CN100540575C - Modified Teflon and manufacture method thereof - Google Patents

Modified Teflon and manufacture method thereof Download PDF

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CN100540575C
CN100540575C CNB2005101057402A CN200510105740A CN100540575C CN 100540575 C CN100540575 C CN 100540575C CN B2005101057402 A CNB2005101057402 A CN B2005101057402A CN 200510105740 A CN200510105740 A CN 200510105740A CN 100540575 C CN100540575 C CN 100540575C
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modified ptfe
aqueous dispersion
polymerization
mentioned
modified teflon
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CN1754894A (en
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中谷安利
泽田又彦
加藤丈人
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Daikin Industries Ltd
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Daikin Industries Ltd
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Abstract

The invention provides the manufacture method that film-forming properties is superior, can form modified Teflon, its aqueous dispersion, aqueous dispersion composition and the above-mentioned modified Teflon of the superior overlay film of the transparency.Described modified Teflon is polymerizing tetrafluoroethylene and comonomer and the modified Teflon that obtains, it is characterized in that, the comonomer unit that described comonomer forms accounts for the 0.1 quality %～1.0 quality % of described modified Teflon, the average primary particle diameter of described modified Teflon is 220nm～500nm, and described comonomer is R 1216, perfluor (alkyl vinyl ether) and/or vinylidene.

Description

Modified Teflon and manufacture method thereof
Technical field
The present invention relates to manufacture method, modified Teflon aqueous dispersion and the modified Teflon aqueous dispersion composition of modified Teflon, this modified Teflon.
Background technology
The aqueous dispersion composition that in the past contained the polytetrafluoroethylene (PTFE) resin particle is by being impregnated into dipping bodies such as being used to make roof Material in glass fibre, carbon fiber, the gram Port Vila fiber etc., in addition, high frequency printed base plate, conveyance with purposes such as being with, packing in, be used to form film and fire by described composition being coated on be coated with to fire on the jewelry.
For the aqueous dispersion composition that contains the PTFE resin particle in the past, if make per 1 time dipping and glue spread surpass certain thickness, then overlay film can crack, and has the problem of damaging quality.In order to address this problem, when requiring the processed goods of thick film, be to adopt to flood repeatedly or the method for painting process, but this method exist production cost to increase, and produce the problem of advancing to split always.
As the manufacture method of PTFE, proposed when letex polymerization to add intermittently with the method (for example with reference to patent documentation 1) of whole emulsifying agent portion-wise addition, when the letex polymerization in the past emulsifying agent method (for example with reference to patent documentation 2), the 1st stage of polymerization with not enough 4kg/cm 2Pressure, the 2nd stage with 6kg/cm 2～30kg/cm 2Pressure carry out polymeric method (for example with reference to patent documentation 3) etc.
Manufacture method as PTFE, following method has also been proposed, carry out polymerization with certain temperature, after at least 30 weight % polymerizations of answering polymerizing tetrafluoroethylene (TFE) total amount, the change polymerization temperature, the amorphous index of the polymkeric substance that obtains with at the identical tetrafluoroethylene of above-mentioned certain temperature polymerizing tetrafluoroethylene total amount the time in polymerization total amount under the temperature after changing is than the amorphous index high at least by 0.01 (for example with reference to patent documentation 4) of the polymkeric substance that polymerizing tetrafluoroethylene obtains under above-mentioned certain temperature.
But, at the temperature change in this polymerization way only put down in writing from 40 ℃ to 18 ℃, from 70 ℃ to 90 ℃ or from 70 ℃ to 92 ℃ modification.In addition, in patent documentation 4,, and be the technology that obtains the fines that the slurry extrusion moulding uses at the not special record of modified ptfe.
As the method for in PTFE polymerization way, carrying out the temperature change, following method has also been proposed, polymerization begin temperature for smaller or equal to 60 ℃, be preferably smaller or equal to 55 ℃, more preferably 50 ℃, finish polymerization in the temperature that is higher than 55 ℃, make this final temperature be higher than at least 5 ℃ of above-mentioned beginning temperature, preferably high at least 10 ℃ (for example with reference to patent documentation 2).
In patent documentation 2, only put down in writing 40 ℃ of beginning polymerizations and at 80 ℃ of termination polymeric embodiment at modified ptfe.In addition, in patent documentation 2, put down in writing to exist the temperature that causes by reaction heat to rise and raise point-blank, off and on or continuously and begun to the temperature between stopping from polymerization.Need there be liquid stabilisers such as paraffin in this method when polymerization stops, and preferably this liquid stabilisers can not begin in low polymerization to exist under the temperature.
As the aqueous dispersion composition that contains the PTFE resin particle, know, if will contain the overlay film that the aqueous dispersion composition of modified ptfe resin particle is processed into coating etc., then can obtain having the overlay film of the transparency.
As modified ptfe, following modified ptfe is for example disclosed: contain as comonomer 0.001 mole of %～2 mole % chlorotrifluoroethylene the about 0.2 μ m of median size～0.5 μ m modified ptfe (for example with reference to patent documentation 5), as comonomer and contain the chlorotrifluoroethylene of 0.04 weight %～0.25 weight % at housing department, modified ptfe (for example with reference to patent documentation 6) that the median size that contains the fluoroalkyl vinyl ether of 0.01 weight %～0.15 weight % at core is about 0.1 μ m～0.6 μ m.
But as necessary monomer, for some purposes, there is the insufficient such defective of thermotolerance in these modified ptfes with chlorotrifluoroethylene.
As having used the modified ptfe fines of perfluor (alkyl vinyl ether) [PAVE] as the comonomer of modified ptfe, the median size that has proposed PAVE and be 0.02 weight %～0.3 weight % is about the material (for example with reference to patent documentation 8) that the material (for example with reference to patent documentation 7) of 0.05 μ m～0.6 μ m, median size that PAVE is 0.02 weight %～0.3 weight % are about 0.05 μ m～0.5 μ m.
But as these modified ptfes, in fact comonomer unit is few or median size is little, has that the crackle limiting film thickness is not enough, the problem of the transparency difference of the overlay film that obtains.
[patent documentation 1] special public clear 46-14466 communique
[patent documentation 2] spy opens the 2000-143707 communique
[patent documentation 3] spy opens clear 60-76516 communique
[patent documentation 4] spy opens clear 52-112686 communique
[patent documentation 5] spy opens clear 51-36291 communique
[patent documentation 6] spy opens clear 63-56532 communique
[patent documentation 7] spy opens clear 64-1711 communique
[patent documentation 8] spy opens flat 10-53624 communique
Summary of the invention
In view of above-mentioned present situation, the object of the present invention is to provide the manufacture method that film-forming properties is superior, can form modified Teflon, its aqueous dispersion, aqueous dispersion composition and the above-mentioned modified Teflon of the superior overlay film of the transparency.
Modified Teflon of the present invention, it is polymerizing tetrafluoroethylene and comonomer and the modified Teflon that obtains, it is characterized in that, the comonomer unit that above-mentioned comonomer forms accounts for the 0.1 quality %～1.0 quality % of above-mentioned modified Teflon, the average primary particle diameter of above-mentioned modified Teflon is 220～500nm, and described comonomer is R 1216, perfluor (alkyl vinyl ether) and/or vinylidene.
Modified Teflon manufacture method of the present invention, it is a modified Teflon manufacture method (below be sometimes referred to as modified ptfe manufacture method (P)) of making modified Teflon by the polymerization of carrying out tetrafluoroethylene and comonomer in water-based polymer medium, it is characterized in that, above-mentioned polymerization comprises step (1) and step (2), in step (1), above-mentioned polymerization begin the back up to respect to per 1 go up state that water-based polymer medium has that above-mentioned tetrafluoroethylene more than or equal to 1g is consumed during in, under smaller or equal to the polymerization pressure of 0.3MPa, carry out polyreaction; In step (2), after above-mentioned steps (1), under the polymerization pressure of 1MPa～3Mpa, carry out polyreaction.
