CN100475867C - Fluorine-containing polymer and treating agent composition - Google Patents
Fluorine-containing polymer and treating agent composition Download PDFInfo
- Publication number
- CN100475867C CN100475867C CNB2005800112218A CN200580011221A CN100475867C CN 100475867 C CN100475867 C CN 100475867C CN B2005800112218 A CNB2005800112218 A CN B2005800112218A CN 200580011221 A CN200580011221 A CN 200580011221A CN 100475867 C CN100475867 C CN 100475867C
- Authority
- CN
- China
- Prior art keywords
- hydrogen atom
- paper
- fluoropolymer
- agent composition
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A fluorine-containing polymer which comprises (a) a fluorine-containing (meth)acrylate monomer and (b) a nitrogen-containing monomer represented by the general formula (I): wherein R<20> represents a hydrogen atom or a group containing a sulfonic acid group, R<21> represents a hydrogen atom or an alkyl group having one to four carbon atoms, and R<22> represents a hydrogen atom or a methyl group; and a treating agent composition comprising said fluorine-containing polymer. The fluorine-containing polymer and the treating agent composition can be used for imparting satisfactory water repellency and oil resistance to a sheet of paper by the use of a reduced amount thereof.
Description
Technical field
The composition that the present invention relates to fluoropolymer and be used to handle base material (paper and masonry solid substrates such as (masonry)).The base material that the present invention also relates to the treatment process of base material and be attached with said composition.
Background technology
In the past, as the Waterproofing/oilproofing machining agent that paper is used, have document to propose following machining agent: (1) with the phosphate compound with Polyfluoroalkyl (Rf yl hereinafter referred to as) serve as must composition machining agent (spy opens clear 64-6196 communique, the spy opens flat 3-123786 communique); (2) with the multipolymer of acrylate, dimethylamino alkylmethacrylate and vinyl-acetic ester with Rf base serve as must composition machining agent (spy opens flat 7-206942 communique).
For machining agent (1) because the phosphate compound with Rf base is a water-soluble cpds, therefore exist can not imparting water repellency for paper problem.In addition, when using the higher water of the hardness contain calcium, magnesium etc., also exist effective constituent to separate out and can not bring into play the problem of the performance of being expected.For for machining agent (2),, generally acknowledge to have the problem that must increase its usage quantity in order to bring into play high oil-proofness.
Though Te Kaiping 7-34384 communique discloses the method for giving water and oil-resistant to paper, does not obtain sufficient performance.
In the light of recent researches the result (EPA report " PRELIMINARY RISKASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATEDWITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS " (http://www.epa.gov/opptintr/pfoa/pfoara.pdf) etc., the load of PFOA (Perfluorocaprylic Acid) to environment has been unequivocally established; EPA (the U.S. environment protection Room) investigates in the science that on April 14th, 2003 indicated to strengthen PFOA.
On the other hand, federal register (Federal Register) (FR Vol.68, No.73/2003 April 16 [FRL-2303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), the EPA Environmental News of issue on April 14th, 2003 (Monday): " EPA INTENSIFIESSCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID " (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf), the EPAOPPT FACT SHEET (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) on April 14th, 2003 has announced that " telomer (telomer) " has the possibility that generates PFOA by decomposition or metabolism.And, announced that also " telomer " can be used in a lot of goods, comprising fire foam, health-care products, cleaning article; And be arranged on waterproof and oilproof serving and antifouling processing serving on carpet, yarn fabric, paper, the leather.
Summary of the invention
The object of the present invention is to provide a kind of agent composition, this agent composition can be given sufficient water-repellancy and oil-proofness to paper by a small amount of use.
Other purpose of the present invention is to provide a kind of fluoropolymer, and this fluoropolymer is given higher water and oil-resistant and didirtresistance to paper and masonry.
The inventor finds, by paper or masonry being handled for paper composition for treating that must composition in order to specific polymkeric substance, can bring into play higher water-repellancy, oil-proofness and didirtresistance.
The present invention relates to fluoropolymer, this fluoropolymer has the straight or branched fluoro-alkyl that contains 1～6 carbon atoms, and its extension glass transition end temp (Teg) is more than or equal to 25 ℃.
