CN103242553A

CN103242553A - Surface modification method and surface modified elastomer

Info

Publication number: CN103242553A
Application number: CN2013100299875A
Authority: CN
Inventors: 皆川康久
Original assignee: Sumitomo Rubber Industries Ltd
Current assignee: Sumitomo Rubber Industries Ltd
Priority date: 2012-02-01
Filing date: 2013-01-25
Publication date: 2013-08-14
Anticipated expiration: 2033-01-25
Also published as: JP2013159629A; JP5763564B2; CN103242553B

Abstract

The present invention aims to provide a surface modification method of a vulcanized rubber or a thermoplastic elastomer, which can be economically and advantageously given functionalities, such as sliding performance, biocompatibility, etc., according to uses. The present invention relates to the surface modification method of taking the vulcanized rubber or the thermoplastic elastomer as a surface modification object, and the method comprises a step 1 of forming photopolymerization point on the surface of the surface modification object, and a step 2 of growing a non-functionality polymeric chain via a free radical polymerization non-functionality monomer by taking the above photopolymerization point as a starting point, and further growing a functionality polymeric chain via a free radical polymerization functionality monomer.

Description

The elastomerics of surface modifying method and surface modification

Technical field

The present invention relates to a kind of method of surface modification, and the syringe with modified surface that at least a portion obtains by this method of modifying with gasket seal, have the surface modified elastic body of the tire etc. of at least a portion tire rooved face.

Background technology

Keep the part of sealed state and slip, for example the gasket seal of syringe is integrated with the plunger of syringe, sealed plunger and syringe cylinder, and it payes attention to stopping property, used the elastomerics of rubber etc., but there are a little problems (referring to Patent Document 1) in sliding.Therefore at the slip modifying agent of slipping plane coating silicone wet goods, but silicone oil is pointed out the biotechnological formulation to nearest listing bad influence may be arranged.On the other hand, because it is poor not to be coated with the gasket seal sliding of sliding modifying agent, depression of plunger and produce vibrations successfully in the time of administration, it is incorrect to produce injection rate, brings the problem of misery etc. to the patient.

In order to satisfy the requirement opposite with sliding of such a stopping property, proposition coats the technology (referring to Patent Document 2) of the PTFE film with self-oilness, but usually owing to high price, and manufacturing cost rising, the range of application of fabricated product are restricted.In addition, the goods that coat the PTFE film be applicable to slide repeatedly etc. require the purposes of weather resistance the time, credible unstable sometimes.Further, because PTFE radioresistens not, the problem that can not sterilize by illuminated line is arranged.

In addition, also consider the purposes that is applied to other, require the sliding in the presence of water.That is, the fluid resistance that the syringe cylinder internal surface of precharging type syringe or be used for transports the internal surface of the pipe of water or tube (tube) descends, or increases or reduce to transport significantly losslessly water with the contact angle of water.The fluid resistance of the rooved face by making tire descends, or increases with the contact angle of water, perhaps significantly reduces, and draining or row's snow on wetland or snow road surface are good, and the result has improved adherence properties, skidding property of moisture-resistant road, has improved security.By the sidewall face of minimizing tire or the sliding resistance of buildings wall, or the contact angle of raising and water, also can expect to make rubbish or dust be difficult to adhere to.

Further can also expect following etc. favourable effect, the pressure-losses when using the barrier film fluming water of surge pump, diaphragm valve etc. or the aqueous solution etc. diminishes.The sliding of the planing surface by improving the two plates of skiing or skiing veneer, making slides becomes easy.By the sliding that improves way mark or signboard snow is slided easily, make sign become easier and see.By reducing the sliding resistance of outboard perimeter surface, or the contact angle of increase and water, make outer surface be difficult to particle-bound bacteria in the time of the resistance of minimizing water.The sliding on the surface by improvement swimming suit yarn reduces the resistance of water.

[prior art document]

[patent documentation]

Patent documentation 1: the Japanese Patent spy opens the 2004-298220 communique

Patent documentation 2: the Japanese Patent spy opens the 2010-142537 communique

Summary of the invention

[problem that invention will solve]

The surface modifying method that the purpose of this invention is to provide a kind of vulcanized rubber or thermoplastic elastomer solves above-mentioned problem, according to purposes, advantageously gives all functional of vulcanized rubber or thermoplastic elastomer sliding, biocompatibility etc. economically.In addition, the object of the invention also is to provide a kind of syringe gasket seal with modified surface that at least a portion obtains by this method of modifying, has the surface modified elastic body of the tire etc. of at least a portion tire rooved face.

[solving the means of problem]

The present invention relates to vulcanized rubber or the thermoplastic elastomer surface modifying method as the modification object, it comprises following operation: form the operation 1 that polymerization causes point on the surface of above-mentioned modification object, be starting point with causing point with above-mentioned polymerization, the radical polymerization of non-functional monomer, make the growth of non-functional polymer chain, further, functional monomer radical polymerization makes the operation 2 of functional polymer chain growth.

The surface of the preferred above-mentioned modification object of LED rayed with 300 ~ 400nm of above-mentioned operation 1 forms the operation that the polymerization initiation is put by above-mentioned lip-deep photosensitizers; It is starting point that above-mentioned operation 2 preferably causes point with above-mentioned polymerization, and the radical polymerization of non-functional monomer makes the growth of non-functional polymer chain, and further, functional monomer radical polymerization makes the operation of functional polymer chain growth.

Above-mentioned vulcanized rubber or thermoplastic elastomer are preferred, and having in abutting connection with the carbon atom of two keys is the material of allyl group position carbon atom.

As above-mentioned photosensitizers, the benzophenone based compound of preferred following formula (1) expression.

[changing 1]

(R in the formula (1) ¹~ R ⁵And R ^{1 '}~ R ^5'Expression hydrogen atom, alkyl, halogen, hydroxyl, primary ~ tertiary amine groups, sulfydryl, it perhaps also can be the alkyl that contains Sauerstoffatom, nitrogen-atoms or sulphur atom, they can be identical or different, adjacent any two can be interconnection, they also can form ring structure with the carbon atom of phase bonding.）

Above-mentioned operation 2 is fashionable at the radical polymerization of above-mentioned non-functional monomer and/or above-mentioned functions monomer, preferably adds reductive agent or antioxidant.Herein, as above-mentioned reductive agent or antioxidant, the preferred use is selected from least a in the group that riboflavin, xitix, alpha-tocopherol, β-Hu Luobusu and uric acid form.

Above-mentioned surface modifying method, preferably when above-mentioned rayed or pre-irradiation in reaction vessel and reaction liquid, import non-active gas, with its displacement polymerization in the non-active gas atmosphere.

Above-mentioned non-functional monomer is preferably selected from least a in the group that vinylformic acid, acrylate, alkali metal salts of acrylic acids, vinylformic acid amine salt, methacrylic acid, methacrylic ester, methacrylic acid alkali metal salt, methacrylic acid amine salt and vinyl cyanide form.

The above-mentioned functions monomer, preferred fluorochemical monomer.Herein, as above-mentioned fluorochemical monomer, the preferred use contains the fluoro-alkyl monomer.

The above-mentioned monomer that contains the fluoro alkyl is preferably selected from

vinylformic acid

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-21 fluorine dodecyl ester (H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₉CF ₃),

vinylformic acid

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine ester in the last of the ten Heavenly stems (H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₇CF ₃), vinylformic acid-3-(perfluoro butyl)-2-hydroxypropyl acrylate (F (CF ₂) ₄CH ₂CH (OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-perfluoro hexyl-2-hydroxypropyl acrylate (F (CF ₂) ₆CH ₂CH (OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF (CF ₂) ₂CH ₂CH (OH) CH ₂OCOCH=CH ₂) and vinylformic acid-3-(perfluor-5-methyl hexyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF (CF ₂) ₄CH ₂CH (OH) CH ₂OCOCH=CH ₂) group that forms at least a.

