05 quality % (in also the claiming sometimes hereinafter of this specification sheets " PTFE membranoid substance (1) ") of described modified ptfe.
The light transmission of PTFE membranoid substance of the present invention (1) is outstanding, for example, is I when setting the incident light intensity
o, the transmission light intensity is the thickness of I and membranoid substance when being d μ m, the α that calculates by following formula (Ib) is more than or equal to 185.Formula (Ib) is α=d/ln (I
o/ I).
In described PTFE membranoid substance (1), from outstanding this point of light transmission of the tunicle that obtains, preferred described comonomer is PAVE and/or HFP, more preferably PAVE.
When setting the incident light intensity is I
o, the transmission light intensity is the thickness of I and membranoid substance when being d μ m, the α that calculates by following formula (Ib) also is one of the present invention (in also the claiming sometimes hereinafter of this specification sheets " PTFE membranoid substance (2) ") more than or equal to 185 PTFE membranoid substance.
In above-mentioned formula (Ib) and formula described later (Ia), the α value is high more, represents that then light transmission is excellent more.
As the α value is represented, the light transmission height of PTFE membranoid substance of the present invention.
In this manual, when measuring with direct-reading film turbidimetry device (Japan smart mechanism do manufacturing), according to the I that obtains for PTFE membranoid substance with specific thickness (d value)
oValue and I value utilize described formula (Ib) or formula (Ia) to calculate separately α value respectively.
By reducing the thickness of PTFE membranoid substance of the present invention relatively, can be easy to reach the α value in the described scope.When using described modified ptfe as the fluoropolymer that constitutes described PTFE membranoid substance, the side chain that TFE such as HFP, PAVE comonomer is had helps noncrystallineization, can realize higher light transmission, at this moment, the thickness that increases the PTFE membranoid substance also can be realized light transmission.
Do not have particular restriction for PTFE membranoid substance of the present invention (2), so long as contain described fluoropolymer, that is, contain TFE homopolymer and/or modified ptfe and have a membranoid substance of the α value in the described scope just passable.From outstanding this point of light transmission, the fluoropolymer that preferably constitutes this PTFE membranoid substance (2) is described modified ptfe.
As mentioned above, be above-mentioned PAVE and/or HFP preferably as the comonomer in the modified ptfe of the fluoropolymer that constitutes described PTFE membranoid substance (2), preferably the comonomer unit of this comonomer formation accounts at least 0.05 quality % of described modified ptfe.
In this manual, not additional (1), (2) or (2a) described later, and only be that what to be expressed as that the term of " PTFE membranoid substance " represents is described PTFE membranoid substance (1) and described PTFE membranoid substance (2) (comprising PTFE membranoid substance described later (2a)) not to be distinguished and comprised both notion.
When PTFE membranoid substance of the present invention comprised the base material of described (A), the α value of calculating by described formula (Ib) was preferably greater than or equals 187.
When PTFE membranoid substance of the present invention comprised the base material of described (A), described α value also can be smaller or equal to 500 as long as in described scope.
When PTFE membranoid substance of the present invention is that preferred described α value also can be more than or equal to 300 more than or equal to 260 when only containing the membranoid substance (B) of described fluoropolymer.
When PTFE membranoid substance of the present invention is that more preferably described α value is more than or equal to 330 when only containing the membranoid substance (B) of described fluoropolymer.When PTFE membranoid substance of the present invention is when only containing the membranoid substance (B) of described fluoropolymer, as long as described α value is in described scope, even also can show enough light transmissions smaller or equal to 600.
If PTFE membranoid substance of the present invention is described " the membranaceous thing of tetrafluoroethylene that does not comprise base material ", when the thickness d μ m of membranoid substance in the described formula (Ib) is set at 10 μ m, that is, be I when setting the incident light intensity
o, the transmission light intensity is that the thickness of I and membranoid substance is when being 10 μ m, by following formula (Ia) α=10/ln (I
o/ the α that I) calculates more preferably greater than or equaled for 260 (also claiming " PTFE membranoid substance (2a) " in this manual sometimes).