Modified Teflon manufacture method of the present invention, it is a modified Teflon manufacture method (below be sometimes referred to as modified ptfe manufacture method (Q)) of making modified Teflon by the polymerization of carrying out tetrafluoroethylene and comonomer in water-based polymer medium, it is characterized in that, above-mentioned polymerization comprises step (i) and step (ii), in step (i), above-mentioned polymerization begin the back up to respect to per 1 go up state that water-based polymer medium has that above-mentioned tetrafluoroethylene more than or equal to 1g is consumed during in, carry out polyreaction with polymerization temperature X ℃ (55＜X＜70); Step (ii) in, after above-mentioned steps (i), carry out polyreaction with polymerization temperature Y ℃ (Y 〉=X+3, X is same as described above).
Modified Teflon of the present invention is characterized in that, makes by above-mentioned modified ptfe manufacture method (P) and modified ptfe manufacture method (Q).Modified Teflon aqueous dispersion of the present invention is characterized in that the particle that is formed by above-mentioned modified Teflon is dispersed in the aqueous medium.Modified Teflon aqueous dispersion composition of the present invention, it is the modified Teflon aqueous dispersion composition that contains the tensio-active agent that adds after modified Teflon aqueous dispersion and the polymerization, it is characterized in that this modified Teflon aqueous dispersion is above-mentioned modified Teflon aqueous dispersion.
Below explain the present invention.
Modified ptfe of the present invention does not have special restriction, can be used as powder yet and is used for formed material, but be applicable to coating composition as the resin particle that constitutes aqueous dispersion composition.During as coating composition, be coated with on the jewelry or be immersed in the impregnated body, can be coated with on the jewelry or form the overlay film that contains modified ptfe on the impregnated surface by described coating composition is covered with paint, lacquer, colour wash, etc.
In this manual, for comprising the above-mentioned notion that is coated with jewelry and impregnated body, be called " base material " sometimes.Cover with paint, lacquer, colour wash, etc. and flood and generally be meant the operation that comprises the steps, above-mentioned coating composition is coated on is coated with on the jewelry or is immersed in the impregnated body (being sometimes referred to as " application " as the notion that can comprise coating and dipping in this manual), wait by heating as required and carry out drying, then, fire at the fusing point of modified ptfe or the temperature more than it.
Modified Teflon of the present invention (modified ptfe) obtains by polymerizing tetrafluoroethylene (TFE) and comonomer.
Above-mentioned comonomer be R 1216 (HFP), perfluor (alkyl vinyl ether) (PAVE) and/or vinylidene (VdF).
In this manual, above-mentioned " HFP; PAVE and/or VdF " can be any one in the following situation: use HFP but do not use the situation of PAVE and VdF, use PAVE but do not use the situation of HFP and VdF, use VdF but do not use the situation of HFP and PAVE, use HFP and PAVE but do not use the situation of VdF, use VdF and PAVE but do not use the situation of HFP, use VdF and HFP but do not use the situation of PAVE, use VdF, the situation of HFP and PAVE, no matter be any of these situations, can use a kind as this PAVE when using PAVE, more than 2 kinds or 2 kinds.
As above-mentioned comonomer, preferred PAVE and/or HFP especially consider to make the transparent superior of resultant overlay film, more preferably PAVE.
As above-mentioned PAVE, for example can enumerate perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) etc., especially preferred PMVE and/or PPVE.
In the modified ptfe of the present invention, the comonomer unit that is formed by above-mentioned comonomer is the 0.1 quality %～1.0 quality % of this modified ptfe.
For modified ptfe of the present invention, during 0.1 quality % of not enough this modified ptfe of comonomer unit, then can not form the transparency superior formed body and overlay film; When surpassing 1.0 quality %, then can damage the proterties of tetrafluoroethylene.
In this manual, the part on the molecular structure that above-mentioned " comonomer unit " is modified ptfe is meant the part that is formed by comonomer.When for example comonomer is PPVE, comonomer unit be on the molecular structure of modified ptfe by PPVE form with-[CF 2-CF (O-C 3F 7)]-expression part.
The preferred upper limit of the comonomer unit that contains in above-mentioned modified ptfe is 0.7 quality %, can obtain the transparency that adapts with the monomeric usage quantity of copolymerization in order to make to film, the preferred upper limit is 0.5 quality %, and then preferably the upper limit is 0.35 quality %, and the particularly preferred upper limit is 0.3 quality %.
For modified ptfe of the present invention, average primary particle diameter is 220nm～500nm.
The preferred lower limit of above-mentioned average primary particle diameter is 230nm, and preferred lower limit is 280nm, and the preferred upper limit is 400nm, and the preferred upper limit is 350nm.In this manual, so-called average primary particle diameter is meant that the aftermentioned polymerization stops the median size of the primary particle in the aqueous dispersion of back.
For modified ptfe of the present invention, since average primary particle diameter above-mentioned in a big way in, during especially for coating composition, can reduce the mud crack and the minimizing that are applied to when drying, be produced behind the base material simultaneously in the past and fire the back shrinkage crack that resin shrinkage produced along with cooling in the past, and, by greatly increasing the crackle limiting film thickness of 1 covering with paint or dipping, also can thick filmization (thick coating) even adopt 1 covering with paint or flood.
In this manual, above-mentioned can reduce that crackle produces and the character that forms overlay film is sometimes referred to as " film-forming properties ".
For modified ptfe of the present invention, if the not enough 220nm of average primary particle diameter then is modulated into coating composition and when using, above-mentioned film-forming properties is poor; If average primary particle diameter surpasses 500nm, when then being modulated into aqueous dispersion composition, the sedimentation of the particle that is formed by modified ptfe is obvious, the poor stability of composition.
Although modified ptfe of the present invention is modified ptfe as mentioned above, its average primary particle diameter is big, even the ratio of comonomer unit is bigger as above-mentioned scope, also can keep the size of average primary particle diameter.Thereby, for modified ptfe of the present invention,, also can form superior and transparent also superior formed body of anti-crackle and overlay film although certain thickness is arranged.
Modified ptfe of the present invention (below be sometimes referred to as " modified ptfe of the present invention (a) ") can be made aptly by modified ptfe manufacture method of the present invention described later.In this manual, when not adding (P) or (Q) and only saying " modified ptfe manufacture method ", be not to distinguish with above-mentioned modified ptfe manufacture method (P) or modified ptfe manufacture method (Q), it uses as the term of summarizing two manufacture method.
Modified ptfe of the present invention (a) also can be by following method manufacturing: when carrying out the polymerization of TFE and comonomer in the presence of emulsifying agent in water-based polymer medium, add emulsifying agent (being sometimes referred to as " the continuous addition method of emulsifying agent " in this manual) in batches or continuously.Describe in the back about above-mentioned water-based polymer medium.
In the continuous addition method of mentioned emulsifier, the initial stage addition of emulsifying agent is preferably 1.0 * 10 with respect to 100 mass parts water-based polymer mediums -4～5.0 * 10 -2Mass parts.Less than 1.0 * 10 -4During mass parts, then the emulsification of polymerization reaction system is insufficient sometimes; Surpass 5.0 * 10 -2During mass parts, the average primary particle diameter of the formed particle of modified ptfe that then obtains diminishes sometimes.With respect to 100 mass parts water-based polymer mediums, be limited to 1.0 * 10 under the initial stage addition of mentioned emulsifier preferred -3Mass parts is limited to 3.0 * 10 on preferred -2Mass parts.Above-mentioned " the initial stage addition of emulsifying agent " is the amount that is present in the emulsifying agent in the polymerization reaction system when polyreaction begins.