As the above-mentioned monomer that contains the fluoro alkyl, also suit to use the compound of following formula (3), (4), (5) or (6).

[changing 2]

(R ³¹Expression hydrogen, methyl, ethyl or propyl group.R ³²Expression-O-,-NH-.R ⁴¹Expression methylene radical, ethylidene or propylidene.R ⁵¹The expression ketone group can not exist yet.W1 represents 1 ~ 100 integer.Z represents 1 ~ 6 integer.）

[changing 3]

(R ³¹Expression hydrogen, methyl, ethyl or propyl group.W2 represents 4 ~ 10 integer.Z represents 1 ~ 6 integer.）

[changing 4]

(R ³¹Expression hydrogen, methyl, ethyl or propyl group.W3 and w4 represent 1 ~ 6 integer independently of one another.Z represents 1 ~ 6 integer.）

[changing 5]

(R ³¹Expression hydrogen, methyl, ethyl or propyl group.W3 and w4 represent 1 ~ 6 integer independently of one another.Z represents 1 ~ 6 integer.α represents 0 ~ 2 integer.）

Above-mentioned fluorochemical monomer, preferred fluoro alkylidene group or fluoro benzyl monomer.

The suitable use of described fluorochemical monomer is selected from by ［ 1H; 1H-perfluor (2; 5-dimethyl-3; 6-two oxa-nonanoyl) ］ acrylate, ［ 1H, 1H-perfluor (2,5-dimethyl-3; 6-two oxa-nonanoyl) ］ methacrylic ester, vinylformic acid PFBBR ester, methacrylic acid PFBBR ester and methacrylic acid-2; at least a kind of the group that 3,5,6-tetrafluoro phenylester is formed.

As the above-mentioned functions monomer, the zwitterionic monomer that contains carboxylic acid beet base, sulphonic acid betaine base or phosphoric acid betaine base in the side chain is also suitable.In addition, as the above-mentioned functions monomer, the suitable 2-(methyl that is selected from) acryloxy ethyl Phosphorylcholine, 2-(methyl) acryloxy ethyl carboxylic acid trimethyl-glycine and 2-(methyl) at least a in the group that forms of acryloxy ethylsulfonic acid trimethyl-glycine.Further, the preferred vinylformic acid silver of above-mentioned functions monomer and/or methacrylic acid silver.

Above-mentioned surface modifying method, preferred above-mentioned non-functional, above-mentioned functions monomer (liquid) or their solution contain stopper, polymerization in the presence of this stopper.Herein, the 4-methylphenol is suitable to above-mentioned stopper.

Preferred 10 ~ the 50000nm of length of the whole polymer chain that above-mentioned non-functional polymer chain and above-mentioned functions polymer chain are combined into.

The length of above-mentioned non-functional polymer chain and above-mentioned functions polymer chain is than preferred 50:50 ~ 99.9:0.01.

The present invention relates to the surface modified elastic body that obtains by above-mentioned surface modifying method.

The present invention relates to the surface modified elastic body that obtains by above-mentioned surface modifying method, it requires in the presence of the water or the sliding under the drying regime, low frictional properties or low water resistance.

The invention still further relates to the surface modified elastic body of at least a portion of the solid surface by above-mentioned surface modifying method modified 3 D shape.Herein, above-mentioned surface modified elastic body preferred polymers brush.

The present invention relates to a kind of syringe gasket seal that has by at least a portion of above-mentioned surface modifying method modified surface.

The invention still further relates to the tire of at least a portion of a kind of rooved face with the tire by above-mentioned surface modifying method modification.

The effect of invention

According to the present invention, owing to comprise the surface modifying method of following operation, namely form the operation 1 that polymerization causes point on the surface of vulcanized rubber or thermoplastic elastomer (modification object), be starting point with causing point with above-mentioned polymerization, the non-functional monomer is grown to the non-functional polymeric chain through radical polymerization, further, functional monomer is grown to the operation 2 of functional polymerization chain through radical polymerization, thereby the polymer layer that the most surperficial formation of polymer chain is made of the functional polymer chain can be given desirable function thus.In addition, other parts of polymer chain form the polymer layer that is made of the non-functional polymer chain, and are therefore also favourable economically.

Description of drawings

Fig. 1 is the example that syringe is used the side elevational view of gasket seal embodiment.

Fig. 2 is an example of the tread portion stretch-out view of pneumatic tyre (integral body does not illustrate).

Fig. 3 is an example of the sectional view of Fig. 2.

[nomenclature]

1 gasket seal

11a, 11b, 11c circular protrusion part

The surface of 13 bottoms

2 tread portions

3a central authorities pod

3b tire shoulder pod

5 strias

6 intermediate, inclined grooves

7 connective slots

8,8a, 8b tire shoulder translot

Embodiment

The present invention relates to a kind of with vulcanized rubber or the thermoplastic elastomer surface modifying method as the modification object, it comprises following operation: form the operation 1 that polymerization causes point on the surface of above-mentioned modification object, be starting point with causing point with above-mentioned polymerization, the non-functional monomer is grown to the non-functional polymeric chain through radical polymerization, further, functional monomer is grown to the operation 2 of functional polymerization chain through radical polymerization.

Usually in order to form polymer chain at concavo-convex big vulcanized rubber or the surface of thermoplastic elastomer, give functional, need form the approximately polymer chain of certain height (length) from its surface, expose the functional polymer chain from the surface, but because the common high price very of functional monomer, thereby do not keep bringing into play the MIN words of the polymer chain amount of functional requisite, unfavorable economically.Given this, the present invention is such surface modifying method: at first form polymer chain on modification object surface by cheap non-functional monomer, make up foothold in a way, the polymerizable functional monomer makes up the MIN functional polymer chain that needs on it, thereby at the most surperficial formation functional polymer layer.Thereby can provide the surface modified elastic body of the desirable function of having given sliding, biocompatibility, germ resistance etc. very economically.

For example, contain the monomer of fluoro-alkyl, because surface free energy is low, it is used as functional monomer, by at the most surperficial formation functional polymer chain, make the high surface of sliding.In addition, have the functional monomer of carboxylic acid beet base, sulphonic acid betaine base, phosphoric acid betaine base (phosphatide base) in the side chain, owing to have biocompatibility, can prevent absorption of proteins or aggegation in the biotechnological formulation.Further, contain the germ resistance material with silver etc. in the side chain, can bring into play anti-microbial effect.

The surface of the thermoplastic elastomer (modification object) of operation 1 after the rubber behind the vulcanization forming or shaping forms polymerization and causes point.

Above-mentioned vulcanized rubber or above-mentioned thermoplastic elastomer, suitable use have in abutting connection with the material of the carbon atom (allyl group position carbon atom) of two keys.

Rubber as the modification object, can enumerate, the diene series rubber of styrene butadiene ribber, divinyl rubber, synthetic polyisoprene, natural rubber, DPNR etc., and contain the isoprene unit of hundreds of proportions by subtraction as the isoprene-isobutylene rubber of degree of unsaturation, halogenated butyl rubber etc.Under the situation of isoprene-isobutylene rubber, halogenated butyl rubber, consider from the angle that the extract of vulcanized rubber tails off, preferably by triazine crosslinked rubber.At this moment, sour accepting agent can be contained, as suitable sour accepting agent, sulfuric acid magnalium, magnesiumcarbonate can be enumerated.