For the α of the described PTFE membranoid substance (2a) that calculates by described formula (Ia), more preferably it is more than or equal to 280, and especially preferably it is more than or equal to 300, and most preferably it is more than or equal to 330.As long as in described scope, even smaller or equal to for example 600 also showing enough light transmissions.
PTFE membranoid substance of the present invention has outstanding surface smoothing.For example, the mean roughness of medullary ray can transfer to 2.5 μ m or below it.
The mean roughness of preferred described medullary ray is smaller or equal to 2.3 μ m, and more preferably it is smaller or equal to 2.1 μ m; As long as in described scope, also can be more than or equal to 0.7 μ m.
When PTFE membranoid substance of the present invention is an above-mentioned membranoid substance (B) that contains described fluoropolymer, and when being preferably casting films described later, can reduce the mean roughness of described medullary ray.For example can reduce to 1.3 μ m or below it.When PTFE membranoid substance of the present invention was casting films described later, the mean roughness of preferred described medullary ray needed only in described scope smaller or equal to 1.10 μ m, also can be more than or equal to 0.8 μ m.
In this manual, described center line average roughness is, measuring thickness with roughness tester (trade(brand)name: SURFCOM 470A, the accurate society in Tokyo makes) is the value that the PTFE membranoid substance of d μ m obtains.
By the median size with the aftermentioned fluoropolymer particles is that the described PTFE aqueous dispersion composition of 200nm～500nm is applied to base material, can make the center line average roughness of PTFE membranoid substance of the present invention easily reach described scope.When using the PTFE aqueous dispersion composition and firing PTFE membranoid substance of the present invention, preferably fired 1 minute～30 minutes, under this condition, fire the center line average roughness that easily to realize described scope at 350 ℃～400 ℃.In this manual, so-called " application " be meant, is used to form the known operations such as covering with paint, dipping, casting film of the membranoid substance that contains the PTFE resin.
Can make PTFE membranoid substance of the present invention by application examples such as PTFE aqueous dispersion or PTFE aqueous dispersion composition.
Described PTFE aqueous dispersion is that the fluoropolymer described in the present invention is scattered in the dispersion in the aqueous medium, is to have finished the polymeric aqueous dispersion.
In this manual, described " having finished the polymeric aqueous dispersion " is the polymeric aqueous liquid dispersion of just having finished fluoropolymer, aftertreatments such as polymerization does not concentrate afterwards, dilution.And in this manual, the aqueous dispersion that has only carried out concentration after the polymerization is also referred to as " PTFE aqueous dispersion concentrate " sometimes.
Described PTFE aqueous dispersion composition is as required the PTFE aqueous dispersion to be concentrated, dilutes, and has added the material that obtains behind the additive.Therefore, described PTFE aqueous dispersion composition is that fluoropolymer particles is scattered in the material in the aqueous medium.In the PTFE membranoid substance of using described PTFE aqueous dispersion composition making, the fluoropolymer that constitutes described fluoropolymer particles just becomes described " constituting the fluoropolymer of PTFE membranoid substance ".As mentioned above, the fluoropolymer that constitutes described fluoropolymer particles is TFE homopolymer and/or modified ptfe.
In the described PTFE aqueous dispersion composition, described PTFE aqueous dispersion composition of the present invention not only is used for the making of described PTFE membranoid substance, and it has following characteristics: for using its make and PTFE membranoid substance that do not comprise base material, the α in the described formula (Ia) is more than or equal to 260.
The fluoropolymer that constitutes PTFE membranoid substance of the present invention can obtain by polymerization TFE in aqueous medium usually.From this point of light transmission that improves resulting PTFE membranoid substance, preferred and deposit the polymerization that described comonomer carries out this TFE.
For described aqueous medium, can exemplify mixed solution into water, water and known water-soluble solvent etc.Preferably water wherein.