The invention still further relates to fluoropolymer, this fluoropolymer contains (a) and (b), described (a) is at least a kind in fluorine-containing (methyl) acrylate monomer shown in the following general formula (I) of 55 weight parts～99 weight parts, and described (b) is at least a kind in the nitrogen containing monomer shown in the following general formula (II) of 1 weight part～45 weight parts;
In the general formula (I), Rf represents to contain the straight or branched fluoro-alkyl of 1～6 carbon atoms; A represents divalent organic group, this divalent organic group have with adjacent to the Sauerstoffatom of the A group carbon atom of bonding mutually, and can contain one or more Sauerstoffatoms, sulphur atom and/or nitrogen-atoms as required; R
11And R
12In one the expression hydrogen atom, another the expression hydrogen atom, contain the 1～alkyl of 4 carbon atoms, halogen atom, CFX
1X
2Group, cyano group, carbonatoms are 1～20 straight chain shape or the benzyl of catenate fluoro-alkyl, replacement or non-replacement or the phenyl of replacement or non-replacement; CFX
1X
2In the group, X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom;
In the general formula (II), R
20Represent hydrogen atom, contain sulfonic group, R
21Expression hydrogen atom or contain the alkyl of 1～4 carbon atoms, R
22Expression hydrogen atom or methyl.
The invention still further relates to agent composition, this agent composition contains following (1) and (2), the fluoropolymer (particularly fluorinated copolymer) that described (1) is above-mentioned, and described (2) are liquid medium.
The invention further relates to the treatment process of base material, this treatment process adopts above-mentioned agent composition that solid substrate is handled.
Use even treatment agent of the present invention is a small amount of, also give higher water-repellancy, oil-proofness and didirtresistance to base material (particularly paper or masonry).For paper, oil-proofness is important usually, and treatment agent of the present invention can be given excellent oil-proofness to paper.
Embodiment
So-called extension glass transition end temp (Teg) be meant the energy input of fluoropolymer poor-a flex point (with reference to JIS K7121-1987) on the temperature curve (DSC curve).Teg is more than or equal to 25 ℃, for example more than or equal to 30 ℃, further more than or equal to 35 ℃, particularly more than or equal to 40 ℃.
In this specification sheets, acrylate and methacrylic ester are generically and collectively referred to as (methyl) acrylate, also identical for the record of (methyl) acrylamide etc.
In fluorine-containing (methyl) acrylate monomer (a), so-called Rf base is that at least 2 hydrogen atoms of alkyl are replaced by fluorine atom and the group that obtains.The Rf base can be linear chain structure or branched structure.The carbonatoms of Rf base is 1～6, for example is 2～6, particularly 4.When the number of fluorine atoms ratio in the Rf base is represented with following calculating formula, be preferably greater than and equal 60%, be preferably greater than especially and equal 80%, be preferably 100% in fact especially, described calculating formula is: (number of fluorine atoms in the Rf base)/(having number of hydrogen atoms in the alkyl of same carbon atoms number with corresponding Rf base) * 100 (%).In addition, hereinafter all hydrogen atoms of alkyl are replaced by fluorine atom and the group that obtains is called perfluoroalkyl.The Rf base is preferably perfluoroalkyl.
The example of Rf base has :-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3,-(CF
2)
5CF
3,-(CF
2)
3CF (CF
3)
2Deng.
R
11Or R
12Can be halogen atom, preferred halogen atom is fluorine atom, chlorine atom, bromine atoms and iodine atom.
Among the present invention, (methyl) acrylate that what is called has the Rf base is meant the compound that has the Rf group in the ester residue of (methyl) acrylate.(methyl) acrylate with Rf group can be a kind or at least 2 kinds.
As fluorine-containing (methyl) acrylate monomer (a), can enumerate following compound.
CH
2＝CR’COOCH
2CH
2Rf、
CH
2＝CR’COOCH
2CH
2N(CH
2CH
2CH
3)CORf、
CH
2＝CR’COOCH(CH
3)CH
2Rf、
CH
2＝CR’COOCH
2CH
2N(CH
3)SO
2Rf、
CH
2＝CR’COOCH
2CH
2N(CH
3)CORf、
CH
2＝CR’COOCH
2CH
2N(CH
2CH
3)SO
2Rf、
CH
2＝CR’COOCH
2CH
2N(CH
2CH
3)CORf、
CH
2＝CR’COOCH
2CH
2N(CH
2CH
2CH
3)SO
2Rf、
CH
2＝CR’COOCH(CH
2Cl)CH
2OCH
2CH
2N(CH
3)SO
2Rf。
In the above-claimed cpd, R ' represents hydrogen atom, contains the 1～alkyl of 4 carbon atoms, halogen atom, CFX
1X
2Group (X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom), cyano group, carbonatoms is the phenyl (particularly hydrogen atom, halogen atom or methyl) of benzyl, replacement or the non-replacement of 1～20 straight chain shape or catenate fluoro-alkyl, replacement or non-replacement, Rf represents implication same as described above (Rf represents to contain the straight or branched fluoro-alkyl of 1～6 carbon atoms), is preferably perfluoroalkyl especially.
A does not preferably contain S (sulphur atom) or N (nitrogen-atoms).