As mentioned emulsifier, for example can enumerate that fluorine carbon is emulsifying agent, hydrocarbon system emulsifying agent etc., preferred fluorine carbon is emulsifying agent, wherein more preferably carbonatoms is that 8～12 perfluorocarbon is an emulsifying agent.
The addition of mentioned emulsifier preferably adds up to 1.0 * 10 of above-mentioned water-based polymer medium -4Quality %～1.0 quality %.
When using the continuous addition method of mentioned emulsifier, do not need strictness to carry out the management of polymerization pressure in the modified ptfe manufacture method of the present invention described later (P), for example can begin to carry out polyreaction under certain polymerization pressure yet from polymerization to terminating in.In modified ptfe manufacture method of the present invention (P), the continuous addition method preference of mentioned emulsifier is as being that 50 ℃～90 ℃, polymerization pressure are to carry out under 0.5MPa～3MPa at polymerization temperature.
In addition, be set at than low value by initial stage addition when carrying out the continuous addition method of emulsifying agent, also can further increase the average primary particle diameter of the modified ptfe that obtains emulsifying agent.
Below be about the common item of modified ptfe manufacture method of the present invention (P) and modified ptfe manufacture method (Q), put down in writing at modified ptfe manufacture method of the present invention.
Modified ptfe manufacture method of the present invention is to make modified ptfe by carry out tetrafluoroethylene (TFE) and comonomer in water-based polymer medium.
So-called above-mentioned water-based polymer medium is the reaction medium of instigating the polymeric water-based of carrying out TFE and comonomer.
As above-mentioned water-based polymer medium, can enumerate mixed solution of for example water, water and known water-soluble solvent etc., be preferably water.In this manual, the quality of above-mentioned water-based polymer medium does not comprise the quality of polymerization starter described later or other any additives.
As above-mentioned water-soluble solvent, can enumerate for example water soluble alcohols such as methyl alcohol, ethanol, propyl alcohol etc.
Do not have special restriction as above-mentioned comonomer, can enumerate for example HFP, PAVE, VdF, chlorotrifluoroethylene (CTFE) etc., industrial HFP, PAVE and/or the VdF of being preferably.Above-mentioned " HFP, PAVE and/or VdF " be with modified ptfe of the present invention in the identical notion of above-mentioned situation.
In the modified ptfe manufacture method of the present invention, can add known polymerization starter aptly, other additives wait and carry out polymerization.
As above-mentioned polymerization starter, can enumerate for example persulphates such as ammonium persulphate (APS), Potassium Persulphate, peroxidation disuccinic acid organo-peroxides such as (DSP) etc.
If carry out above-mentioned polymerization, can set other conditions aptly according to the composition of target modified ptfe, manufacture etc. with condition enactment polymerization pressure described later.
In the above-mentioned modified ptfe manufacture method, can also carry out polymerization by adding known liquid stabilisers aptly.As the aforesaid liquid stablizer, can enumerate paraffin.This liquid stabilisers can exist when polymerization begins, and also can begin the back in polymerization and add.
As the polymerization process in the modified ptfe manufacture method of the present invention, for example preferred emulsion polymerization.
In the modified ptfe manufacture method of the present invention (P), described polymerization comprises step (1) and step (2), in step (1), polymerization begin the back up to respect to per 1 go up state that water-based polymer medium has that tetrafluoroethylene more than or equal to 1g is consumed during in, under smaller or equal to the polymerization pressure of 0.3MPa, carry out polyreaction; In step (2), after above-mentioned steps (1), under the polymerization pressure of 1MPa～3Mpa, carry out polyreaction.
In the above-mentioned steps (1), the preferred lower limit of polymerization pressure is 0.10MPa, and preferred lower limit is 0.20MPa; The preferred upper limit is 0.28MPa, and the preferred upper limit is 0.25MPa.
In this manual, polymerization pressure is the notion that comprises 1.00 ± 0.05MPa～3.00 ± 0.05MPa for " 1MPa～3MPa " in the above-mentioned steps (2).
In the above-mentioned steps (2), the preferred lower limit of polymerization pressure is 1.3MPa, and preferred lower limit is 1.5MPa; The preferred upper limit is 2.8MPa, and the preferred upper limit is 2.5MPa.
In general, if polymerization pressure height when making modified ptfe, then copolymerization of copolymerization monomer can reduce, and the average primary particle diameter of the resin particle that obtains also tends to reduce.But, for modified ptfe manufacture method of the present invention (P), owing to carried out carrying out the step (1) of polyreaction before in the step (2) of carrying out polyreaction with above-mentioned specific high pressure, thereby can under the condition of not damaging copolymerization of copolymerization monomer, make the big modified ptfe of average primary particle diameter with above-mentioned specific low pressure.
Modified ptfe manufacture method of the present invention (P) is owing to comprise above-mentioned steps (2), thereby can also shorten polymerization time, boost productivity.
In the modified ptfe manufacture method of the present invention (Q), described polymerization comprises step (i) and step (ii), in step (i), polymerization begin the back up to respect to per 1 go up state that water-based polymer medium has that TFE more than or equal to 1g is consumed during in, carry out polyreaction with polymerization temperature X ℃ (55＜X＜70); Step (ii) in, after above-mentioned steps (i), carry out polyreaction with polymerization temperature Y ℃ (Y 〉=X+3, X is same as described above).
In above-mentioned modified ptfe manufacture method (Q), do not need strictly to carry out the management of polymerization pressure, for example also can begin to carry out polyreaction under certain polymerization pressure from polymerization to terminating in.Above-mentioned steps (ii) in, above-mentioned polymerization pressure is preferably than higher pressure, more preferably more than or equal to 1MPa.
In above-mentioned steps (i), above-mentioned polymerization temperature X ℃ preferred above 60 ℃, more preferably 62～68 ℃.In above-mentioned steps (i), preferably all polymerization temperature is maintained X ℃ in whole steps (i).In polyreaction, because its reaction heat, temperature tends to rise, but owing to be to carry out polymerization in water-based polymer medium, therefore is easy to carry out temperature treatment.
Above-mentioned steps can be carried out polyreaction usually (ii) except polymerization temperature being changed to Y ℃ under the polymerizing condition of above-mentioned steps (i).That is, for above-mentioned steps (ii),, then can directly proceed the polyreaction in the step (i) usually if make polymerization temperature change to Y ℃.Thereby the (ii) middle polyreaction of above-mentioned steps is carried out in water-based polymer medium usually.
Above-mentioned polymerization temperature Y ℃ is than above-mentioned polymerization temperature X ℃ high at least 3 ℃ temperature.When carrying out the polyreaction of step in (ii) in water-based polymer medium, above-mentioned polymerization temperature Y ℃ the preferred upper limit is 100 ℃, and the preferred upper limit is 95 ℃, and then the preferred upper limit is 90 ℃.
For the polymerization temperature X from above-mentioned steps (i) ℃ to polymerization temperature Y ℃ the intensification amplitude of above-mentioned steps in (ii), so long as polymerization temperature Y ℃ be in the above-mentioned scope, 40 ℃ of preferred less thaies, be more preferably less than and equal 30 ℃, and then 20 ℃ of preferred less thaies, especially preferably smaller or equal to 15 ℃, most preferably less than is 5 ℃.For modified ptfe manufacture method of the present invention,, also can realize the application's goal of the invention even the polymerization temperature X from above-mentioned steps (i) ℃ minimum as above-mentioned scope to polymerization temperature Y ℃ the intensification amplitude of above-mentioned steps in (ii).