In this manual, the quality that does not comprise polymerization starter described later or other additives in the quality of described aqueous medium.For described water-soluble solvent, can exemplify and be water soluble alcohols such as methyl alcohol, ethanol, propyl alcohol etc.
Can suitably add known polymerization starter, tensio-active agent and other additives etc. and carry out described polymerization.
Do not have particular restriction for described polymeric method, can exemplify and be letex polymerization, suspension polymerization etc., preferred emulsion polymerization.
Described polymerization can suitably be set conditions such as polymerization pressure and polymerization temperature according to purposes such as the composition of fluoropolymer, manufactures.
Can stir described PTFE aqueous dispersion on one side,, modulate described PTFE aqueous dispersion composition Yi Bian mix after adding tensio-active agent or adding additives such as film forming modifying agent as required.
Can suitably set the condition of each operation such as described stirring, interpolation and mixing according to the kind and the amount of the fluoropolymer that uses, tensio-active agent etc., preferably under 5 ℃～40 ℃ temperature, carry out.
The tensio-active agent that adds when modulating described PTFE aqueous dispersion composition, the kind of the tensio-active agent that had been added in the time of both can be with the polymerization fluoropolymer is identical, also can be different.
There is not particular restriction for described tensio-active agent, preferred known nonionic surface active agent or hydrocarbon-surfactant, the material that contains polyoxyalkylene alkyl phenylate that the material that contains the polyoxyalkylene alkyl oxide of more preferably following general formula (i) expression and following general formula are (ii) represented.
R-O-A
1-H (i)
In the formula (i), R is that carbonatoms is the alkyl of 8～19 straight or branched, and preferred carbonatoms is 10～16; A
1It for carbonatoms 8～58 polyoxyalkylene chain.
R
1-C
6H
4-O-A
2-H (ii)
Formula (ii) in, R
1It for carbonatoms the alkyl of 4～12 straight or branched; A
2It for carbonatoms 8～58 polyoxyalkylene chain.
Also can comprise the described tensio-active agent that adds after a kind or at least 2 kinds of polymerizations in the described PTFE aqueous dispersion composition.
For the tensio-active agent in the described PTFE aqueous dispersion composition, aspect film-forming properties, if with the solids component of PTFE is 100 mass parts, the total quality optimization of the tensio-active agent that adds when then modulating the PTFE aqueous dispersion composition after the tensio-active agent that adds during the fluoropolymer polymerization and the polymerization is greater than 5 mass parts; Aspect the rerum natura of the PTFE of gained membranoid substance, then preferred its smaller or equal to 20 mass parts.
With respect to the PTFE solids component of 100 mass parts, it is 6 mass parts that described tensio-active agent adds up to the preferred lower limit of quality, is limited to 16 mass parts on preferred.
In this manual, the amount of described tensio-active agent can be obtained with the quality % of fluoropolymer according to aftermentioned fluoropolymer solids constituent concentration and modulation PTFE aqueous dispersion composition time institute blended amount (combined amount when comprising modulation PTFE aqueous dispersion); Perhaps can obtain according to following method: with the PTFE aqueous dispersion composition of 10g 100 ℃ of dryings 60 minutes, the residue that obtains with hexane extraction, the ratio that accounts for the quality of the fluoropolymer before dry with the quality of the residue that obtains behind the volatilization hexane is obtained the amount of described tensio-active agent.
In the described PTFE aqueous dispersion composition,, in the scope that does not influence the character of fluoropolymer among the present invention, also can suitably add the additive of film forming modifying agent etc. except described PTFE aqueous dispersion and tensio-active agent.
About described " film forming modifying agent ", compare when not mixing, as long as can improve film-forming properties by mixing.
Do not have particular restriction for described film forming modifying agent, preferred acrylic resins, silicone tensio-active agent, at 380 ℃ residue decompositions more than or equal to 5% nonionic surfactant and/or dry delayed-action activator.