In the time of other rubber, preferably use sulfur vulcanization.At this moment, also can add mixture with the general vulcanization accelerator that uses of sulfur vulcanization, zinc oxide, packing material, silane coupling agent.As packing material, suitable carbon black, silicon-dioxide, clay, talcum powder, the calcium carbonate etc. of using.

In addition, the cure conditions of rubber can suitably be set, and the curing temperature of rubber is preferred more than 150 ℃, and is more preferably more than 170 ℃, further preferred more than 175 ℃.

As thermoplastic elastomer, can enumerate as, bring into play the effect of cross-linking set by the assembly of plasticity-composition (hard segment), and has the macromolecular compound (thermoplastic elastomer of styrene butadiene styrene copolymer etc. (TPE) etc.) of caoutchouc elasticity at normal temperatures, macromolecular compound with caoutchouc elasticity, by mixture heat plasticity composition and rubber components, carry out dynamic crosslinking by linking agent and obtain (containing styrene block copolymer or ethylene series resin, with thermoplastic elastomer (TPV) of polymer alloy of crosslinked rubber constituent etc. etc.).

In addition, as other suitable thermoplastic elastomer, can enumerate nylon, polyester, urethane, polypropylene and their dynamic crosslinking thermoplastic elastomer.The dynamic crosslinking thermoplastic elastomer preferably carries out the dynamic crosslinking halogenated butyl rubber and obtains in thermoplastic elastomer.The thermoplastic elastomer of this moment, preferred nylon, urethane, polypropylene, SIBS(vinylbenzene-different ethene-styrene block copolymer).

Polymerization causes point, forms by for example surface adsorption photosensitizers at the modification object.As photosensitizers, can enumerate as, the organosulfur compound of carbonyl compound, Thiuram disulfide etc., persulfide, redox based compound, azo-compound, diazonium compound, halogenated compound, photoreduction pigment etc., wherein preferred carbonyl compound.

As the carbonyl compound of photosensitizers, preferred benzophenone and derivative thereof, for example suitable benzophenone based compound that uses following formula (1) expression.

[changing 6]

R in the formula (1) ¹~ R ⁵And R ¹' ~ R ⁵' expression hydrogen atom, alkyl, halogen (fluorine, chlorine, bromine, iodine), hydroxyl, primary ~ tertiary amine groups, sulfydryl or also can be the alkyl that contains Sauerstoffatom, carbon atom or sulphur atom, they are identical or different, adjacent any two interconnection, they also can form ring structure with the carbon atom of phase bonding.

Object lesson as the benzophenone based compound, can enumerate benzophenone, xanthone, 9-Fluorenone, 2,4-dichloro benzophenone, methyl o-benzoylbenzoate, 4,4'-two (dimethylamine) benzophenone, 4,4'-two (diethylamine) benzophenone etc.Wherein, consider preferred especially benzophenone, xanthone, 9-Fluorenone from the angle that obtains polymer brush well.

As the benzophenone based compound, also go for fluorine benzophenone based compound, can enumerate as, following formula represent 2,3,4,5,6-five fluorine benzophenone, ten fluorine benzophenone etc.

[changing 7]

The photosensitizers of benzophenone based compound etc. is adsorbed in the method on modification object surface, can uses known method.For example, for the benzophenone based compound, by be dissolved in the modified surface position of the solution-treated object that organic solvent obtains with the benzophenone based compound, make it be adsorbed in the surface, the evaporation drying organic solvent causes point thereby form polymerization as required.As surface treatment method, as long as can make the surface of modification object contact this benzophenone series compound solution, just there is no particular limitation, for example, can be suitable for coating, spray this benzophenone series compound solution, and it is medium to be soaked into this solution.Further, when only surface modification need be carried out in a part of surface, can only make a part of surface adsorption sensitizing agent that needs, at this moment, suit for example to be coated with this solution, to spray this solution etc.As above-mentioned solvent, can use methyl alcohol, ethanol, acetone, benzene, toluene, methyl ethyl ketone, ethyl acetate, THF etc., from the not swelling of modification object, drying, evaporate rapidly angle and consider preferred acetone.

In addition, preferably with the benzophenone series compound solution surface treatment is implemented at modification object position, behind the absorption photosensitizers, further used rayed, make the surface of itself and modification object carry out chemical bonding.For example, preferred 300 ~ 400 with wavelength 300 ~ 450nm(, more preferably 350 ~ 400nm) uviolizing makes the benzophenone based compound can be fixed in the surface.In above-mentioned operation 1 and this immobilization, the hydrogen of rubber surface is captured, and when the carbon atom of the C=O of benzophenone and the carbon atom of rubber surface formed covalent linkage, the hydrogen bond of being captured was incorporated on the Sauerstoffatom of C=O, formed C-O-H.In addition, this takes out H-H reaction and is undertaken by the hydrogen selectivity of the allyl group position of modification object, so rubber preferably contains the divinyl with allylic hydrogen, the material of isoprene unit.

[changing 8]

R: the alkyl of hydrogen or carbonatoms 1 ~ 4

Wherein, preferred, make this photosensitizers be adsorbed in the surface by the surface of handling the modification object with photosensitizers, then, with the surface after the LED photo-irradiation treatment of 300 ~ 400nm, thereby form polymerization starter; Especially preferred, by with the benzophenone series compound solution surface treatment being implemented on the surface of modification object, behind the absorption photosensitizers, use the surface after the LED photo-irradiation treatment of 300 ~ 400nm further, thereby make the photosensitizers of absorption and surface carry out chemical bonding.Herein, the LED light wavelength is suitably 355 ~ 380nm.

In the operation 2, causing point with above-mentioned polymerization is starting point, and the radical polymerization of non-functional monomer makes the growth of non-functional polymer chain, and further, functional monomer radical polymerization makes the functional polymer chain growth.Concrete, at first causing point with the polymerization that forms in the operation 1 is starting point, make the incompatible manufacturing non-functional of non-functional monomer radical polymerization polymer chain, then, further radical polymerization functional monomer on this non-functional polymer chain that obtains, prolong polymer chain manufacturing function polymer chain, thereby at the most surperficial formation functional polymer layer, make the surface modified elastic body.

The non-functional monomer of operation 2 refers to that for the manufacture of the monomer of non-functional polymer chain, this non-functional polymer chain does not have according to suitable functions of setting such as purposes.For example, when giving function such as modification object sliding, biocompatibility, germ resistance, the monomer of not giving these functions just belongs to this class, considers from viewpoints such as economy, can suitably select.On the other hand, functional monomer refers to make the monomer of the functional polymer chain of bringing into play desirable function, the monomer that contains fluoro-alkyl when giving sliding, zwitterionic monomer when giving biocompatibility, (methyl) vinylformic acid silver during endowing antibacterial etc. is equivalent to functional monomer.

The non-functional monomer, can suitably select with above-mentioned viewpoint, for example can use vinylformic acid, acrylate (methyl acrylate, ethyl propenoate etc.), alkali metal salts of acrylic acids (sodium acrylate, potassium acrylate etc.), vinylformic acid amine salt, methacrylic acid, methacrylic ester (methyl methacrylate, Jia Jibingxisuanyizhi etc.), methacrylic acid alkali metal salt (sodium methacrylate, methacrylic acid potassium etc.), methacrylic acid amine salt, vinyl cyanide etc.They may be used alone, used in two or more.