Above-mentioned steps (ii) in, preferably (ii) all polymerization temperature is maintained Y ℃ in whole steps.In polyreaction, because its reaction heat, temperature tends to rise, but owing to be to carry out polymerization in water-based polymer medium, therefore is easy to carry out temperature treatment.
As mentioned above, modified ptfe manufacture method of the present invention (Q) is owing to the polymerization temperature with above-mentioned specified range in step (i) begins polymerization, and the polymerization temperature of the polyreaction of step in (ii) is than at least 3 ℃ of the polymerization temperature height of the middle polyreaction of above-mentioned steps (i), thereby can make the big modified ptfe of average primary particle diameter under the condition of not damaging copolymerization of copolymerization monomer.
For modified ptfe manufacture method of the present invention (Q), even the polymerization temperature from above-mentioned steps (i) is minimum as above-mentioned scope to the intensification amplitude of the polymerization temperature of above-mentioned steps in (ii), also can realize the application's goal of the invention, thereby the efficiency height, can also boost productivity.
In the modified ptfe manufacture method of the present invention, make modified ptfe by the polymerization of in water-based polymer medium, carrying out TFE and comonomer, it comprises the 1st polymerization procedure and the 2nd polymerization procedure, and the 1st polymerization procedure carries out polyreaction in the following period: polymerization begin the back up to respect to per 1 go up state that water-based polymer medium has that above-mentioned TFE more than or equal to 1g is consumed during; In the 2nd polymerization procedure, behind the 1st polymerization procedure, carry out polyreaction.If making the 2nd polymerization procedure is that 1～3MPa carries out polyreaction with polymerization pressure, then also can be understood as (p) and under smaller or equal to the polymerization pressure of 0.3MPa, carry out the polyreaction of above-mentioned the 1st polymerization procedure or (q) to carry out the polyreaction in above-mentioned the 1st polymerization procedure at least than the temperature of low 3 ℃ of the polymerization temperature that carries out polyreaction in the 2nd polymerization procedure.
The modified ptfe of making by modified ptfe manufacture method of the present invention (following be also referred to as sometimes " modified ptfe of the present invention (b) ") also is one of the present invention.The modified ptfe of the present invention (a) that modified ptfe of the present invention (b) is preferably above-mentioned, but might not be identical by the modified ptfe of modified ptfe manufacture method manufacturing of the present invention with modified ptfe (a).
Below during general designation modified ptfe of the present invention (a) and modified ptfe (b), do not add (a) or (b), only be called " modified ptfe of the present invention ".The above-mentioned modified ptfe manufacture method according to the present invention, modified ptfe of the present invention (b) is to make with the form that is dispersed in the resin in the modified ptfe aqueous dispersion (being sometimes referred to as " polymerization terminated aqueous dispersion "), and described modified ptfe aqueous dispersion obtains by polymerizing tetrafluoroethylene in water-based polymer medium and comonomer.Above-mentioned water-based polymer medium exists as " aqueous medium " in above-mentioned modified ptfe aqueous dispersion.
Above-mentioned modified ptfe aqueous dispersion (polymerization terminated aqueous dispersion) is to be dispersed in dispersion system in the above-mentioned aqueous medium by the particle (primary particle) that modified ptfe forms.
Above-mentioned modified ptfe aqueous dispersion can have following purposes: (A) modulate the modified ptfe aqueous liquid dispersion concentrate that has improved polymer concentration by adding tensio-active agent; (B) thus remove aqueous medium and carry out drying modulation modified ptfe powder by the above-mentioned modified ptfe aqueous dispersion of condensation; (C) by modulating the modified ptfe aqueous dispersion composition to above-mentioned modified ptfe aqueous dispersion or above-mentioned modified ptfe aqueous liquid dispersion concentrate interpolation tensio-active agent and needed additive etc.
In addition, by the condensation of above-mentioned (B), the primary particle that is dispersed in the polymerization terminated aqueous dispersion is understood aggegation and is formed offspring.
In this manual, above-mentioned " modified ptfe aqueous dispersion " after polymerization, do not add above-mentioned (A) and (C) record tensio-active agent, this point its with polymerization after added the distinguishing notion of tensio-active agent " modified ptfe aqueous dispersion composition ".
Modified ptfe of the present invention (b) is owing to be modified ptfe, thereby can form the transparency superior formed body or overlay film.
The average primary particle diameter of modified ptfe of the present invention (b) is in the scope of 220nm～500nm usually.Thereby the film-forming properties of modified ptfe of the present invention (b) is superior.
Modified ptfe aqueous dispersion of the present invention is that the above-mentioned formed particle of modified ptfe of the present invention is dispersed in the dispersion in the aqueous medium.
In the modified ptfe aqueous dispersion of the present invention, the amount that preferred modified ptfe resin forms branch admittedly accounts for the 20 quality %～40 quality % of this modified ptfe aqueous dispersion.
In this manual, it is the following numerical value of obtaining that above-mentioned modified ptfe resin forms branch admittedly: under 380 ℃ temperature, dry 45 minutes of 10g modified ptfe aqueous dispersion or modified ptfe aqueous dispersion composition are obtained residue, calculates the percentage that residue obtained quality accounts for the mass ratio of dry preceding above-mentioned modified ptfe aqueous dispersion or modified ptfe aqueous dispersion composition.
Modified ptfe aqueous dispersion of the present invention normally obtains by above-mentioned modified ptfe manufacture method of the present invention, is polymerization terminated aqueous dispersion at this moment.
Modified ptfe aqueous dispersion of the present invention is owing to contain modified ptfe of the present invention, thereby film-forming properties is superior, can form the superior overlay film of the transparency, thereby can suit as coating material.
When modified ptfe aqueous dispersion of the present invention is used as coating material, can be modulated into above-mentioned modified ptfe aqueous liquid dispersion concentrate, modified ptfe powder, modified ptfe aqueous dispersion composition etc. according to purposes.
Modified ptfe aqueous dispersion of the present invention is owing to contain modified ptfe of the present invention, thereby chemical resistant properties, thermotolerance etc. are superior, thereby also can be modulated into the modified ptfe powder, and is processed into formed body.
Modified ptfe aqueous dispersion composition of the present invention contains the tensio-active agent that adds after modified ptfe aqueous dispersion and the polymerization, the modified ptfe aqueous dispersion that above-mentioned modified ptfe aqueous dispersion is the invention described above.
In modified ptfe aqueous dispersion composition of the present invention, the above-mentioned tensio-active agent that adds after the polymerization can be identical with the tensio-active agent in being included in the modified ptfe aqueous dispersion, also can be different.
Do not have special restriction as the above-mentioned tensio-active agent that adds after the polymerization, preferred known hydrocarbon system tensio-active agent more preferably comprises the tensio-active agent of the polyoxygenated alkene alkyl oxide of following general formula (I) expression,
R-O-A 1-H (I)
In the formula, R is that a straight chain shape or a catenate carbonatoms are 8～19, preferred 10～16 alkyl, A 1Be that carbonatoms is 8～58 polyoxyalkylene hydrocarbon chain.Above-mentioned A 1The polyoxyalkylene hydrocarbon chain that preferably has 4～20 ethylene oxide units and 0～6 propylene oxide unit.
Modified ptfe aqueous dispersion composition of the present invention can contain the above-mentioned tensio-active agent that adds behind a kind, the polymerization more than 2 kinds or 2 kinds.
In the modified ptfe aqueous dispersion composition of the present invention, form branch admittedly with respect to 100 mass parts modified ptfe resins, the total amount of the above-mentioned tensio-active agent that adds after the polymerization is preferably 3 mass parts～20 mass parts.Admittedly form branch with respect to 100 mass parts modified ptfe resins, it is 5 mass parts that the total of the above-mentioned tensio-active agent that adds after the polymerization is measured preferred lower limit, and the preferred upper limit is 16 mass parts.