The object lesson of fluorine-containing (methyl) acrylate monomer (a) is as described below.
F(CF
2)
5CH
2OCOCR’＝CH
2、
F(CF
2)
4CH
2CH
2OCOCR’＝CH
2、F(CF
2)
6CH
2CH
2OCOCR’＝CH
2、
H(CF
2)
6CH
2OCOCR’＝CH
2、
H(CF
2)
4CH
2OCOCR’＝CH
2、
H(CF
2)
4CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
2CH
2CH
2OCOCR’＝CH
2、
(CF
3)
2CFCH
2CH
2OCOCR’＝CH
2、
(CF
3)
2CF(CF
2)
3CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6SO
2N(C
3H
7)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6CON(C
3H
7)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6CH
2CH(CH
3)OCOCR’＝CH
2、
F(CF
2)
6(CH
2)
4OCOCR’＝CH
2、
F(CF
2)
6SO
2N(CH
3)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6CON(CH
3)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6SO
2N(C
2H
5)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6CON(C
2H
5)CH
2CH
2OCOCR’＝CH
2、
F(CF
2)
6CONHCH
2CH
2OCOCR’＝CH
2、
(CF
3)
2CF(CF
2)
3(CH
2)
3OCOCR’＝CH
2、
(CF
3)
2CF(CF
2)
3CH
2CH(OCOCH
3)OCOCR’＝CH
2
(CF
3)
2CF(CF
2)
3CH
2CH(OH)CH
2OCOCR’＝CH
2、。
In the following formula, R ' represents hydrogen atom, halogen atom or methyl.
The example of nitrogen containing monomer (b) has: (b-1) contain sulfonic monomer and (b-2) acrylamide.
The example that contains the monomer (b-1) of sulfonic acid group has the monomer shown in the following general formula (III);
In the general formula (III), B represents to contain the straight or branched alkylidene group of 1～5 carbon atoms, and M represents the basic metal or the NR of hydrogen atom, 1 valency
30 4(each R
30For hydrogen atom, carbonatoms are that 1～10 alkyl or carbonatoms are 1～10 hydroxyalkyl), R
21Expression hydrogen atom or contain the alkyl of 1～4 carbon atoms, R
22Expression hydrogen atom or methyl.
Contain in the sulfonic monomer (b-1), when M was basic metal, the example of M had: potassium, sodium, lithium.M is that the example of quaternary ammonium salt has: N (CH
3)
4The example of B has: propylidene, butylidene, pentylidene.
The object lesson that contains sulfonic monomer (b-1) has: 2-acrylamide-2-methyl propane sulfonic acid, 2-Methacrylamide-2-ethyl propanesulfonic acid, 2-acrylamide fourth sulfonic acid etc.Be preferably 2-acrylamide-2-methyl propane sulfonic acid.
As fluoropolymer, except that contain monomer (a) and (b), also can contain other monomer (c).Example as other monomer (c), can enumerate for example following monomer: ethene, vinyl-acetic ester, ethylene halide (for example, vinylchlorid), vinylidene halide (for example, vinylidene chloride), vinyl cyanide, vinylbenzene, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, single (methyl) vinylformic acid glyceryl ester, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, tetrahydrofurfuryl (methyl) acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, divinyl etc., but be not limited to this.
The weight-average molecular weight of fluoropolymer for example can be 2000～5000000, further is 3000～5000000, particularly 10000～1000000.The weight-average molecular weight of fluoropolymer records (being converted into polystyrene) by GPC (gel permeation chromatography).
In the fluoropolymer (particularly fluorinated copolymer), the amount of monomer (a) can be 60 weight parts～95 weight parts, for example is 65 weight parts～90 weight parts; The amount of monomer (b) can be 5 weight parts～40 weight parts, particularly 10 weight parts～30 weight parts, for example is 15 weight parts～25 weight parts; Monomer (c) is 0 weight part～20 weight parts in gross weight, for example is 0.1 weight part～8 weight parts.
Fluoropolymer among the present invention can be made with in the conventional polymerization process any one, and the condition of polyreaction also can at random be selected in addition.As this polymerization process, can enumerate solution polymerization, letex polymerization.
Polymerization is undertaken by using at least a initiator, and described initiator is 0.1%～2.0% with respect to the ratio of whole monomer weights.As initiator, can use benzoyl peroxide, lauroyl peroxide, succinyl peroxide, the tertiary butyl to cross superoxide such as trimethylacetic acid; Or such as 2,2-Diisopropyl azodicarboxylate, 4, azo-compounds such as 4-azo two (4-cyanopentanoic acid), azodicarboamide.
Polymerization procedure can carry out in the temperature range of the boiling point from 40 ℃ to reaction mixture.Polymerization procedure preferably carries out between 60 ℃～90 ℃.