Functional monomer can suitably be selected according to purposes as above, for example can use fluorochemical monomer.As fluorochemical monomer, can enumerate as the fluoro-alkyl monomer.Contain the monomer of fluoro-alkyl, so long as have a compound of 1 free-radical polymerised group of vinyl etc. and at least 1 fluoro-alkyl just there is no particular limitation and can use.Herein, fluoro-alkyl refers to the group that at least one hydrogen atom of alkyl is replaced by fluorine atom, the fluoro-alkyl of further preferred carbonatoms 7 ~ 30, and preferred especially end has the fluoro-alkyl of the carbonatoms 7 ~ 30 of perfluoroalkyl.

The monomer that contains fluoro-alkyl, the ratio of fluorine atom amount is more than the 45 quality % with respect to the monomer molecule amount preferably in the monomer, more preferably more than the 50 quality %.

As the monomer that contains fluoro-alkyl, can suit to use A-B(A to represent that free-radical polymerised group, B represent fluoro-alkyl.) expression compound.For example following formula is represented.

[changing 9]

(in the formula, Ra represents hydrogen atom, methyl, ethyl or propyl group.A represents-O-,-NH-.B represents to have substituting group or does not have substituent alkylidene group or polyoxyalkylene, also can not exist.C represents ketone group, also can not exist.Rf represents to have substituting group or does not have substituent fluoro-alkyl.）

The carbonatoms of the alkylidene group that B represents is preferred 1 ~ 15, and polyoxyalkylene is (RO) _wThe material of expression, the carbonatoms of R is preferred 1 ~ 10, and polymerization degree w is preferred 1 ~ 150, and this alkylidene group and this polyoxyalkylene also can be to have substituent material.Further, the preferred end of Rf has the fluoro-alkyl of the carbonatoms 2 ~ 40 of perfluoroalkyl.Can be to have substituent material.Be not particularly limited as the substituting group among B and the Rf, can enumerate hydroxyl etc.

As the above-mentioned monomer that contains fluoro-alkyl, consider the compound of preferred following formula (2) expression from the angle of easy polymerization.

[changing 10]

(in the formula, R ²¹Expression hydrogen atom, methyl, ethyl or propyl group, R ²²The alkylidene group of expression carbonatoms 1 ~ 4, Rf represents that end has the fluoro-alkyl of the carbonatoms 7 ~ 30 of perfluoroalkyl.）

R ²¹Preferred hydrogen atom or methyl, R ²²The alkylidene group of preferred carbonatoms 1 ~ 3.In addition, the preferred end of Rf has the fluoro-alkyl of the carbonatoms 7 ~ 20 of perfluoroalkyl.

(methyl) acrylic compound of following formula (2-1)～(2-3) expression etc. is arranged for example as the suitable compounds of above-mentioned formula (2) expression.

[changing 11]

(in the formula, R ²³Expression hydrogen atom or methyl, k represents 7,8,9,10,11 or 12.）

As the object lesson of the monomer that contains fluoro-alkyl, can enumerate vinylformic acid 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-21 fluorine dodecyl ester (H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₉CF ₃), vinylformic acid 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine ester in the last of the ten Heavenly stems (H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₇CF ₃), methacrylic acid H ₂C=CHCO ₂CH ₂(CF ₂) ₉CF ₃, H ₂C=CHCO ₂CH ₂(CF ₂) ₇CF ₃, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-, 21 fluorine dodecyl esters, methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-, 17 fluorine esters in the last of the ten Heavenly stems, vinylformic acid-3-(perfluoro butyl)-2-hydroxypropyl acrylate (F(CF ₂) 4CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluoro hexyl)-2-hydroxypropyl acrylate (F(CF ₂) ₆CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF(CF ₂) ₂CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluor-5-methyl hexyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF(CF ₂) ₄CH ₂CH(OH) CH ₂OCOCH=CH ₂) etc.Wherein, low from surface free energy is that the good angle of sliding is considered, preferred vinylformic acid 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine ester in the last of the ten Heavenly stems (H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₇CF ₃), vinylformic acid-3-(perfluoro butyl)-2-hydroxypropyl acrylate (F(CF ₂) ₄CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluoro hexyl)-2-hydroxypropyl acrylate (F(CF ₂) ₆CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF(CF ₂) ₂CH ₂CH(OH) CH ₂OCOCH=CH ₂), vinylformic acid-3-(perfluor-5-methyl hexyl)-2-hydroxypropyl acrylate ((CF ₃) ₂CF(CF ₂) ₄CH ₂CH(OH) CH ₂OCOCH=CH ₂).These can use separately also can two or more and usefulness.

As containing the fluoro-alkyl monomer, can use the vinyl monomer that has fluoro-alkyl in the side chain, wherein the end of preferred side chain has fluoro-alkyl, has the monomer of oxyalkylene group near the position of two key sides.Concrete, can be suitable for the monomer as following formula (3) expression.

[changing 12]

In the formula (3), R ³¹Expression hydrogen, methyl, ethyl or propyl group.R ³²Expression-O-,-NH-.R ⁴¹Expression methylene radical, ethylidene, propylidene.R ⁵¹The expression ketone group can not exist yet.W1 represents 1 ~ 100 integer.Z represents 1 ~ 6 integer.）

In addition, as the monomer that contains fluoro-alkyl, also suit to use the compound of following formula (4), (5), (6) expression.

[changing 13]

(in the formula (4), R ³¹Expression hydrogen, methyl, ethyl or propyl group.W2 represents 4 ~ 10 integer.Z represents 1 ~ 6 integer.）

[changing 14]

(in the formula (5), R ³¹Expression hydrogen, methyl, ethyl or propyl group.W3 and w4 represent 1 ~ 6 integer independently of one another.Z represents 1 ~ 6 integer.）

[changing 15]

(in the formula (6), R ³¹Expression hydrogen, methyl, ethyl or propyl group.W3 and w4 represent 1 ~ 6 integer independently of one another.Z represents 1 ~ 6 integer.α represents 0 ~ 2 integer.）

By with (R ⁴¹O) _W1, (CH ₂) _W2Deng the high structure of transport properties of molecules be positioned over, become the CH of main chain after the polymerization ₂=CR ³¹With (CF ₂) _zCF ₃The fluoropropenes acyloxy between, (CF ₂) _zCF ₃Base or CF ₃Base is easy to distribute unevenly under drying regime and concentrates on the surface, the angle that sliding improves, thereby preferred.In addition, but be placed on the CH that becomes main chain after the polymerization by the structure of hydrogen bonds with OH base, COOH base, C=O base, NH base etc. ₂=CR ³¹, with (CF ₂) _zCF ₃The fluoropropenes base between, thereby side chain is limited, (CF ₂) _zCF ₃Base or CF ₃Even base also is easy to be fixed in the surface or is easy to distribute unevenly and to concentrate on surface arrangement inhomogeneous in drying regime, sliding improves, thereby preferred.

Other object lesson as fluorochemical monomer; ［ the 1H that preferred following formula is represented; 1H-perfluor (2,5-dimethyl-3,6-two oxa-nonanoyl) ］ acrylate, ［ 1H; 1H-perfluor (2; 5-dimethyl-3,6-two oxa-nonanoyl) ］ methacrylic ester, vinylformic acid PFBBR ester, methacrylic acid PFBBR ester and methacrylic acid-2,3; 5,6-tetrafluoro phenylester.

[changing 16]

As functional monomer, can use the zwitterionic monomer (compound that contains the zwitter-ion group: the compound with permanent cationic species and anionic centers) of carboxylic acid trimethyl-glycine, sulphonic acid betaine, phosphoric acid betaine etc.From obtaining excellent sliding, weather resistance, and the angle that can keep good sealing property considers, as zwitterionic monomer, can use the compound of following formula (7) expression, wherein, and the suitable compound that uses following formula (8) expression.