In this manual, the amount (use level when also comprising the modulation of PTFE aqueous dispersion) of the tensio-active agent that the total amount of above-mentioned tensio-active agent is cooperated in the time of can forming branch and modulation PTFE aqueous dispersion composition admittedly by above-mentioned modified ptfe resin is obtained and account for the quality % that the modified ptfe resin forms branch admittedly with the use level of tensio-active agent; Also can obtain: 100 ℃ temperature by following method, dry 60 minutes of 10g PTFE aqueous dispersion composition is obtained residue, again with this residue of hexane extraction, make hexane volatilization subsequently and obtain residue, obtain and account for the percentage of ratio that modified ptfe resin before this drying forms the quality of branch admittedly with the quality of this residue.
In modified ptfe aqueous dispersion composition of the present invention, above-mentioned modified ptfe aqueous dispersion is above-mentioned modified ptfe aqueous dispersion of the present invention.
In modified ptfe aqueous dispersion composition of the present invention, above-mentioned modified ptfe aqueous dispersion can form the scope of amount that branch accounts for the 30 quality %～75 quality % of modified ptfe aqueous dispersion composition admittedly at the modified ptfe resin and cooperate.
In modified ptfe aqueous dispersion composition of the present invention, the preferred lower limit that the modified ptfe resin forms the amount of branch admittedly is 40 quality % of modified ptfe aqueous dispersion composition, and the preferred upper limit is 65 quality % of modified ptfe aqueous dispersion composition.
As modified ptfe aqueous dispersion composition of the present invention, and then preferably contain the film forming modifying agent.
In this manual, for above-mentioned " film forming modifying agent ", so long as by cooperating this modifying agent, compare with the situation that not have cooperation that can to improve film-forming properties just passable.
In the overlay film that obtains in that modified ptfe aqueous dispersion composition of the present invention is applied to base material, the tensio-active agent of described modified ptfe aqueous dispersion composition is filled in the modified ptfe resin particle gap to each other, thereby described film forming modifying agent is exactly to be used for this filling situation is replenished the material that has improved film-forming properties.
In the present invention, do not have special restriction as above-mentioned film forming modifying agent, preferably acrylic resin, silicone-based tensio-active agent, at 380 ℃ residue decompositions more than or equal to 5% nonionic surface active agent and/or dry delayed-action activator.
In this manual, can use in above-mentioned " acrylic resin, silicone-based tensio-active agent, at 380 ℃ residue decompositions more than or equal to 5% nonionic surface active agent and/or dry delayed-action activator " these 4 kinds a kind, more than 2 kinds or 2 kinds.
There is not special restriction as the aforesaid propylene acid resin, preferably the polymkeric substance that forms by the methyl acrylic ester monomer.
As above-mentioned methyl acrylic ester monomer, can enumerate for example methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, dimethylaminoethyl acrylate methyl propyl ester, butyl methacrylate, methacrylic acid pentyl ester etc.
The aforesaid propylene acid resin preferably is modulated into aqueous dispersion and uses.
Even aforesaid propylene acid resin homopolymer also can be modulated into the stabilized aqueous dispersion, but from being easy to be modulated into this point of stabilized aqueous dispersion, preferably with monomer with carboxyl or hydroxyl multipolymer as the comonomer that suits.The aforesaid propylene acid resin is modulated into aqueous dispersion and when using,, can in this aqueous dispersion, adds nonionic surface active agent as required in order further to improve stability.
The aforesaid propylene acid resin is aspect the film-forming properties of the aqueous dispersion composition that obtains, preferred about 25 quality %～50 quality % before 300 ℃～320 ℃ the remaining heating of temperature range, the about 10 quality %～20 quality % before 330 ℃～345 ℃ the remaining heating of temperature range.
As above-mentioned silicone-based tensio-active agent, can enumerate the material of for example representing with following general formula,
R 1 3SiO-(SiR 1 2O) n-(SiR 1R 2O) m-SiR 1 3
In the formula, n represents 0～20 integer, and m represents 0～20 integer, n+m＞1; R 1Identical or different, the expression carbonatoms is that 1～30 alkyl, carbonatoms are that 6～30 aryl, carbonatoms are that 1～30 alkoxyl group, carbonatoms are 6～30 aryloxy or hydrogen atom; R 2Expression usefulness-R 3-(C 2H 4O) q-(C 3H 6O) rThe substituting group that-Y represents, R 3The expression carbonatoms is 1～30 alkylidene group, and Y represents that carbonatoms is 1～30 alkyl, and q is identical with r or different, the integer of expression 0～20, q+r＞1.
The manufacturers that has will have the compound of above-mentioned general formula sells as modified silicone oil, and in this application it is treated as the silicone-based tensio-active agent.
As at 380 ℃ residue decomposition more than or equal to 5% nonionic surface active agent, can enumerate for example known polyethylene oxide derivatives etc.
In this manual, " at 380 ℃ residue decompositions more than or equal to 5% " are meant 5 quality % before residue after 380 ℃ are heated 10 minutes at least is more than or equal to described heating.
Above-mentioned dry delayed-action activator so long as those skilled in the art to be commonly referred to be the material of " dry delayed-action activator " just passable, can enumerate for example to have 200 ℃～solvent of about 300 ℃ boiling point etc., and then preferred water miscible solvent.
As such solvent preferably glycerine, diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monobutyl ether (diethylene glycol monobutyl ether), triethylene glycol, ethylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2-butylene-1,4-glycol, 2-ethyl-2-methylol-1, ammediol etc.
It is generally acknowledged, modified ptfe aqueous dispersion composition of the present invention is applied to base material and obtains overlay film, by the gained overlay film is carried out drying or heating reduces or remove anhydrate, behind the tensio-active agent etc., above-mentioned dry delayed-action activator still is present in the described overlay film and has given play to carrying out the effect of landfill in the formed particle of modified ptfe gap to each other, thereby can improve film-forming properties.
In the dry delayed-action activator, the Diethylene Glycol monoalky lether is owing to have the effect of dissolving acrylic resin, thereby by can further improving film-forming properties with acrylic resin is shared.
In the modified ptfe aqueous dispersion composition of the present invention, as above-mentioned film forming modifying agent especially preferably contain acrylic resin, silicone-based tensio-active agent or at 380 ℃ residue decomposition more than or equal to 5% nonionic surface active agent, more preferably contain acrylic resin.
When firing behind the dry modified ptfe aqueous dispersion composition of the present invention of coating as the acrylic resin of film forming modifying agent in the present invention, owing to can the limit keep the bonding effect limit of modified ptfe is slowly decomposed, thereby can prevent to produce shrinkage crack.
In the modified ptfe aqueous dispersion composition of the present invention, above-mentioned film forming modifying agent can be set use level aptly according to its kind, admittedly form branch with respect to 100 mass parts modified ptfe resins, the use level of described film forming modifying agent is preferably smaller or equal to 10 mass parts.
Modified ptfe resin with respect to 100 mass parts forms branch admittedly, the preferred upper limit of above-mentioned film forming modifying agent is 5 mass parts, lower limit does not have special restriction, but aspect the effect that can obtain cooperating above-mentioned film forming modifying agent to be produced, preferred lower limit is 0.1 mass parts.
Except above-mentioned modified ptfe aqueous dispersion, tensio-active agent and film forming modifying agent, in the scope of the character of not damaging modified ptfe of the present invention, also can add known additive aptly in the modified ptfe aqueous dispersion composition of the present invention.
As above-mentioned additive, can enumerate for example pigment, weighting agent, defoamer, siccative, tackifier, smooth agent, buffer reagent (Ha ジ キ prevents drug), short stablizer etc.