As organic solvent, can be for being inert for monomer and dissolving these monomeric solvents, for example can enumerate, acetone, chloroform, HCHC225, N, dinethylformamide, Virahol, pentane, hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, sherwood oil, tetrahydrofuran (THF), 1,4-diox, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butylacetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trieline, tetrachloroethylene, C2Cl4F2, Refrigerant R 113, hydrogen fluorine ethers etc.With respect to the total amount is the monomer of 100 weight parts, and employed organic solvent is 50 weight parts～2000 weight parts, for example in the scope of 50 weight parts～1000 weight parts.
Treatment agent of the present invention can be solution, emulsion or aerocolloidal form.Treatment agent contains fluoropolymer and medium (for example, liquid medium such as organic solvent and water).
For fluoropolymer of the present invention, even there is not emulsifying agent, also can self emulsification and form emulsion (particularly water-based emulsion) and maybe can dissolve and form the aqueous solution.As required, emulsion also can contain emulsifying agent (with respect to the fluoropolymer of 100 weight parts, the amount of emulsifying agent for example is 0.01 weight part～40 weight parts, is in particular 0.1 weight part～20 weight parts).
In the treatment agent, the concentration of fluoropolymer for example can be 0.01 weight %～50 weight %.
Treatment agent of the present invention can be used for handling (for example, surface treatment) paper or masonry.
Treatment agent of the present invention can be applied to object being treated by known method in the past.Usually adopt following method (surface treatment): treatment agent is disperseed, dilutes with organic solvent or water,, make its surface that is attached to object being treated, and carry out drying by known method such as dip-coating, spraying, foaming coatings.In addition, when the manufacturing paper with pulp of paper, also can in paper pulp, add treatment agent (in add processing).When carrying out surface treatment, fluorine atom in the fluoropolymer can be 0.01 weight %～0.5 weight % with respect to the ratio of the weight of paper, for example can be 0.05 weight %～0.2 weight %, in carrying out, add when handling, fluorine atom can be 0.05 weight %～0.5 weight % with respect to the ratio of the weight of paper pulp, for example can be 0.2 weight %～0.4 weight %.Fluoropolymer of the present invention is attached to base material particularly on the paper well.
Paper can be made by known pulping method in the past.Can use treatment agent made an addition to the internal addition method in the paper pulp before manufacturing paper with pulp or treatment agent is applied to manufacture paper with pulp after the external addition method of paper.Base material through so handling carries out simple drying in room temperature or high temperature, and optional then heat-treating makes base material show excellent oleophobic property and hydrophobicity in view of the above, and described thermal treatment can be taked to be up to 200 ℃ temperature according to the character of base material and carry out.
The present invention can be used for plasterboard body paper, coating body paper, matter paper, general liner and medium, neutral pure white coil paper, neutral liner, antirust liner and metlbond paper, kraft paper etc.In addition, also can be used for neutral printing writing paper, neutral coating body paper, neutral PPC with paper, neutral sensible heat with paper, neutral pressure-sensitive body paper, neutral ink-jet with paper and neutral information paper.Further, can also be used to use a model the pattern paper of moulding, particularly the model container.Paper pulp model container for example can be opened flat 9-183429 number described method by the spy and make.
As pulpwood, following raw material all can use: bleaching such as kraft pulp or sulfite pulp or not bleaching such as bleached chemical paper pulps, wood fragments paper pulp, mechanical pulp or thermomechanical pulp or not old paper paper pulp such as high yield paper pulp bleaching, the old paper of newspaper, the old paper of magazine, the old paper of corrugated cardboard or the old paper of deinking.In addition, also can use the mixture of synthon such as above-mentioned pulpwood and asbestos, polymeric amide, polyimide, polyester, polyolefine or polyvinyl alcohol.
Can add slurry (sizing agent) and improve the water tolerance of paper.The example of slurry has: cationic slurry, anionic property slurry, rosin based slurry (for example, acid rosin class slurry, neutral rosin based slurry).The amount of slurry can be 0.01 weight part～5 weight parts with respect to paper pulp.
As usually in paper as required and the system paper that uses with chemical (medicine), can use employed additives in the manufacturing of paper such as paper power toughener, yield rising agent, dyestuff, fluorescence dye, slimicide (slimecontrolling agent), defoamer such as various treated starches beyond starch, the above-mentioned starch, carboxymethyl cellulose, polymeric amide polyamine-epichlorohydrin resins.
As required, treatment agent etc. can be utilized sizing applicator, door roll-coater, two-sided knife coater, rolling press etc. to coat on the paper with starch, polyvinyl alcohol, dyestuff, coating color, slipproofing agent etc.