[changing 17]

(in the formula, R ¹¹Expression-H-or-CH ₃, X represents-O-or NH-that m represents the integer more than 1, Y represents the zwitter-ion group.）

In the formula (7), R ¹¹Preferably-CH ₃, X is preferred-O-, and m preferred 1 ~ 10.In the zwitter-ion group that Y represents, the quaternary ammonium of tetraalkyl amine etc. can be enumerated as positively charged ion, carboxylic acid, sulfonic acid, phosphoric acid ester etc. can be enumerated as negatively charged ion.

[changing 18]

(in the formula, R ¹¹Expression-H-or-CH ₃, p and q represent the integer more than 1, Y ¹And Y ²Expression has the ionic functional group of opposite charges.

In the formula (8), the preferred integer more than 2 of p, more preferably 2～10 integer.The integer of q preferred 1～10, more preferably 2～4 integer.In addition, R ¹¹Preferably same as described above.Y ¹And Y ²Identical with above-mentioned positively charged ion, negatively charged ion.

As the suitable typical example of above-mentioned zwitterionic monomer, can enumerate the compound of following formula (8-1)～(8-4) expression.

[changing 19]

(in the formula, R ¹¹Expression hydrogen atom or methyl, p and q represent 1 ~ 10 integer.）

[changing 20]

[changing 21]

(in the formula, R ¹¹Expression hydrogen atom or methyl, R ¹²The alkyl of expression carbonatoms 1 ~ 6, p and q represent 1 ~ 10 integer.）

[changing 22]

(in the formula, R ¹¹Expression hydrogen atom or methyl, R ¹³, R ¹⁴, and R ¹⁵Represent the alkyl of carbonatoms 1 or 2, they can be identical or different, and p and q represent 1 ~ 10 integer.

Compound as above-mentioned formula (8-1) expression; can enumerate dimethyl (3-sulfopropyl) (2-(methyl) acrylyl oxy-ethyl) the ammonium trimethyl-glycine etc.; compound as formula (8-2) expression; can enumerate dimethyl (2-propyloic) (2-(methyl) acrylyl oxy-ethyl) the ammonium trimethyl-glycine etc.; compound as formula (8-3) expression; can enumerate dimethyl (3-methoxyl group sulfopropyl) (2-(methyl) acrylyl oxy-ethyl) the ammonium trimethyl-glycine etc.; as the compound of formula (8-4) expression, can enumerate the 2-(methyl) acryl oxygen ethyl sulphonyl choline etc.In addition, as zwitterionic monomer, can enumerate the 2-(methyl) acrylyl oxy-ethyl carboxylic acid trimethyl-glycine, the 2-(methyl) the acrylyl oxy-ethyl sulphonic acid betaine etc.Wherein, from the biocompatibility height, the angle that adsorption of protein is low is considered, preferred especially 2-(methyl) acrylyl oxy-ethyl sulphonyl choline.

As functional monomer, can enumerate vinylformic acid silver, methacrylic acid silver.By using such monomer, can form the polymer chain with germ resistance.

Non-functional monomer as operation 2, functional monomer free radical polymerisation process separately, by, absorption or covalent bonding benzophenone based compound etc. the modification object the surface or formed on the modification object of non-functional polymer chain, coating (spraying) non-functional monomer or functional monomer (liquid) or their solution, perhaps, this modification object or the modification object that formed the non-functional polymer chain are dipped in non-functional monomer or functional monomer (liquid) or their solution, rayed with ultraviolet ray etc., carry out radical polymerization (optical free radical polymerization) respectively, for this modification object surface, non-functional polymer chain, the functional polymer chain can be by such order growth.Further, after the above-mentioned coating, on the surface with coverings such as transparent glass, PET, polycarbonate, from rayed such as top usefulness ultraviolet rays, carry out radical polymerization (optical free radical polymerization) separately, for modification object surface, non-functional polymer chain, functional polymer chain also can be by such order growths.

Operation 2 has preferably been added reductive agent or antioxidant with rayed non-functional monomer or functional monomer carry out radical polymerization (optical free radical polymerization).At this moment, it is desirable to the interior oxygen of reductive agent or antioxidant top-up system.Added the monomer of reductive agent or antioxidant, composition separately can mix, and also can separate.In addition, after the modification object that operation 1 obtains has contacted the non-functional monomer, after the modification object that has perhaps formed the non-functional polymer chain has contacted functional monomer, further to wherein adding reductive agent, antioxidant, also can at first mix mentioned component, make mixing material contact this modification object or form the modification object of this non-functional polymer chain.

Concrete, operation 1 obtains passes through photosensitizers and forms the modification object that polymerization causes point on the surface, having added the solution contact back of reductive agent or antioxidant in nand function monomer (liquid) or their solution (soaks, coating etc.), perhaps, this modification object nand function monomer (liquid) or the contact of their solution, further, place thereon after the solution of reductive agent or antioxidant, carry out the rayed operation, then, for the modification object that has formed the non-functional polymer chain, functions of use monomer (liquid) or their solution, the solution of reductive agent or antioxidant carries out same operation etc., thereby implement radical polymerization respectively, form the non-functional polymer chain according to priority, the functional polymer chain.

For example, because it is bigger than 1 to contain the proportion of monomer of fluoro-alkyl, also do not mix mutually with water, so reductive agent or antioxidant solution are isolated in free radical polymerization monomer (liquid) or their solution upper strata.

There is no particular limitation as reductive agent, antioxidant, can suit to use the compound of such effect.Can enumerate Vitamin A class, its derivative and salt thereof as Vogan-Neu, dehydroretinol, Vitamin A1 acetate, hexadecanoic acid Vogan-Neu, retinene, vitamin A acid, Vitamin A wet goods; Carotenoids and derivatives thereof such as alpha-carotene, β-Hu Luobusu, gamma carotene, cryptoxanthin, astaxanthin, black wrack xanthin; Vitamin b6 usp category-B, its derivative and the salt thereof of pyridoxol, pyridoxal, pyridoxal 5-phosphate ester, Pyridoxylamine etc.; Vitamin C class, its derivative and salt thereof such as xitix, sodium ascorbate, ascorbyl stearate, Quicifal, Vitamin C dipalmitate, magnesium ascorbyl phosphate;

Ergocalciferol, cholecalciferol, 1,2, vitamin D class, its derivative and salt thereof such as 5-dihydroxyl cholecalciferol; Vitamin E class, its derivative and salt thereof such as alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol, alpha-tocotrienol, β-tocotrienols, γ-tocotrienols, δ-tocotrienols, tocopherol acetate, tocopheryl nicotinate; Quino dimethacrylate (Trolox), its derivative and salt thereof; Orcin, butylhydroxy toluene, butyl hydroxyanisole, butylated hydroxytoluene, alpha-lipoic acid, dehydrogenation Thioctic Acid, gsh, its derivative and salt thereof; Saccharosonic acid, its derivative and salt thereof such as uric acid, saccharosonic acid, SODIUM ISOVITAMIN C; Gallic acid such as gallic acid, Tenox PG, its derivative and salt thereof; Violaguercitrin, its derivative and salt thereof such as violaguercitrin, alpha-glycosyl violaguercitrin;