For described additive,, the film forming modifying agent is pigment, weighting agent, defoamer, siccative, adhesion agent, flow agent, anti-creasing agent (Ha ジ キ prevents drug), stablizer etc. except can also exemplifying.
In described PTFE aqueous dispersion composition, consider film-forming properties and dispersion stabilization, preferred described fluoropolymer is the 30 quality %～70 quality % of described PTFE aqueous dispersion composition.
Consider film-forming properties, the amount of preferred described fluoropolymer is more than or equal to 40 quality % of described PTFE aqueous dispersion composition; Consider dispersion stabilization, be limited to 65 quality % of described PTFE aqueous dispersion composition on the preferred described fluoropolymer amount.
In this manual, described " film-forming properties " be meant, can form the character of tunicle under reducing the fissured situation that produces when using described PTFE aqueous dispersion composition.
In this manual, the amount of fluoropolymer in described PTFE aqueous dispersion composition obtained as follows: with the PTFE aqueous dispersion composition of 10g 380 ℃ of dryings after 45 minutes residue obtained quality account for the ratio of the described PTFE aqueous dispersion composition quality before dry.
In the described PTFE aqueous dispersion composition, preferred fluoropolymer particulate median size is 200nm～500nm.The more preferably following 300nm that is limited to of described median size is limited to 400nm on preferred.If greater than 200nm, the crack limiting film thickness improves greatly, film-forming properties obtains the capable outstanding PTFE membranoid substance of surface smoothing remarkably, easily; But, if greater than 500nm, then particle precipitates easily, and the stability of aqueous dispersion composition reduces.
In this manual, the concentration of the PTFE solids component of PTFE aqueous dispersion is adjusted to 0.22 quality %, based on the 550nm projection light to the transmitance of this dispersion of unit length and by the footpath of measuring the certain orientation in the transmission electron microscope photo detection line of definite median size, determine described median size according to described transmitance.
The fibrosis degree of preferred described PTFE aqueous dispersion composition is smaller or equal to 2.5%, and more preferably it is smaller or equal to 2.3%.As long as in described scope, described fibrosis degree also can be more than or equal to 2.0%.
Described PTFE aqueous dispersion composition has fibrosis in the described scope when spending, and is difficult for aggegation during dipping, easy handling when making PTFE membranoid substance of the present invention, obtains the outstanding PTFE membranoid substance of surface smoothing easily.
And, when the fluoropolymer in the described PTFE aqueous dispersion composition is modified ptfe, can adjust described fibrosis degree simply to described scope.
In this manual, described fibrosis degree is meant, the quantitative liquid-feeding pump of high strength silicone tubing has been installed in use, in speed that 25 ℃ of atmosphere gas divide with 200mL/ the PTFE aqueous dispersion composition circulation of 100ml after 2 hours, is filtered the mass ratio that the fibrosis agglutinator that obtains accounts for fluoropolymer in this PTFE aqueous dispersion composition.
In the present invention, do not have particular restriction, can exemplify and be known forming methods such as dipping, coating, casting film for the mode of using described PTFE aqueous dispersion or described PTFE aqueous dispersion composition.
Can PTFE membranoid substance according to the present invention be the described membranoid substance (A) that contains base material and described fluoropolymer, still only contain the membranoid substance (B) of described fluoropolymer, suitably select described application mode.
When PTFE membranoid substance of the present invention is the membranoid substance of described (A), can exemplifies to (A1) and have impregnated body and membranoid substance (being also referred to as " PTFE floods body " in this specification sheets sometimes) by described PTFE aqueous dispersion composition being immersed in the tunicle that obtains on the described impregnated body; Or (A2) have applied thing and a laminate (being also referred to as " PTFE laminate " in this specification sheets sometimes) by described PTFE aqueous dispersion composition being coated the tunicle that obtains on the described applied thing etc.
Consider to be easy to processing that preferred PTFE membranoid substance of the present invention is (A1) PTFE dipping body.
The impregnated body that floods in the body for described (A1) PTFE does not have particular restriction, can exemplify to be glass fibre, vinyl fiber, carbon fiber, Kafra fiber etc.