Base material can be masonries such as stone material.The example of masonry has: stone, brick, watt.The example of stone has natural stone (for example, marble, granite), rostone.
For masonry,, handles by treatment agent by being coated on the base material.The amount of the treatment agent that is coated with can be 20g/m
2～1000g/m
2, be preferably 50g/m
2～500g/m
2Coating can 1 time or is divided into repeatedly and carries out.As the method for coating, can be brushing, spraying, roller coat, treatment agent be impregnated in the cloth sheet, and (ウ エ ス rags) is coated with, arbitrary method such as dip-coating, can wipe excessive composition away as required.Then with the treatment agent drying.Drying can be carried out in room temperature, also can fire at 80 ℃～250 ℃.Fluoropolymer can form 0.01g/m on masonry
2～100g/m
2Film.
Treated object being treated (base material) can be fibre product, filter (for example, the static filter), the element of dw, fuel cell (for example, gas diffusion electrode and gaseous diffusion supporter), glass, wood, leather, fur, asbestos, brick, cement, metal and oxide compound, ceramic, plastics, be coated with face and gypsum etc.
In this specification sheets, " processing " refers to by dipping, spraying, coating etc. treatment agent is applied to object being treated.By handling, infiltrate into the inside of object being treated and/or attached to the surface of object being treated as the fluoropolymer of the effective constituent of treatment agent.
Embodiment
The present invention will be described in detail hereinafter to enumerate embodiment.
Embodiment hereinafter is used to illustrate the present invention, but and is used for not limiting the present invention.If there is not other explanation, then part and per-cent (%) hereinafter is weight part and weight percent (weight %).
Employed test method is as described below.
Oil-proofness
Oil-proofness is measured according to the extension method of TAPPI UM-557.Test oil shown in the table 1 is placed on the paper, observe the infiltration state of oil after 15 seconds.To not show the vertex of the oil resistant degree that test oil provided of infiltration as oil-proofness.
[table 1]
| The oil resistant degree | Viscotrol C | Toluene | Heptane |
| 1 | 100 | 0 | 0 |
| 2 | 90 | 5 | 5 |
| 3 | 80 | 10 | 10 |
| 4 | 70 | 15 | 15 |
| 5 | 60 | 20 | 20 |
| 6 | 50 | 25 | 25 |
| 7 | 40 | 30 | 30 |
| 8 | 30 | 35 | 35 |
| 9 | 20 | 40 | 40 |
| 10 | 10 | 45 | 45 |
| 11 | 0 | 50 | 50 |
| 12 | 0 | 45 | 55 |
| 13 | 0 | 35 | 65 |
| 14 | 0 | 25 | 75 |
| 15 | 0 | 15 | 85 |
| 16 | 0 | 0 | 100 |
In addition, HCFC225 uses Asahi Glass (strain) system AK-225.
In addition, DMF represents dimethyl formamide, and AMPS represents 2-acrylamide-2-methyl propane sulfonic acid, and DM represents dimethyl amino ethyl methacrylate, and AAm represents acrylamide, and VAc represents vinyl-acetic ester.
The body paper of polymers soln coating usefulness is according to following order manufacturing.
The mixture of the softwood tree bleached kraft pulp of 90 parts bleached hardwood kraft pulps and 10 parts is made the aqueous liquid dispersion of 1 weight %, get this aqueous liquid dispersion of 500g, when stirring, add the solution of polymeric amide polyamine-Epicholorohydrin reactant (Japanese PMC (strain) makes WS-570) of 2g, it is 1% that the solid formation of this solution divides content, and stirs 2 minutes.Use JIS P8209 described standard page machine (standard papermaking system) that this paper pulp is copied paper.L Water Paper is sandwiched between the filter paper, with 3.5kg/cm
2Pressure push, to draw water fully, carry out drying (100 ℃ * 2 minutes) with cylinder type dryer, obtain body paper.The level ground amount of this paper is 80g/m
2
Synthesis example 1
It is 100 parts (1L) and have in the reactor of whipping appts, thermometer, reflux cooler, addition funnel, nitrogen influx and heating unit that 22.6 parts AK-225,22.6 parts DMF, 2.79 parts AMPS and the fluorinated acrylate (V) shown in 8.4 parts of following formulas are put into volume.
This mixture was exposed to stream of nitrogen gas following 30 minutes, be warming up to 60 ℃ after, add 0.16 part tert-butyl hydroperoxide trimethylacetic acid ester 70% solution, reacted 6 hours.The rate of consumption that records fluorinated acrylate (V) by vapor-phase chromatography is 100%.
Then, this reaction mixture is cooled to room temperature.Obtain 56 parts clear solution (S1) thus, the solid formation branch concentration of this solution is 19.8%.