Tryptophane, its derivative and salt thereof; Histidine and derivative thereof and salt thereof; Cysteine derivative and salt thereof such as N-acetylcysteine, N-ethanoyl homocysteine, N-capryloyl halfcystine, N-acetylcysteine methyl esters; N, N '-diacetyl cystine dimethyl, N, N '-two capryloyl cystine dimethyl, N, cystine derivatives and salt thereof such as N '-two capryloyl homocystine dimethyl ester; Carnosine, its derivative and salt thereof; Homocarnosine, its derivative and salt thereof; Anserine, its derivative and salt thereof; β-alanyl histamine (carcinine), its derivative and salt thereof;

The dipeptides or tripeptide derivative and the salt thereof that contain Histidine and/or tryptophane and/or histamine; The flavonoid class of flavanone, flavones, cyanin, anthocyanidin, flavonol, Xanthaurine, Quercitroside, ampelopsin, fisetin, Hamamelitannin, catechin, l-Epicatechol, l-Epigallocatechol, epigallocatechin, L-Epicatechin gallate, NVP-XAA 723 etc.;

Weibull; coffic acid; forulic acid; Protocatechuic Acid; phenyl styryl ketone; thiaminogen; carnosol; sesamol; sesamin; sesamolin; zingiberone; curcumine; tetrahydro curcumin; 3-(3; the 4-dihydroxyphenyl)-2-[(3-(3; the 4-dihydroxyphenyl) propionic acid (clovamide) acrylamido)]; deoxidation 3-(3; the 4-dihydroxy phenyl)-(3-(3 for 2-; the 4-dihydroxy phenyl) propionic acid (deoxyclovamide) acrylamido); salad oil; capsaicine; the vanilla acid amides; ellagic acid; bromophenol; flavoglaucin; melanoidin; riboflavin; Riboflavine Tertrabutyrate; vitamin B2 phosphate; flavin adenine Nucleotide; ubiquinone; panthenol; N.F,USP MANNITOL; bilirubin; cholesterol; ebselen; Sethotope; copper-protein; Transferrins,iron complexes; lactoferrin; albumin; superoxide dismutase; catalase; glutathione peroxidase; metallothionein(MT), the inferior pyridine alcohol of O-phosphono rhodamine etc.They can use or make up two or more uses separately.

Wherein, consider preferred riboflavin, xitix, alpha-tocopherol, β-Hu Luobusu, uric acid, preferred especially riboflavin, xitix from the reason that the additional energy of oxygen is high.

When using the solution of reductive agent, antioxidant, the concentration of this reductive agent, antioxidant preferred 1 ^-41 quality %, more preferably 10 ^-3~ 0.1 quality %.

In addition, the usage quantity of free radical polymerization monomer can be according to the length of the polymer chain that forms, the suitable settings such as performance of its chain performance.Further, also can consider from the angle of the additional grade of oxygen in the system, suitably set the usage quantity of reductive agent, antioxidant.

Coating (spraying) solvent, coating (spraying) method, immersion process, illuminate condition etc. can use material known and method in the past.In addition, as the solution of free radical polymerization monomer, use the aqueous solution or be dissolved in the solution that the organic solvent that do not dissolve employed photosensitizers (benzophenone based compound etc.) obtains.In addition, free radical polymerization monomer (liquid) as its solution, can use the known stopper of 4-methylphenol etc.

Among the present invention, behind coating monomer (liquid) or their solution, after perhaps soaking monomer or solution, carry out the radical polymerization of non-functional monomer, functional monomer respectively by rayed, the main suitable UV radiation source that uses high pressure mercury vapour lamp with ultra-violet light-emitting wavelength, metal halide lamp, LED lamp etc.Consider the homogeneity that polymerization time or reaction are carried out, can suitably set the irradiation light quantity.In addition, for the reactive gas that prevents the oxygen etc. in the reaction vessel hinders polymerization, preferably when rayed or before the rayed, remove in the reaction vessel or the oxygen in the reaction solution.Therefore, the suitable non-active gas that imports nitrogen or argon gas etc. in reaction vessel or in the reaction solution is discharged the reactive gas of oxygen etc. outside the reaction system, will be replaced as non-active gas atmosphere etc. in the reaction system.Further, react in order to prevent obstructions such as oxygen, the UV radiation source is arranged at the inaccessiable position of gas cloud (oxygen content is more than 15%), this position is between the reaction vessel and reaction solution or modification object of glass or plastics etc.

In the time of irradiation ultraviolet radiation, the preferred 300 ~ 450nm of its wavelength, more preferably 300 ~ 400nm.Like this, the surface energy of modification object forms polymer chain well.Can use high pressure mercury vapour lamp or have the centre wavelength of 365nm LED, have the LED etc. of centre wavelength of 375nm as light source.Wherein, preferably shine the LED light of 300 ~ 400nm, more preferably shine the LED light of 355 ~ 380nm.Especially, consider the LED that preferably has the centre wavelength of the 365nm close with the excitation wavelength 366nm of benzophenone from the angle of efficient.

In addition, as the polymer chain that operation 2 forms, the material that the monomer polymerization that contains fluoro-alkyl of preferred above-mentioned formula (2) expression forms.Like this, just can obtain excellent sliding, weather resistance, and can keep good sealing property.The polymerization degree of the polymer chain that forms is preferred 20 ~ 200000, and more preferably 350 ~ 50000.

Preferred 10 ~ the 50000nm of length of the whole polymer chain that the non-functional polymer chain that operation 2 forms and functional polymer chain are combined into, more preferably 100 ~ 50000nm.During deficiency 10nm, the tendency that can not obtain good sliding is arranged.When surpassing 50000nm, can not expect that sliding further improves, because the tendency of using the monomer of high price to have raw materials cost to rise, as seen the picture on surface that forms by surface treatment becomes naked eyes in addition, have diminish attractive in appearance, the tendency that stopping property descends.

In the whole polymer chain that operation 2 forms, the length of non-functional polymer chain and functional polymer chain is than (the length of non-functional polymer chain: the length of functional polymer chain) preferred 50:50 ~ 99.9:0.01, more preferably 90:10 ~ 99.5:0.5.During functional polymer chain less than 1%, may not give desirable function, surpass at 50% o'clock, disadvantageous tendency is economically arranged.

In the above-mentioned operation 2, cause point as starting point with polymerization, the two or more non-functional monomer of radical polymerization simultaneously in addition also can the two or more functional monomer of while radical polymerization.Further, non-functional, functional polymer chain can be distinguished the two-layer above material of lamination.Further, the surface of the modification object plural polymer chain of can growing.Surface modifying method of the present invention also can make between polymer chain crosslinked.At this moment, between polymer chain, can form ionomer,, halogen group by iodine etc. crosslinked by the hydrophilic radical with Sauerstoffatom and crosslinked.

By vulcanized rubber or thermoplastic elastomer are suitable for above-mentioned surface modifying method, obtain the surface modified elastic body.For example, obtain water and exist down or the surface modified elastic body of the excellent in sliding property under the drying regime, it the resistance of low friction, water so less aspect performance excellent.In addition, at least a portion of the solid (elastomerics etc.) by aforesaid method being applicable to 3D shape obtains the elastomerics of the surface modification of modification.Further, as the preferred example of this surface modified elastic body, can enumerate polymer brush (polymer brush).Herein, polymer brush refers to, the meaning of the graftomer of the grafting form that forms by surperficial initiating activity radical polymerization.In addition, preferred grafted chain because Entropy Changes is little, the molecular motion step-down of grafted chain, can obtain sliding when the direction that is approximately perpendicular to modification object surface is directed.Further, as brush density, preferred 0.01chains/nm ²Above accurate concentration and concentration brush.