For the PTFE aqueous dispersion composition in described (A1) PTFE dipping body, can exemplify and be above-mentioned substance.
For the thickness of described (A1) PTFE dipping body, preferred 50 μ m～3000 μ m are limited to 100 μ m under preferred, are limited to 2000 μ m on preferred.
Described (A1) PTFE dipping body is suitable for for example roof Material of membrane structure buildings (tent film), carry strap, high frequency printed base plate, liner etc.
Material for the applied thing in described (A2) PTFE laminate does not have particular restriction, can exemplify to be the fluorine resin that contains described fluoropolymer fluoropolymer in addition, not fluorine-containing heat stable resin, glass etc.
For the PTFE aqueous dispersion composition in described (A2) PTFE laminate, can exemplify and be above-mentioned substance.
For the thickness of described (A2) PTFE laminate, preferred 5 μ m～1000 μ m are limited to 10 μ m under preferred, are limited to 500 μ m on preferred.
For above-mentioned (A2) PTFE laminate,, can be suitable for use as the material of various mechanicalss such as sealing material for example even also can be as PTFE membranoid substance with good mechanical strength for thin layer.
When PTFE membranoid substance of the present invention is described membranoid substance (B), be preferably casting films.
Described casting films can be according to the ordinary method manufacturing, and the method for making this film usually is, thereby the PTFE aqueous dispersion composition is applied on the base material and dryly obtains tunicle, fires as required, strips down from this base material then.Above-mentioned for example peeling off from base material can be adopted following method: will be dropped into the water by the laminate that the PTFE aqueous dispersion composition is coated with and the dry tunicle that obtains and base material constitute, and just can peel off tunicle from described base material simply.
The base material that uses during for the described casting films of making does not have particular restriction, can exemplify to be described applied thing.But under the situation about when making casting films, not firing,, can also use and contain the material that does not have the thermotolerance material usually except described applied thing; For example, the profiled sheeting etc. that contains polyimide, polyethylene resins for universal use such as (PE).
The base material that uses during for the described casting films of making, because base material will be stripped from and be removed and be not included in the casting films in making the back segment operation of casting films, so it is not had the requirement of light transmission, also can be nonmetal inorganicss such as metal, silicon such as aluminium etc. for example.
The thickness of preferred described casting films is 5 μ m～200 μ m, is limited to 10 μ m under preferred, is limited to 100 μ m on preferred.
The suitable insulating film as for example electrical condenser etc. of described casting films etc.
Roof Material of the present invention is the roof Material in the membrane structure buildings; It is characterized in that described roof Material contains above-mentioned PTFE membranoid substance of the present invention.
PTFE membranoid substance in the roof Material of the present invention is preferably the described membranoid substance (A) that comprises base material.
Base material for the PTFE membranoid substance that is used for roof Material of the present invention does not have particular restriction, preference as fiber, contain as described in the weaving cotton cloth or non woven fabric of fiber.
Preferred described fiber is glass fibre, vinyl fiber, carbon fiber, Kafra fiber etc.
Described fiber also can be the regenerated fiber that is coated with the various coated materials of aftermentioned.
The thickness of roof Material of the present invention is generally 100 μ m～3000 μ m.
The thickness of roof Material of the present invention preferably is limited to 150 μ m down, is limited to 2000 μ m on preferred.
In the roof Material of the present invention, described PTFE membranoid substance is preferably described PTFE dipping body (A1).
In the roof Material of the present invention, the described PTFE dipping body (A1) of described PTFE membranoid substance is preferably made by described PTFE aqueous dispersion composition.
In the roof Material of the present invention, the thickness of described PTFE membranoid substance is preferably 100 μ m～3000 μ m.
In the roof Material of the present invention, the thickness of described PTFE membranoid substance is more preferably more than or equal to 150 μ m, and more preferably smaller or equal to 2000 μ m.