Modified ptfe aqueous dispersion composition of the present invention does not have special restriction, for example can stir modified ptfe aqueous dispersion of the present invention limit and add tensio-active agent and needed film forming modifying agent and other additives, mix with this and modulate described composition by the limit.
The condition of each operation of above-mentioned stirring, interpolation and blended can be set aptly according to the kind and the usage quantity of the composition that uses, and preferably carries out under 5 ℃～40 ℃ temperature.
Modified ptfe aqueous dispersion composition of the present invention is owing to have above-mentioned formation, thereby except can improving anti-crackle, thick coating as mentioned above, can also greatly increase the crackle limiting film thickness of 1 application, crackle limiting film thickness for 1 application, only can reach about 2 μ m in the past, yet for example can reach according to the present invention, and then can also be for more than or equal to 15 μ m more than or equal to about 10 μ m.
In this manual, the following mensuration of above-mentioned crackle limiting film thickness, on the aluminium sheet of 20cm * 10cm * 1.5mm, drip modified ptfe aqueous dispersion composition (5ml), use coating material feeder (peace Tian Jingji society system) surpassing 0 μ m, changing continuously between smaller or equal to 30 μ m and be coated with thickness, fired 15 minutes at 380 ℃ after 10 minutes 100 ℃ of dryings again, measure the maximum film thickness that does not crack this moment.
Modified ptfe aqueous dispersion composition of the present invention can obtain the overlay film of thick film, and surprisingly, overlay film has the transparency and high light transmission.A part that is incident upon the light of sample reflects, and other light then see through.And then the part of the light that sees through spreads, and other light then directly advance.At this, the transparency is meant directly advances light and the full impregnated ratio of light excessively.In addition, light transmission is meant that full impregnated crosses the ratio of light and incident light.
Modified ptfe of the present invention is owing to have an above-mentioned formation, thereby suitable material as modified ptfe aqueous dispersion composition of the present invention.
Modified ptfe manufacture method of the present invention is owing to have above-mentioned formation, thereby can modulate modified ptfe of the present invention easily.
Modified ptfe aqueous dispersion of the present invention and modified ptfe aqueous dispersion composition of the present invention be owing to have above-mentioned formation, thus can be processed as that film-forming properties is superior, the transparency and the superior overlay film of light transmission.
Embodiment
Illustrate in greater detail the present invention by the following examples, but the present invention is not limited to these embodiment and comparative example.
The mensuration of carrying out among each embodiment is undertaken by following method.
(1) the modified ptfe resin forms branch admittedly
Under 380 ℃ temperature, dry 45 minutes of 10g modified ptfe aqueous dispersion or modified ptfe aqueous dispersion composition are obtained residue, calculate the percentage that residue obtained quality accounts for the mass ratio of preceding above-mentioned modified ptfe aqueous dispersion of described drying or modified ptfe aqueous dispersion composition, thereby obtain the described solid content that divides that forms.
(2) average primary particle diameter
Utilization is determined average primary particle diameter based on the typical curve of transmitance and median size by described transmitance.Described transmitance forms the transmitance of element length that branch concentration is adjusted to the polytetrafluoroethylene (PTFE) aqueous liquid dispersion of 0.22 quality % for the projection light of 550nm is projected to solid; Described median size is for passing through to measure the definite median size of directed diameter in the transmission electron microscope photo.
(3) perfluor (propyl vinyl ether) comonomer unit amount (PPVE)
The powder that uses condensation, washing, dry PTFE aqueous liquid dispersion and obtain is by the 995cm of infrared absorption spectrum band -1Light absorption ratio and 2360cm -1The ratio of light absorption ratio multiply by 0.95 and obtain described quantity of units.
(4) perfluor (methylvinylether) comonomer unit amount (PMVE)
By the residual quantity in the gas chromatograph for determination reaction system, by obtaining described quantity of units by calculating consumption with the relation of add-on.
(5) the comonomer unit amount of R 1216 (HFP)
The powder that uses condensation, washing, dry PTFE aqueous liquid dispersion and obtain is by the 983cm of infrared absorption spectrum band -1Light absorption ratio and 935cm -1The ratio of light absorption ratio multiply by 0.3 and obtain described quantity of units.
(6) amount of surfactant
The use level of tensio-active agent (use level when also comprising the modulation of modified ptfe aqueous dispersion) when forming branch and modulation modified ptfe aqueous dispersion composition admittedly by the modified ptfe resin of obtaining by above-mentioned (1) is obtained and account for the quality % that the modified ptfe resin forms branch admittedly with the use level of tensio-active agent.
(7) crackle limiting film thickness
Dropwise 5 ml modified ptfe aqueous dispersion composition on the aluminium sheet of 20cm * 10cm * 1.5mm, use coating material feeder (peace Tian Jingji society system) with thickness surpassing 0 μ m, changing continuously between smaller or equal to 30 μ m and carry out 1 coating, fired 15 minutes at 380 ℃ after 10 minutes 100 ℃ of dryings again.The part that thickness is thicker can crack, with the maximum film thickness that do not crack as the crackle limiting film thickness.
(8) transparency and light transmission
The overlay film that to make when estimating above-mentioned crackle limiting film thickness is peeled off from aluminium sheet, uses direct-reading haze meter (the smart mechanism of Japan is made society of institute system) to measure the full transmittance and the haze value of the position of thickness 5 μ m.
Full impregnated light rate is represented the ratio of light transmission, and the big more light transmission that then shows of value is superior more.Haze value represents to see through the ratio of diffusion light in the light, and the more little transparency that then shows of value is superior more.
Embodiment 1
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 3.6g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 70 ℃ with 160rpm.
Then, be pressed into 2g perfluor (propyl ethylene base alcohol) (PPVE) with TFE, be pressed into that ammonium persulphate (APS) with 65mg is dissolved in the 10g water and the aqueous solution that forms with TFE again, making internal pressure is that 0.25MPa stops to add TFE, and then beginning step (1).Subsequently, along with the carrying out of reaction, internal pressure can reduce, and adds TFE when being reduced to 0.20MPa, and internal pressure is increased to 1.50MPa, beginning step (2).
To keep internal temperature be that 70 ℃, stirring velocity are 160rpm on the limit in the reaction, and step (2) is continued on the limit, always remains on 1.50 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.
After adding APS, when the TFE that consumes in reaction reaches 1500g (reaction times is 4.8 hours: the total reaction times of step (1) and step (2), below same), stop to stir and supplying with TFE, emit the interior gas of autoclave until normal pressure, thereby obtain the modified ptfe aqueous dispersion.In the modified ptfe aqueous dispersion that obtains, the modified ptfe resin forms branch admittedly and is approximately 30%, and average primary particle diameter is 329nm, and the comonomer unit of modified ptfe is 0.11 quality % of modified ptfe.
In the modified ptfe aqueous dispersion of 1000g gained, add 40g tensio-active agent TDS-80C (the first industrial pharmacy society system, Voranol EP 2001) and 160g pure water, under 70 ℃, leave standstill, form branch admittedly more than or equal to 65% modified ptfe aqueous liquid dispersion concentrate thereby obtain the modified ptfe resin.To wherein adding tensio-active agent TDS-120 (the first industrial pharmacy society system, Voranol EP 2001) and pure water, obtain the modified ptfe resin form admittedly be divided into 53 quality %, amount of surfactant is the modified ptfe aqueous dispersion composition of 13 quality % of modified ptfe.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 14 μ m, and full transmittance is 94.6%, and haze value is 11.3%.