In addition, by vulcanized rubber or thermoplastic elastomer are suitable for above-mentioned surface modifying method, can make the syringe gasket seal with at least a portion modified surface.Modification, preferred at least in the slipper execution on gasket seal surface, also can implement on whole surface.

Fig. 1 is the example that syringe is used gasket seal embodiment side elevational view.Gasket seal 1 shown in Fig. 1, its with outer surface that perimeter surface in the injection tube of syringe contacts on, 3

continuous jut

11a, 11b, 11c are along the circumferential direction arranged.In the gasket seal 1, as the position that is applicable to above-mentioned surface modification, can enumerate the surface of the jut that contacts with syringe cylinder of (1)

circular protrusion part

11a, 11b, 11c etc., (2) contain whole side surfaces of

circular protrusion part

11a, 11b, 11c, the surface 13 of (3) these whole side surfaces and bottom etc.

Further, be suitable for above-mentioned surface modifying method on the groove that the tire tread that the vehicle of car etc. uses forms, by generating polymer brush at groove, rooved face descends for the fluid resistance of wet road surface or ice and snow road, become big with the contact angle of water, draining or row's snow improve, and adherence properties has improved.

Fig. 2 is an example of the tread portion stretch-out view of pneumatic tyre (integral body does not illustrate).One example of the A1-A1 sectional view of Fig. 3 presentation graphs 2.

In Fig. 2 ~ 3, central pod 3a(groove depth D1), tire shoulder pod 3b(groove depth D2) constituted by the straight trough along the circumferential linearly extension of tire.Such straight trough, resistance of water drainage is little, can bring into play high drainage performance during straight line moving.

In addition, pneumatic tyre is provided with, the stria 5(groove depth D3 along tire Zhou Fangxiang extension of tire shoulder pod 3b side), from then on stria 5 is to the intermediate, inclined groove 6(groove depth D4 of central pod 3a inclination extension), be positioned at than stria 5 more near the tire axial inboard, and with the connective slot 7(groove depth D5 that connects between the circumferential adjacent intermediate, inclined groove 6 of tire, 6), from tire shoulder translot 8,8a, the 8b(groove depth D6 of tire shoulder depth 3b outside tire), such a groove can be brought into play drainage performance.And, by being suitable for aforesaid method to these grooves, can bring into play above-mentioned effect.

[embodiment]

Following according to embodiment, the present invention is specifically described, but the present invention is not limited to this.

(embodiment 1)

With the triazine crosslinked chloroprene rubber (degree of unsaturation: 1 ~ 2%) obtain vulcanized rubber gasket seal (180 ℃ were vulcanized 10 minutes) that contains isoprene unit, this vulcanized rubber gasket seal is immersed in the acetone soln of 3wt% of benzophenone, vulcanising rubber surface absorption benzophenone, drying.Then, with the LED-UV rayed vulcanized rubber gasket seal surface with 365nm wavelength 10 minutes, after the chemical bonding benzophenone, with its surface of washing with acetone to remove unreacted benzophenone.Then, take out vulcanized rubber, drying.

Dried vulcanized rubber gasket seal is soaked in the glass reaction container that has added acrylic acid aqueous solution (vinylformic acid of 2.5M:18g is dissolved in the 100mL water), with the LED-UV rayed with 365nm wavelength 1 hour, carry out radical polymerization, at rubber surface growth non-functional polymer chain.Then, washing surface, dry.

Then, the polyacrylic vulcanized rubber gasket seal of will having grown is soaked into vinylformic acid 3-perfluoro hexyl-2-hydroxypropyl ester (ダイキ Application industry system: R1633) in the monomer solution (containing stopper).To wherein adding the riboflavin aqueous solution (concentration 1 * 10 ^-5Mol/L) (because the ratio of monomer liquid is great, monomer liquid does not mix mutually with the aqueous solution, forms the riboflavin aqueous layer at monomer liquid), with the LED-UV rayed with 365nm wavelength 16 hours, carry out radical polymerization, further at rubber surface growth functional polymer chain.Obtain surface modified elastic body (polymer brush of lamination) like this.

(embodiment 2)

Use 2-methylacryoyloxyethyl Phosphorylcholine to replace vinylformic acid 3-perfluoro hexyl-2-hydroxypropyl acrylate, making polymerization time is 10 hours, in addition identical with embodiment 1, obtains surface modified elastic body (polymer brush of lamination).

(embodiment 3)

Dried vulcanized rubber gasket seal is soaked in the glass reaction container that has added acrylic acid aqueous solution (vinylformic acid of 2.5M:18g is dissolved in the 100mL water), with have the 365nm wavelength LED-UV rayed 1 hour, carry out radical polymerization, at rubber surface growth non-functional polymer chain.Then, washing surface, dry.

Then, in the polyacrylic surface coated vinylformic acid 3-perfluoro hexyl-2-hydroxypropyl ester of having grown (ダイキ Application industry system: R1633) in the monomer liquid (containing stopper).This vulcanized rubber gasket seal is soaked into the riboflavin aqueous solution (concentration 1 * 10 ^-5MolL) in, with the LED-UV rayed 15 hours with 365nm wavelength, carry out radical polymerization, at rubber surface further growth polymer chain.Obtain surface modified elastic body (polymer brush of lamination) like this.

(embodiment 4)

Except vinylformic acid 3-perfluoro hexyl-2-hydroxypropyl ester is changed to

vinylformic acid

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, beyond the 10-17 fluorine esters in the last of the ten Heavenly stems, use method similarly to Example 3 to obtain surface modified elastic body (polymer brush of lamination).

(comparative example 1)

Use the chlorobutyl rubber (degree of unsaturation: the vulcanized rubber that 1 ~ 2%) obtains (180 ℃ were vulcanized 10 minutes) that contains isoprene unit with triazine crosslinked.

Estimate the surface modified elastic body of embodiment, comparative example manufacturing in order to following method.

(length of polymer chain)

The length of the polymer chain that forms about vulcanising rubber surface is used SEM, under acceleration voltage 15kV, 1000 times condition, the modified rubber cross section that is formed with polymer chain is measured.The thickness of the polymer layer of photography is the length of polymer chain.

(friction resistance)

In order to measure the surface friction drag of surface modified elastic body, the vulcanized rubber gasket seal of embodiment, comparative example manufacturing is fixed in the COP resin injector tube of syringe, be pressed into tensile testing machine, measure the friction resistance (press-in speed: 30mm/min) of this moment.Friction resistance with comparative example 1 is 100, uses following formula, represents the friction resistance index of each embodiment.Index is little, and expression friction resistance is low.

Friction resistance * 100 of friction resistance/comparative example 1 of (friction resistance index)=each embodiment

[table 1]

According to table 1 as can be known, the friction resistance of the surface modified elastic surface of embodiment declines to a great extent, and obtains good sliding.In addition, owing to be the material of modified surface only, stopping property is identical with comparative example 1.

Therefore, when being used in the gasket seal of syringe plunger, alleviated the frictional force of plunger for syringe cylinder when having guaranteed sufficient stopping property, can handle with syringe easily and exactly.In addition, because the difference of static friction coefficient and the coefficient of sliding friction is little, beginning plunger depressed and plunger enter action can not have vibrations smoothly.Further, with the syringe cylinder of thermoplastic elastomer making syringe, when internal surface is produced polymer chain, with the above-mentioned processing of similarly easily carrying out syringe.

In addition, by groove, sidewall, the barrier film that forms in the tire tread of uses such as car, the surface of the planing surface of skiing veneer or the two plates of skiing, swimming suit, way mark, signboard etc. forms polymer chain, also can expect above-mentioned effect.