Form described PTFE dipping body (A1) by the PTFE aqueous dispersion composition being impregnated into described impregnated body, can make roof Material of the present invention.In the described making processes, before being impregnated into the PTFE aqueous dispersion composition, can be in advance on described fiber, using various coated materials to carry out painted and strengthen etc.
For described coated material, can exemplify and be various common coating and thermoplastic resin etc.
In order to improve for example didirtresistance and water-repellancy etc., the PTFE membranoid substance in the roof Material of the present invention also can have the coating that contains described fluoropolymer fluorine resin in addition.
Roof Material of the present invention both can only contain the PTFE membranoid substance, also can contain PTFE membranoid substance and the other materials that is used to make roof structure.
Because PTFE aqueous dispersion composition of the present invention contains described composition, can be applied to the material of the outstanding membranoid substance of light transmission and surface smoothing etc.Because PTFE membranoid substance of the present invention and roof Material of the present invention contain described composition, not only light transmission is outstanding, and is easy to make, process, and is easier to be processed into the outstanding article of surface smoothing.
Below will be by experiment example and comparative example the present invention will be described in more detail, but the present invention is not only limited to these embodiment and comparative example.
In each experimental example and comparative example, measure as follows.
(1) (PPVE) comonomer unit amount of perfluor (propyl vinyl ether)
The PTFE aqueous dispersion is carried out condensation, cleaning, drying, use the PTFE powder that obtains, measure with Fourier transform type infrared spectrophotometer 1760X (perkin elmer manufacturing), the infrared absorption spectrum band is in 995cm
-1Absorbancy with in 2360cm
-1The ratio of absorbancy multiply by 0.95 value that obtains as PPVE comonomer unit amount.
(2) median size
The concentration of the PTFE solids component of PTFE aqueous dispersion is adjusted to 0.22 quality %, the detection line of the median size of determining to the transmitance of this dispersion of unit length with by the footpath of measuring the certain orientation in the infiltration type electron micrograph based on the 550nm projection light is determined median size according to described transmitance.
(3) fluoropolymer solids constituent concentration
With PTFE aqueous dispersion, PTFE aqueous dispersion concentrate or the PTFE water dispersion medium composition of 10g 380 ℃ of dryings 45 minutes, according to the residue quality that obtains after the drying account for dry before the per-cent of ratio of quality of described PTFE aqueous dispersion etc. calculate.
(4) surfactant concentration
The amount (combined amount when comprising modulation PTFE aqueous dispersion) of blended tensio-active agent is obtained with its quality % that accounts for fluoropolymer by according to fluoropolymer solids constituent concentration of obtaining in described (3) and modulation PTFE water dispersion medium composition the time.
(5) mensuration of light transmission α
For thickness is the PTFE membranoid substance of d μ m, measures incident intensity (I with direct-reading hazemeter (the smart mechanism of Japan is done manufacturing)
o) and transmitted intensity (I), (Ib) estimates according to formula.Formula (Ib) is α=d/ln (I
o/ I).Wherein, I
oBe incident intensity, I is a transmitted intensity, and d is the thickness (μ m) of membranoid substance.
(6) mensuration of center line average roughness (surface smoothing)
For thickness is the PTFE membranoid substance of d μ m, and (trade(brand)name: SURFCOM470A, the accurate society in Tokyo makes) measures with roughness tester.
(7) evaluation of fibrosis degree
Use and external diameter has been installed is 7.9mm, the internal diameter quantitative liquid-feeding pump as the high strength silicone tubing of 4.8mm, the speed of dividing with 200mL/ under 25 ℃ the atmosphere gas was with the PTFE aqueous dispersion composition circulation of 100ml 2 hours.Finishing the back filters with 200 purpose stainless (steel) wires, the fibrosis agglutinator that filtration is obtained cleaned 5 minutes with flowing water, again in 100 ℃ of dryings 2 hours, measure dried quality, calculate the ratio of its quality (hereinafter being also referred to as " PTFE solids component ") with respect to fluoropolymer in the PTFE aqueous dispersion composition of 100ml.
Embodiment 1
Making median size by letex polymerization is that 313nm, fluoropolymer substrate concentration (P.C.) are 31.7%, the PPVE quantity of units is the PTFE aqueous dispersion of 0.12 quality % of PPVE solids component.
Use is as the nonionic surface active agent (polyoxyalkylene alkyl of tensio-active agent, commodity are called TDS-80C, the first industrial pharmacy commercial firm makes) the above-mentioned PTFE aqueous liquid dispersion that obtains is concentrated, modulation P.C. is 71.6 quality %, surfactant concentration (N.C.) the PTFE aqueous liquid dispersion concentrate for 3.1 quality % of PTFE solids component.
In this PTFE aqueous liquid dispersion concentrate, add tensio-active agent (Voranol EP 2001, commodity are called TDS-120, the first industrial pharmacy commercial firm makes) and pure water, obtaining P.C. is that 53 quality %, N.C. are the PTFE aqueous dispersion composition of 13 quality % of PTFE solids component.
Measure the fibrosis degree of this PTFE aqueous dispersion composition, make glass fiber impregnated body and casting films then as follows, measure its light transmission and center line average roughness (surface smoothing).
(1) manufacturing of glass fiber impregnated film
(linear density is that vertical 60/25mm, horizontal 46/25mm), thickness are 50 μ m and glass fiber impregnated in the PTFE aqueous dispersion composition through overheated washing with plain weave, flooded for 10 seconds, in about 100 ℃ of dryings and in about 380 ℃ fire 3 minutes after, be positioned over that (20 ℃～25 ℃) cool off in the normal temperature.This operation amounts to 3 times repeatedly, obtains fluoropolymer resin content and is about 60%～65% membranoid substance.After carrying out 1 this operation again, it is about 70%～75% that fluoropolymer resin content reaches, and obtaining by thickness is the glass fiber impregnated film that the PTFE membranoid substance of 80 μ m or 95 μ m forms.
(2) manufacturing of casting films
The PTFE aqueous dispersion composition of 5ml is dropped on the aluminium sheet of 20cm * 10cm * 1.5mm, uses coating machine (peace field smart chance society makes) coating 1 time, thickness is being changed between smaller or equal to 30 μ m continuously greater than 0 μ m; In 100 ℃ of dryings 10 minutes and in 380 ℃ fire 15 minutes after, be positioned in the normal temperature and cool off.This tunicle is stripped down from aluminium sheet, obtain casting films.To not having crackle and thickness is the mensuration that light transmission and center line average roughness are carried out in the position of 8 μ m and 10 μ m.
Comparative example 1
Making median size by letex polymerization is that 322nm, P.C. are 30.3% PTFE aqueous dispersion (TFE homopolymer).Concentrate the above-mentioned PTFE aqueous dispersion that obtains with TDS-80C, modulation P.C. is that 71.1 quality %, N.C. are the PTFE aqueous liquid dispersion concentrate of 2.9 quality % of PTFE solids component.Add TDS-120 and pure water in this PTFE aqueous liquid dispersion concentrate, obtaining P.C. is that 53 quality %, N.C. are the PTFE aqueous dispersion composition of 13 quality % of PTFE solids component.
Measure the fibrosis degree of this PTFE aqueous dispersion composition, make glass fiber impregnated body and casting films according to the method identical then, measure its light transmission and center line average roughness (surface smoothing) with embodiment 1.
[table 1]
| Embodiment 1 | Comparative example 1 | ||||
| Glass fiber impregnated body | Sample thickness (μ m) | 80 (flooding 3 times) | 95 (flooding 4 times) | 80 (flooding 3 times) | 95 (flooding 4 times) |
| Light transmission | 187.1 | 189.4 | 179.6 | 180.6 | |
| Center line average roughness (μ m) | 2.44 | 2.08 | 2.88 | 2.56 | |
| Casting films | Sample thickness (μ m) | 8 | 10 | 8 | 10 |
| Light transmission | 331.3 | 335.8 | 253.0 | 256.4 | |
| Center line average roughness (μ m) | 1.08 | 0.76 | 1.48 | 1.32 | |
| Fibrosis degree (%) | 2.22 | 3.19 | |||
Although the glass fiber impregnated body among the embodiment 1 and casting films have with comparative example 1 in the identical thickness of material that obtains, its light transmission height, and surface smoothing is better than comparative example 1.