Embodiment 2
Except adding 4g PPVE, implement operation similarly to Example 1, be to obtain the modified ptfe aqueous dispersion in 5.4 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 283nm, and the comonomer unit of modified ptfe is 0.25 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 11 μ m, and full transmittance is 96.3%, and haze value is 8.4%.
Embodiment 3
Except adding 8g PPVE, implement operation similarly to Example 1, be to obtain the modified ptfe aqueous dispersion in 8.0 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 234nm, and the comonomer unit that the modified ptfe resin forms branch admittedly is 0.48 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 6 μ m, and full transmittance is 98.1%, and haze value is 6.8%.
Embodiment 4
(PMVE) replacing implementing operation similarly to Example 1 the 2g PPVE except adding 2g perfluor (methylvinylether), is to obtain the modified ptfe aqueous dispersion in 5.8 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 305nm, and the comonomer unit of modified ptfe is 0.13 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 14 μ m, and full transmittance is 94.0%, and haze value is 13.1%.
Embodiment 5
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 4g PMVE, is to obtain the modified ptfe aqueous dispersion in 6.5 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 258nm, and the comonomer unit of modified ptfe is 0.29 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 10 μ m, and full transmittance is 95.4%, and haze value is 11.4%.
Embodiment 6
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 8g PMVE, is to obtain the modified ptfe aqueous dispersion in 9.4 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 221nm, and the comonomer unit of modified ptfe is 0.64 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 6 μ m, and full transmittance is 98.0%, and haze value is 7.2%.
Embodiment 7
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 3g R 1216 (HFP), is to obtain the modified ptfe aqueous dispersion in 4.8 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 298nm, and the comonomer unit of modified ptfe is 0.12 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 13 μ m, and full transmittance is 94.0%, and haze value is 13.4%.
Embodiment 8
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 4g HFP, is to obtain the modified ptfe aqueous dispersion in 5.2 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 290nm, and the comonomer unit of modified ptfe is 0.15 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 12 μ m, and full transmittance is 94.4%, and haze value is 12.8%.
Embodiment 9
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 8g HFP, is to obtain the modified ptfe aqueous dispersion in 7.1 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 228nm, and the comonomer unit of modified ptfe is 0.28 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 7 μ m, and full transmittance is 95.1%, and haze value is 11.5%.
Embodiment 10
Except adding 4g PPVE, be to continue 1.00 ± 0.05MPa under the step (2) in internal pressure, enforcement operation similarly to Example 1 is to obtain the modified ptfe aqueous dispersion in 7.4 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 301nm, and the comonomer unit of modified ptfe is 0.28 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 12 μ m, and full transmittance is 96.1%, and haze value is 8.0%.
Embodiment 11
Except adding 4g PPVE, be to continue 2.70 ± 0.05MPa under the step (2) in internal pressure, enforcement operation similarly to Example 1 is to obtain the modified ptfe aqueous dispersion in 3.5 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 237nm, and the comonomer unit of modified ptfe is 0.20 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 8 μ m, and full transmittance is 95.7%, and haze value is 8.9%.
Embodiment 12
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with TFE gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 70 ℃ with 160rpm.
Then, be pressed into 6g PPVE with TFE, be pressed into that APS with 65mg is dissolved in the 10g water and the aqueous solution that forms with TFE again, making internal pressure is 2.0MPa, beginning step (2).
To keep internal temperature be that 70 ℃, stirring velocity are 160rpm on the limit in the reaction, and step (2) is continued on the limit, always remains on 2.00 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, when the TFE that consumes reaches 1500g (reaction times is 3.9 hours), stop to stir and supplying with TFE in reaction.The add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 293nm, and the comonomer unit of modified ptfe is 0.26 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 10 μ m, and full transmittance is 95.8%, and haze value is 9.1%.
Embodiment 13
Replacing implementing operation similarly to Example 12 the 6g PPVE except adding 6g PMVE, is to obtain the modified ptfe aqueous dispersion in 4.8 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 280nm, and the comonomer unit of modified ptfe is 0.32 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 10 μ m, and full transmittance is 95.7%, and haze value is 11.0%.
Embodiment 14
Replacing implementing operation similarly to Example 12 the 6g PPVE except adding 6g HFP, is to obtain the modified ptfe aqueous dispersion in 3.8 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 301nm, and the comonomer unit of modified ptfe is 0.18 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 13 μ m, and full transmittance is 94.9%, and haze value is 12.3%.
Embodiment 15
Except adding 1g PPVE, implement operation similarly to Example 1, be to obtain the modified ptfe aqueous dispersion in 4.1 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 350nm, and the comonomer unit of modified ptfe is 0.07 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 16 μ m, and full transmittance is 93.8%, and haze value is 15.4%.The numerical value of crackle limiting film thickness is good, but to compare light transmission poor with embodiment 1.
Embodiment 16
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 1g PMVE, is to obtain the modified ptfe aqueous dispersion in 5.0 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 327nm, and the comonomer unit of modified ptfe is 0.09 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 14 μ m, and full transmittance is 93.5%, and haze value is 16.3%.The numerical value of crackle limiting film thickness is good, but to compare light transmission poor with embodiment 4.
Embodiment 17
Replacing implementing operation similarly to Example 1 the 2g PPVE except adding 1g HFP, is to obtain the modified ptfe aqueous dispersion in 3.3 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 354nm, and the comonomer unit of modified ptfe is 0.03 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 18 μ m, and full transmittance is 92.8%, and haze value is 17.9%.The numerical value of crackle limiting film thickness is good, but to compare light transmission poor with embodiment 7.
Embodiment 18
Except adding 5.4g ammonium perfluorocaprylate and 10g PPVE, implement operation similarly to Example 1, be to obtain the modified ptfe aqueous dispersion in 5.8 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 197nm, and the comonomer unit of modified ptfe is 0.64 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, crackle limiting film thickness less than 5 μ m.
Embodiment 19
Except adding 4g PPVE, making inner pressure constant is that the scope of 0.80 ± 0.05MPa is proceeded to implement operation similarly to Example 1 the polyreaction, is to obtain the modified ptfe aqueous dispersion in 10.2 hours with the reaction times.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 308nm, and the comonomer unit of modified ptfe is 0.30 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 12 μ m, and full transmittance is 96.4%, and haze value is 7.8%.
The numerical value of crackle limiting film thickness and light transmission is good, but to compare polymerization time extremely long with embodiment 2.
Embodiment 20
Add 4g PPVE, next be pressed into the aqueous solution that 65mg APS is dissolved in the 10g water and forms with TFE, stop to add TFE during for 0.40MPa in internal pressure, begin the 1st polymerization procedure, adding TFE when internal pressure is reduced to 0.35MPa, is to continue the 2nd polymerization procedure under 1.50 ± 0.05MPa in internal pressure, in addition, implementing operation similarly to Example 1, is to obtain the modified ptfe aqueous dispersion in 4.4 hours with the reaction times.
In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 204nm, and the comonomer unit of modified ptfe is 0.18 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, crackle limiting film thickness less than 5 μ m.
Embodiment 21
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 65 ℃ with 160rpm.
Then, be pressed into 4.0g PPVE with TFE, be pressed into the aqueous solution that 18mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, beginning step (i).After 30 minutes internal temperature is increased to 68 ℃, the beginning step (ii).
To keep internal temperature be that 68 ℃, stirring velocity are 160rpm on the limit in the reaction, and step is continued (ii) in the limit, always remains on 2.70 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, for the 0.1g/TFE consumption is that the speed of 43g is supplied with ammonium perfluorocaprylate continuously, be that the speed of 150g is supplied with PPVE continuously for the 0.1g/TFE consumption with the ammonium perfluorocaprylate with PPVE.
After adding APS, when the TFE that consumes in reaction reaches 1500g (reaction times is 4.6 hours), stop to stir and supplying with TFE, the add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g, and the add-on of PPVE comprises that the add-on before the reaction is total up to 5.0g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 248nm, and the comonomer unit of modified ptfe is 0.11 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 8 μ m, and full transmittance is 94.0%, and haze value is 11.6%.
Embodiment 22
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 65 ℃ with 160rpm.
Then, be pressed into 5.0g PPVE with TFE, be pressed into the aqueous solution that 25mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, beginning step (i).After 30 minutes internal temperature is increased to 70 ℃, the beginning step (ii).
To keep internal temperature be that 70 ℃, stirring velocity are 160rpm on the limit in the reaction, and step is continued (ii) in the limit, always remains on 2.70 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, when the TFE that consumes reaches 1500g (reaction times is 2.7 hours), stop to stir and supplying with TFE in reaction, the add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 260nm, and the comonomer unit of modified ptfe is 0.11 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 10 μ m, and full transmittance is 94.4%, and haze value is 12.1%.
Embodiment 23
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 65 ℃ with 160rpm.
Then, be pressed into 5.0g PPVE with TFE, be pressed into the aqueous solution that 18mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, beginning step (i).After 30 minutes internal temperature is increased to 70 ℃, the beginning step (ii).
To keep internal temperature be that 70 ℃, stirring velocity are 160rpm on the limit in the reaction, and step is continued (ii) in the limit, always remains on 2.70 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, when the TFE that consumes reaches 1500g (reaction times is 3.9 hours), stop to stir and supplying with TFE in reaction, the add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 271nm, and the comonomer unit of modified ptfe is 0.11 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, the crackle limiting film thickness is 11 μ m, and full transmittance is 94.3%, and haze value is 11.8%.
Embodiment 24
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 70 ℃ with 160rpm.
Then, be pressed into 5.0g PPVE with TFE, be pressed into the aqueous solution that 18mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, the beginning polymerization procedure.
To keep internal temperature be that 70 ℃, stirring velocity are 160rpm on the limit in the reaction, and polymerization procedure is continued on the limit, always remains on 2.70 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, when the TFE that consumes reaches 1500g (reaction times is 3.4 hours), stop to stir and supplying with TFE in reaction, the add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 216nm, and the comonomer unit of modified ptfe is 0.12 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, crackle limiting film thickness less than 5 μ m.
Embodiment 25
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type stirring rake and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 65 ℃ with 160rpm.
Then, be pressed into 5.0g PPVE with TFE, be pressed into the aqueous solution that 18mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, the beginning polymerization procedure.
To keep internal temperature be that 65 ℃, stirring velocity are 160rpm on the limit in the reaction, and polymerization procedure is continued on the limit, remains on 2.70 ± 0.05MPa often in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, the TFE that is consumed in the reaction reaches 500g needs 2.1 hours, and the modified ptfe resin that obtain about 30 quality % forms branch admittedly needs the longer time, existing problems aspect productivity, thereby stopped stirring and supplying with TFE.
Embodiment 26
Adding 3600g deionized water, 180g fusing point are 56 ℃ paraffin and 0.1g ammonium perfluorocaprylate in having the stainless steel autoclave that stainless steel blade type agitating wing and temperature regulation are 6L with sleeve pipe, inner capacities, with nitrogen replacement 3 times, and remove oxygen in the system with tetrafluoroethylene (TFE) gas displacement 2 times after, being pressed into TFE gas, to make internal pressure be 0.05MPa, stirs and internal temperature is remained on 70 ℃ with 160rpm.
Then, be pressed into 5.0g PPVE with TFE, be pressed into the aqueous solution that 18mg APS is dissolved in the 10g water and forms with TFE again, making internal pressure is 2.7MPa, begins the 1st polymerization procedure.After 30 minutes internal temperature is increased to 75 ℃, begins the 2nd polymerization procedure.
To keep internal temperature be that 75 ℃, stirring velocity are 160rpm on the limit in the reaction, and the 2nd polymerization procedure is continued on the limit, always remains on 2.70 ± 0.05MPa in order to make internal pressure, supplies with TFE continuously.In addition, be that the speed of 43g is supplied with ammonium perfluorocaprylate continuously with the ammonium perfluorocaprylate for the 0.1g/TFE consumption.
After adding APS, when the TFE that consumes reaches 1500g (reaction times is 2.7 hours), stop to stir and supplying with TFE in reaction, the add-on of ammonium perfluorocaprylate comprises that the add-on before the reaction is total up to 3.6g.Emit the interior gas of autoclave until normal pressure, form the modified ptfe aqueous dispersion that branch is approximately 30 quality % admittedly thereby obtain the modified ptfe resin.In the modified ptfe aqueous dispersion that obtains, average primary particle diameter is 209nm, and the comonomer unit of modified ptfe is 0.14 quality % of modified ptfe.
Concentrate this modified ptfe aqueous dispersion similarly to Example 1, obtain the modified ptfe aqueous dispersion composition.For the modified ptfe aqueous dispersion composition that obtains, crackle limiting film thickness less than 5 μ m.
The possibility of using on the industry
Modified ptfe of the present invention is owing to have an above-mentioned formation, thereby suitablely changes as of the present invention The material of property PTFE aqueous dispersion composition.
Modified ptfe manufacture method of the present invention is owing to have above-mentioned formation, thereby can be easily Modulate modified ptfe of the present invention.
Modified ptfe water-borne dispersions of the present invention and modified ptfe aqueous liquid dispersion group of the present invention Compound is owing to have above-mentioned formation, thereby can be processed as that film forming is superior, glossiness and transparent The overlay film that property is superior.

Claims (3)

1, a kind of modified Teflon aqueous dispersion composition, it is characterized in that, it is the modified Teflon aqueous dispersion composition that contains the tensio-active agent that adds after modified Teflon aqueous dispersion and the polymerization, described modified Teflon aqueous dispersion is dispersed in the aqueous medium by the formed particle of modified Teflon and forms, described modified Teflon is polymerizing tetrafluoroethylene and comonomer and the modified Teflon that obtains, wherein, the comonomer unit that described comonomer forms accounts for the 0.1 quality %～1.0 quality % of described modified Teflon, the average primary particle diameter of described modified Teflon is 220nm～500nm, and described comonomer is a R 1216, perfluor (alkyl vinyl ether) and/or vinylidene.
2, a kind of manufacture method of modified Teflon aqueous dispersion composition, it is the manufacture method of the described modified Teflon aqueous dispersion composition of claim 1, this manufacture method is characterised in that, described modified Teflon is to make by the polymerization of carrying out tetrafluoroethylene and comonomer in water-based polymer medium, described polymerization comprises step (1) and step (2), in step (1), described polymerization begin the back during having with respect to per 1 liter of described water-based polymer medium that described tetrafluoroethylene more than or equal to 1g is consumed in, under smaller or equal to the polymerization pressure of 0.3Mpa, carry out polyreaction; In step (2), after described step (1), under the polymerization pressure of 1Mpa～3Mpa, carry out polyreaction.
3, a kind of manufacture method of modified Teflon aqueous dispersion composition, it is the manufacture method of the described modified Teflon aqueous dispersion composition of claim 1, this manufacture method is characterised in that, described modified Teflon is to make by the polymerization of carrying out tetrafluoroethylene and comonomer in water-based polymer medium, described polymerization comprises step (i) and step (ii), in step (i), described polymerization begin the back during having with respect to per 1 liter of described water-based polymer medium that described tetrafluoroethylene more than or equal to 1g is consumed in, carry out polyreaction, wherein 55＜X＜70 with polymerization temperature X ℃; Step (ii) in, after described step (i), carry out polyreaction with polymerization temperature Y ℃, Y 〉=X+3 wherein, X is same as described above.
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