Claims

1. surface modifying method is with vulcanized rubber or the thermoplastic elastomer surface modifying method as the modification object,

Comprise following operation,

Form the operation 1 that polymerization causes point on the surface of described modification object,

Be starting point with causing point with described polymerization, make the non-functional monomer carry out radical polymerization, make the growth of non-functional polymeric chain, further, make functional monomer carry out radical polymerization, make the operation 2 of functional polymerization chain growth.

2. surface modifying method as claimed in claim 1, described operation 1 is the surface with the described modification object of LED rayed of 300 ~ 400nm, forms the operation that polymerization causes point by described lip-deep photosensitizers,

Described operation 2 is to cause point as starting point with described polymerization, makes the non-functional monomer carry out radical polymerization, makes the growth of non-functional polymeric chain, further, makes functional monomer carry out radical polymerization, makes the operation of functional polymerization chain growth.

3. it is allyl group position carbon atom that surface modifying method as claimed in claim 1 or 2, described vulcanized rubber or thermoplastic elastomer have the carbon atom that is adjacent to two keys.

4. as each described surface modifying method of claim 1 ~ 3, described photosensitizers is the benzophenone based compound of following formula (1) expression,

In the formula (1), R ¹~ R ⁵And R ^{1 '}~ R ^{5 '}Identical or different, expression hydrogen atom, alkyl, halogen, hydroxyl, primary ~ tertiary amine groups, sulfydryl, perhaps expression contains or does not contain the alkyl of Sauerstoffatom, nitrogen-atoms or sulphur atom, adjacent any two interconnection, they form or do not form ring structure with the carbon atom of phase bonding.

5. as each described surface modifying method of claim 1 ~ 4, described operation 2 is fashionable at the radical polymerization of described non-functional monomer and/or described functional monomer, adds reductive agent or antioxidant.

6. surface modifying method as claimed in claim 5, described reductive agent or antioxidant are to be selected from least a in the group that riboflavin, xitix, alpha-tocopherol, β-Hu Luobusu and uric acid form.

7. as each described surface modifying method of claim 2 ~ 6, when described rayed or pre-irradiation in reaction vessel and reaction liquid, import non-active gas, it is replaced as non-active gas atmosphere, carry out polymerization.

8. as each described surface modifying method of claim 1 ~ 7, described non-functional monomer is to be selected from least a in the group that vinylformic acid, acrylate, alkali metal salts of acrylic acids, vinylformic acid amine salt, methacrylic acid, methacrylic ester, methacrylic acid alkali metal salt, methacrylic acid amine salt, vinyl cyanide forms.

9. as each described surface modifying method of claim 1 ~ 8, described functional monomer is fluorine-containing monomer.

10. surface modifying method as claimed in claim 9, described fluorine-containing monomer is the monomer that contains fluoro-alkyl.

11. surface modifying method as claimed in claim 10, the described monomer that contains fluoro-alkyl are to be selected from vinylformic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-21 fluorine dodecyl esters are H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₉CF ₃, vinylformic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine esters in the last of the ten Heavenly stems are H ₂C=CHCO ₂CH ₂CH ₂(CF ₂) ₇CF ₃, vinylformic acid-3-(perfluoro butyl)-the 2-hydroxypropyl acrylate is F (CF ₂) ₄CH ₂CH (OH) CH ₂OCOCH=CH ₂, vinylformic acid-3-perfluoro hexyl-2-hydroxypropyl acrylate is F (CF ₂) ₆CH ₂CH (OH) CH ₂OCOCH=CH ₂, vinylformic acid-3-(perfluor-3-methyl butyl)-i.e. (CF of 2-hydroxypropyl acrylate ₃) ₂CF (CF ₂) ₂CH ₂CH (OH) CH ₂OCOCH=CH ₂And vinylformic acid-3-(perfluor-5-methyl hexyl)-the 2-hydroxypropyl acrylate is (CF ₃) ₂CF (CF ₂) ₄CH ₂CH (OH) CH ₂OCOCH=CH ₂At least a in the group that forms.

12. surface modifying method as claimed in claim 10, the described monomer that contains fluoro-alkyl are the compound of following formula (3), (4), (5) or (6) expression,

R ³¹Expression hydrogen, methyl, ethyl or propyl group, R ³²Expression-O-,-NH-, R ⁴¹Expression methylene radical, ethylidene, propylidene, R ⁵¹Expression ketone group, perhaps R ⁵¹Do not exist, w1 represents 1 ~ 100 integer, and z represents 1 ~ 6 integer,

R ³¹Expression hydrogen, methyl, ethyl or propyl group, w2 represents 4 ~ 10 integer, z represents 1 ~ 6 integer,

R ³¹Expression hydrogen, methyl, ethyl or propyl group, w3 and w4 represent 1 ~ 6 integer independently of one another, z represents 1 ~ 6 integer,

R ³¹Expression hydrogen, methyl, ethyl or propyl group, w3 and w4 represent 1 ~ 6 integer independently of one another, and z represents 1 ~ 6 integer, and α represents 0 ~ 2 integer.

13. surface modifying method as claimed in claim 9, described fluorine-containing monomer are the monomers that contains fluoro alkylene oxide or fluoro benzyl.

14. surface modifying method as claimed in claim 9; described fluorine-containing monomer is to be selected from by ［ 1H; 1H-perfluor (2,5-dimethyl-3,6-two oxa-nonanoyl) ］ acrylate, ［ 1H; 1H-perfluor (2; 5-dimethyl-3,6-two oxa-nonanoyl) ］ methacrylic ester, vinylformic acid PFBBR ester, methacrylic acid PFBBR ester and methacrylic acid-2,3; at least a kind of the group that 5,6-tetrafluoro phenylester is formed.

15. as each described surface modifying method of claim 1 ~ 8, described functional monomer is the zwitterionic monomer that contains carboxybetaine base, sultaine base or phosphoric acid betaine base in the side chain.

16. as each described surface modifying method of claim 1 ~ 8, described functional monomer is to be selected from the 2-(methyl) acryloxy ethyl Phosphorylcholine, 2-(methyl) acryloxy ethyl carboxybetaine and 2-(methyl) at least a in the group that forms of acryloxy ethyl sultaine.

17. as each described surface modifying method of claim 1 ~ 8, described functional monomer is vinylformic acid silver and/or methacrylic acid silver.

18. as each described surface modifying method of claim 1 ~ 17, described non-functional, functional monomer (liquid) or their solution contain stopper, polymerization in the presence of this stopper.

19. surface modifying method as claimed in claim 18, described stopper are the 4-methylphenols.

20. as each described surface modifying method of claim 1 ~ 19, the length of the whole polymeric chain that described non-functional polymeric chain and described functional polymerization chain are combined is 10 ~ 50000nm.

21. as each described surface modifying method of claim 1 ~ 20, the length ratio of described non-functional polymeric chain and described functional polymerization chain is 50:50 ~ 99.9:0.01.

22. a surface modified elastic body, each the described surface modifying method by claim 1 ~ 21 obtains.

23. a surface modified elastic body, each the described surface modifying method by claim 1 ~ 21 obtains, and requires to have in the presence of water or the sliding under the drying regime, the low friction or low water resistance.

24. a surface modified elastic body, each the described surface modifying method by claim 1 ~ 21 obtains at least a portion modification of the solid surface of 3D shape.

25. as each described surface modified elastic body of claim 22 ~ 24, it is polymer brush.

26. a syringe gasket seal has at least a portion by the surface of each described surface modifying method modification of claim 1～21.

27. a tire has at least a portion by the rooved face of the tire of each described surface modifying method modification of claim 1～21.