And although the PTFE aqueous dispersion composition that uses in PTFE aqueous dispersion composition that uses among the embodiment 1 and the comparative example 1 is same concentrations, its fibrosis degree is lower than comparative example 1, and floods to add and be difficult for aggegation man-hour.
Industry applications
Form because PTFE aqueous dispersion composition of the present invention contains as above, suitable membranoid substance material outstanding as light transmission, that surface smoothing is good uses.
Form because PTFE membranoid substance of the present invention contains as above, suitable roof Material outstanding as light transmission, that be easy in the good membrane structure buildings of processing and manufacturing and surface smoothing uses.
Form because roof Material of the present invention contains as above, its light transmission is outstanding, and surface smoothing.
Claims (9)
1, aqueous polytetrafluoroethyldispersion dispersion composition, it is the aqueous polytetrafluoroethyldispersion dispersion composition that the fluoropolymer particles that contains proplast and/or modified Teflon is scattered in aqueous medium; It is characterized in that make and do not contain the membranaceous thing of tetrafluoroethylene of base material at using described aqueous polytetrafluoroethyldispersion dispersion composition, establishing its incident light intensity is I
0, the transmission light intensity is I, the thickness of membranoid substance is 10 μ m, then according to following formula (Ia): α=10/ln (I
0/ the α that I) calculates is more than or equal to 260.
2, aqueous polytetrafluoroethyldispersion dispersion composition as claimed in claim 1, wherein, the fluoropolymer that constitutes polytetrafluoroethylene granule is the modified Teflon that tetrafluoroethylene and comonomer polymerization are obtained.
3, aqueous polytetrafluoroethyldispersion dispersion composition as claimed in claim 2, wherein, described comonomer is perfluor (alkyl vinyl ether) and/or R 1216.
4, as claim 2 or 3 described aqueous polytetrafluoroethyldispersion dispersion compositions, wherein, the comonomer unit that described comonomer forms accounts at least 0.05 quality % of modified Teflon.
5, the membranaceous thing of tetrafluoroethylene is characterized by, and has impregnated body and reaches by claim 1,2,3 or 4 described aqueous polytetrafluoroethyldispersion dispersion compositions are immersed in the tunicle that obtains on the described impregnated body.
6, the membranaceous thing of tetrafluoroethylene, it is the membranaceous thing of tetrafluoroethylene that contains the modified Teflon that tetrafluoroethylene and comonomer copolymerization are obtained; It is characterized in that the comonomer unit that described comonomer forms accounts at least 0.05 quality % of described modified Teflon.
7, the membranaceous thing of tetrafluoroethylene as claimed in claim 6, wherein, described comonomer is perfluor (alkyl vinyl ether) and/or R 1216.
8, as claim 6 or the membranaceous thing of 7 described tetrafluoroethylene, it contains modified Teflon and the impregnated body that tetrafluoroethylene and comonomer polymerization are obtained.
9, roof Material, it is the roof Material in the membrane structure buildings; It is characterized in that described roof Material contains claim 5,6, the membranaceous thing of 7 or 8 described tetrafluoroethylene.
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| JP2004280552 | 2004-09-27 | ||
| JP2004280552 | 2004-09-27 | ||
| JP2004376432 | 2004-12-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812578A (en) * | 2012-11-01 | 2015-07-29 | 中兴化成工业株式会社 | Composite body |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812578A (en) * | 2012-11-01 | 2015-07-29 | 中兴化成工业株式会社 | Composite body |
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