Synthesis example 2
Except with 8.4 parts the fluorinated acrylate (V) in fluorinated acrylate (VI) the replacement synthesis example 1 of 8.4 parts of following formulas, repeat and synthesis example 1 identical operations.The rate of consumption that records fluorinated acrylate (VI) by vapor-phase chromatography is 100%.Obtain 56 parts clear amber in color solution (S2) thus, the solid formation branch concentration of this solution is 20.0%.
Synthesis example 3
Except the amount with the fluorinated acrylate in the synthesis example 2 (VI) changes 7.2 parts into, the amount of AMPS is changed into 4 parts, repeat and synthesis example 2 identical operations.The rate of consumption that records fluorinated acrylate (VI) by vapor-phase chromatography is 100%.Obtain 56 parts clear amber in color solution (S3) thus, the solid formation branch concentration of this solution is 20.0%.
Synthesis example 4
Except 2.79 parts AMPS in the synthesis example 1 being changed into 0.8 part acrylamide (AAm), the amount of fluorinated acrylate (V) being changed into 10.4 parts, repeat and synthesis example 1 identical operations.The rate of consumption that records fluorinated acrylate (V) by vapor-phase chromatography is 100%.Obtain 56 parts clear amber in color solution (S4) thus, the solid formation branch concentration of this solution is 19.9%.
Synthesis example 5
Except the amount with acrylamide changes 1.8 parts into, the amount of fluorinated acrylate (V) is changed into 9.4 parts, repeat and synthesis example 4 identical operations.The rate of consumption that records fluorinated acrylate (V) by vapor-phase chromatography is 100%.Obtain 56 parts clear amber in color solution (S5) thus, the solid formation branch concentration of this solution is 20.0%.
Synthesis example 6
To put into volume be 100 parts and have in the reactor of whipping appts, thermometer, reflux cooler, addition funnel, nitrogen influx and heating unit with the fluorinated acrylate (V) of 22.6 parts AK-225,22.6 parts DMF, 2.23 parts DM, 0.56 part vinyl-acetic ester (VAc) and 8.4 parts.
This mixture was exposed to stream of nitrogen gas following 30 minutes, be warming up to 60 ℃ after, add 0.16 part tert-butyl hydroperoxide trimethylacetic acid ester 70% solution, reacted 6 hours.The rate of consumption that records fluorinated acrylate (V) and DM by vapor-phase chromatography is 100%.
Then, this reaction mixture is cooled to room temperature.Obtain 56 parts clear solution (S6) thus, the solid formation branch concentration of this solution is 19.5%.
Synthesis example 7
Except with 8.4 parts the fluorinated acrylate (V) in 8.4 parts fluorinated acrylate (VI) the replacement synthesis example 6, repeat and synthesis example 6 identical operations.The solid formation branch concentration of resulting solution (S7) is 19.5%.The rate of consumption that records fluorinated acrylate (V) and DM by vapor-phase chromatography is 100%.
Synthesis example 8
Except the amount with the fluorinated acrylate in the synthesis example 6 (VI) changes 7.2 parts into, the amount of DM is changed into 3.43 parts, repeat and synthesis example 6 identical operations.The rate of consumption that records fluorinated acrylate (VI) and DM by vapor-phase chromatography is 100%.Obtain 56 parts clear amber in color solution (S8) thus, the solid formation branch concentration of this solution is 19.5%.
Embodiment 1
Solution S 1 is diluted to the solid formation branch concentration of defined with HCFC225.Body paper be impregnated in wherein, uses extrusion machine (Twisted り Machine then) press with squeeze pressure (Twisted り) be 1.0kg/m
2Push at room temperature dry 30 minutes.Then, with the round tube type moisture eliminator 115 ℃ of heat treated 1 minute.Estimate the oil resistant degree of resulting paper.The result is as shown in table 2.
In addition, with the extension glass transition end temp (Teg) of differential scanning calorimeter (DSC-50 that Shimadzu Seisakusho Ltd. makes) with the determination of heating rate polymkeric substance of 20 ℃/min.
Embodiment 2～5
Except the solution S among the embodiment 11 being replaced with S2 (embodiment 2), S3 (embodiment 3), S4 (embodiment 4) or S5 (embodiment 5), repeat and embodiment 1 identical operations.The result is as shown in table 2.
Comparative example 1～3
Except the solution S 1 with embodiment 1 replaces with S6 (comparative example 1), S7 (comparative example 2) or S8 (comparative example 3), repeat and embodiment 1 identical operations.The result is as shown in table 2.
[table 2]
| Experimental liquid | The monomer ratio | Extension glass transition end temp Teg (℃) | Be coated with liquid-solid formation branch concentration [%] | Oil resistant degree [reagent set (kit)] | |
| Embodiment 1 | S1 | (V)/AMPS 75/25 | 40 | 0.075 0.150 0.225 | 9 11 14 |
| Embodiment 2 | S2 | (VI)/AMPS 75/25 | 68 | 0.075 0.150 0.225 | 7 10 15 |
| Embodiment 3 | S3 | (VI)/AMPS 65/35 | 71 | 0.075 0.150 0.225 | 7 11 14 |
| Embodiment 4 | S4 | (V)/AAm 93/7 | 44 | 0.075 0.150 0.225 | 10 11 14 |
| Embodiment 5 | S5 | (V)/AAm 84/16 | 61 | 0.075 0.150 0.225 | 9 10 13 |
| Comparative example 1 | S6 | (V)/DM/VAc 75/20/5 | ＜25 | 0.075 0.150 0.225 | 5 6 7 |
| Comparative example 2 | S7 | (VI)/DM/VAc 75/20/5 | ＜25 | 0.075 0.150 0.225 | 7 9 10 |
| Comparative example 3 | S8 | (VI)/DM/VAc 65/30/5 | ＜25 | 0.075 0.150 0.225 | 5 6 7 |
Preferred implementation of the present invention is as described below.
A. fluoropolymer, this fluoropolymer contains (a) and (b), described (a) is at least a kind in fluorine-containing (methyl) acrylate monomer shown in the following general formula (I) of 55 weight parts～99 weight parts, and described (b) is in the sulfonic monomer at least a kind of containing shown in the following general formula (III) of 1 weight part～45 weight parts;
In the general formula (I), Rf represents to contain the straight or branched fluoro-alkyl of 1～6 carbon atoms; A represents divalent organic group, this divalent organic group have with adjacent to the Sauerstoffatom of the A group carbon atom of bonding mutually, and can contain one or more Sauerstoffatoms, sulphur atom and/or nitrogen-atoms as required; R
11And R
12In one the expression hydrogen atom, another the expression hydrogen atom, contain the 1～alkyl of 4 carbon atoms, halogen atom, CFX
1X
2Group, cyano group, carbonatoms are 1～20 straight chain shape or the benzyl of catenate fluoro-alkyl, replacement or non-replacement or the phenyl of replacement or non-replacement; CFX
1X
2In the group, X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom;
In the general formula (III), B represents to contain the straight or branched alkylidene group of 1～5 carbon atoms; M represents the basic metal or the NR of hydrogen atom, 1 valency
30 4, this NR
30 4In, each R
30For hydrogen atom, carbonatoms are that 1～10 alkyl or carbonatoms are 1～10 hydroxyalkyl; R
21Expression hydrogen atom or contain the alkyl of 1～4 carbon atoms, R
22Expression hydrogen atom or methyl.
B. as the described fluoropolymer of A item, wherein, described fluorine-containing (methyl) acrylate monomer (a) is that the carbonatoms of Rf base is 4 or 6 material, or the mixture of above-mentioned substance.
C. as the described fluoropolymer of A item, wherein, described nitrogen containing monomer (b) is 2-acrylamide-2-methyl propane sulfonic acid.
D. as the described fluoropolymer of A item, wherein, the amount of described nitrogen containing monomer (b) is 10 weight parts～30 weight parts.
E. agent composition, it contains following (1) and (2), and described (1) is the described fluoropolymer of A item, and described (2) are liquid medium.
F. as the described agent composition of E item, wherein, described liquid medium (2) is organic solvent or water.
G. as the described agent composition of E item, this agent composition is the paper treatment agent.
H. the treatment process of a base material, this treatment process adopt the described agent composition of E item that solid substrate is handled.
I. as the described treatment process of H item, wherein, described base material is paper or masonry.
J. base material, this base material adopt the described treatment process of H item to handle.
The described polymkeric substance of K.A item is at solid substrate, particularly in the oleophobic property of paper and ground paper and the application in the hydrophobicity processing.
Claims (11)
1. fluoropolymer, this fluoropolymer contains (a) and (b), described (a) is at least a kind in fluorine-containing (methyl) acrylate monomer shown in the following general formula (I) of 55 weight parts～99 weight parts, and described (b) is in the sulfonic monomer at least a kind of containing shown in the following general formula (III) of 1 weight part～45 weight parts;
In the general formula (I), Rf represents to contain the straight or branched fluoro-alkyl of 1～6 carbon atoms; A represents divalent organic group, this divalent organic group have with adjacent to the Sauerstoffatom of the A group carbon atom of bonding mutually, and contain or do not contain one or more Sauerstoffatoms, sulphur atom and/or nitrogen-atoms; R
11And R
12In, R
11The expression hydrogen atom, contain the alkyl or the halogen atom of 1～4 carbon atoms, R
12The expression hydrogen atom; CFX
1X
2In the group, X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom;
In the general formula (III), B represents to contain the straight or branched alkylidene group of 1～5 carbon atoms; M represents the basic metal or the NR of hydrogen atom, 1 valency
30 4, this NR
30 4In, each R
30For hydrogen atom, carbonatoms are that 1～10 alkyl or carbonatoms are 1～10 hydroxyalkyl; R
21Expression hydrogen atom or contain the alkyl of 1～4 carbon atoms, R
22Expression hydrogen atom or methyl.
2. fluoropolymer as claimed in claim 1, wherein, described fluorine-containing (methyl) acrylate monomer (a) is that the carbonatoms of Rf base is 4 or 6 material, or the mixture of above-mentioned substance.
3. fluoropolymer as claimed in claim 1, wherein, described nitrogen containing monomer (b) is 2-acrylamide-2-methyl propane sulfonic acid.
4. fluoropolymer as claimed in claim 1, wherein, the amount of described nitrogen containing monomer (b) is 10 weight parts～30 weight parts.
5. agent composition, this agent composition contains following (1) and (2), and described (1) is the described fluoropolymer of claim 1, and described (2) are liquid medium.
6. agent composition as claimed in claim 5, wherein, described liquid medium (2) is organic solvent or water.
7. agent composition as claimed in claim 5, this agent composition are the paper treatment agent.
8. the treatment process of a base material, this treatment process adopt the described agent composition of claim 5 that solid substrate is handled.
9. treatment process as claimed in claim 8, wherein, described base material is paper or masonry.
10. base material, this base material adopt the described treatment process of claim 8 to handle.
11. the described polymkeric substance of claim 1 is in the oleophobic property of solid substrate and the application in the hydrophobicity processing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004119793 | 2004-04-15 | ||
| JP119793/2004 | 2004-04-15 | ||
| JP348284/2004 | 2004-12-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1942494A CN1942494A (en) | 2007-04-04 |
| CN100475867C true CN100475867C (en) | 2009-04-08 |
Family
ID=37959794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800112218A Active CN100475867C (en) | 2004-04-15 | 2005-04-13 | Fluorine-containing polymer and treating agent composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100475867C (en) |
| TW (1) | TW200606181A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896515A (en) | 2007-12-13 | 2010-11-24 | 大金工业株式会社 | Fluorine-containing polymer and aqueous treatment agent |
| CN102264858A (en) * | 2009-01-07 | 2011-11-30 | Agc清美化学股份有限公司 | Resin adhesion inhibitor for electronic components, and electronic member and electronic component comprising same |
| FR2986004B1 (en) * | 2012-01-25 | 2014-03-14 | Seppic Sa | NOVEL THICKENING POLYMER THAT REDUCES THE TACKING CHARACTER OF GLYCERINE COSMETIC FORMULAS |
-
2005
- 2005-04-13 CN CNB2005800112218A patent/CN100475867C/en active Active
- 2005-04-15 TW TW094111976A patent/TW200606181A/en unknown
Non-Patent Citations (2)
| Title |
|---|
| CN 1 003 791 A 1986.10.08 |
| JP 2003 246823 A 2003.09.05 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200606181A (en) | 2006-02-16 |
| CN1942494A (en) | 2007-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20070219331A1 (en) | Fluorine-Containing Polymer and Treating Agent Composition | |
| CN102762618B (en) | Water and oil resistant agent for paper and paper treatment process | |
| KR101728576B1 (en) | Water-resistant/oil-resistant agent composition, article treated with the composition, and processes for production of the composition and the article | |
| CN101983212B (en) | Fluorine-containing copolymer, paper processing agent, and coating film-forming agent for cosmetic preparation | |
| CN100577767C (en) | Surface-treating agent comprising fluoropolymer | |
| US5446118A (en) | Fluorinated acrylic monomers containing urethane groups and their polymers | |
| CA2771415C (en) | Copolymer, treatment agent for paper, and treated paper | |
| CN101273171B (en) | Treatment for paper and method for treatment of paper | |
| EP2206735B1 (en) | Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods | |
| CA2867281C (en) | Water-resistant/oil-resistant agent for paper | |
| CN101595142A (en) | Fluorinated copolymer that has excellent washing resistance and stain remover | |
| CN101289525A (en) | Detergent with | |
| CN100475867C (en) | Fluorine-containing polymer and treating agent composition | |
| CN101238158B (en) | Repellent composition containing graft copolymer, graft copolymer and method of preparing graft copolymer | |
| US20050234205A1 (en) | Copolymer, paper-treating agent, and processed paper | |
| CA2861623A1 (en) | Method of preparing a treated article and treated article formed therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |