JP6285233B2 - Surface modification method and surface modified elastic body - Google Patents

Description

The present invention relates to a surface modification method, and at least one of a gasket for a syringe and a syringe for syringe having at least part of a modified surface obtained by the modification method, a groove surface and / or a sidewall surface of a tire. The present invention relates to a surface-modified elastic body such as a tire in a part.

For parts that slide while maintaining a sealed state, for example, gaskets that are integrated with the plunger of a syringe and seal the plunger and syringe, the sealing property is emphasized, and an elastic body such as rubber is used. However, there is a slight problem in slidability (see Patent Document 1). For this reason, a sliding property improving agent such as silicone oil is applied to the sliding surface, but it has been pointed out that silicone oil may adversely affect biopharmaceuticals that have recently been put on the market. On the other hand, gaskets not coated with a slidability improver are inferior in slidability, causing pulsation without smoothly pushing the plunger during administration, resulting in inaccurate injection volume, causing pain to patients, etc. Problem arises.

In order to satisfy such contradictory requirements of sealability and slidability, a technique for coating a self-lubricating PTFE film has been proposed (see Patent Document 2). The manufacturing cost increases and the application range is limited. In addition, there is a concern about reliability when a product coated with a PTFE film is applied to an application in which durability is required due to repeated sliding and the like. Furthermore, since PTFE is vulnerable to radiation, there is also a problem that sterilization by radiation cannot be performed.

In addition, application to other uses that require slidability in the presence of water is also conceivable. That is, water can be sent without loss by lowering the fluid resistance of the syringe inner surface of the prefilled syringe and the inner surface of the tube or tube for feeding water, increasing the contact angle with water, or reducing it significantly. By reducing the surface resistance of the inner and outer surfaces of the catheter tube, the catheter can be easily inserted into the body, and the guide wire can be easily passed through the catheter. By reducing the fluid resistance on the groove surface of the tire, increasing the contact angle with water, or reducing it significantly, water and snow on wet and snowy road surfaces will be better, resulting in improved grip and hydroplaning. And safety is improved. It can also be expected that dust and dust are less likely to adhere by reducing the sliding resistance of the tire sidewall and building walls and increasing the contact angle with water.

Furthermore, pressure loss when water or an aqueous solution is sent by a diaphragm such as a diaphragm pump or a diaphragm valve is reduced. It becomes easy to slip by improving the slidability of the sliding surface of the ski or snowboard. Signs are easier to see by improving the slidability of road signs and billboards and making the snow more slippery. By reducing the sliding resistance of the outer peripheral surface of the ship or increasing the contact angle with water, the resistance of water is reduced and bacteria are less likely to adhere to the outer peripheral surface. It is also possible to expect advantageous effects such as reducing the water resistance by improving the sliding property of the yarn surface of the swimsuit.

JP 2004-298220 A JP 2010-142573 A

An object of the present invention is to solve the above-mentioned problems and to provide a surface modification method for a vulcanized rubber or a thermoplastic elastomer capable of economically and advantageously imparting various functions such as slidability depending on applications. And Further, a surface-modified elastic body such as a syringe gasket or syringe having at least a part of a modified surface obtained by the surface modification method, a tire having at least a part of a tire groove surface or a sidewall surface It is also intended to provide.

The present invention is a surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification target, the step 1 of forming a polymerization start point A on the surface of the modification target, and the polymerization start point A Step 2 is a process of growing a non-functional polymer chain by radical polymerization of a non-functional monomer starting from the above, and further growing a fluorine-containing urethane (meth) acrylate polymer chain by radical polymerization of a fluorine-containing urethane (meth) acrylate monomer. And a surface modification method comprising:

In the step 1, a photopolymerization initiator A is adsorbed on the surface of the object to be modified, or LED light of 300 to 400 nm is further irradiated to form a polymerization start point A from the photopolymerization initiator A on the surface. It is preferable that the

In the step 2, the non-functional monomer is radically polymerized by irradiation with LED light of 300 to 450 nm starting from the polymerization start point A to grow a non-functional polymer chain, and further a fluorine-containing urethane (meth) acrylate monomer It is preferable that the fluorine-containing urethane (meth) acrylate polymer chain is grown by radical polymerization by irradiation of 300 to 450 nm of LED light.

In the step 2, the non-functional monomer is radically polymerized by irradiation with 300 to 450 nm LED light starting from the polymerization start point A to grow a non-functional polymer chain, and then the surface of the non-functional polymer chain is formed. After photopolymerization initiator B is adsorbed or further irradiated with LED light of 300 to 400 nm to form polymerization start point B from photopolymerization initiator B on the surface, fluorine is contained starting from the polymerization start point B It is preferable that the urethane (meth) acrylate monomer is radically polymerized by irradiation with LED light of 300 to 450 nm to grow a fluorine-containing urethane (meth) acrylate polymer chain.

The present invention is also a surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification target, wherein a non-functional monomer is radicalized on the surface of the modification target in the presence of a photopolymerization initiator A. A step I of growing a non-functional polymer chain by polymerization and further radically polymerizing a fluorine-containing urethane (meth) acrylate monomer in the presence of the photopolymerization initiator B to grow a fluorine-containing urethane (meth) acrylate polymer chain. The present invention relates to a surface modification method including the same.

The vulcanized rubber or thermoplastic elastomer preferably has an allylic carbon atom that is a carbon atom adjacent to a double bond.
The photopolymerization initiators A and B are the same or different and are preferably a benzophenone compound and / or a thioxanthone compound.

The surface modification method is preferably polymerized in an inert gas atmosphere.
The surface modification method is preferably polymerized under vacuum degassing conditions.

The non-functional monomer includes acrylic acid, acrylic ester, acrylamide, alkali metal acrylate, amine acrylate, methacrylic acid, methacrylic ester, methacrylamide, alkali metal methacrylate, amine methacrylate, dimethylacrylamide , Diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, methoxymethylacrylamide, acryloylmorpholine, methoxymethyl acrylate, hydroxyethyl acrylate, dimethylmethacrylamide, diethylmethacrylamide, isopropylmethacrylamide, hydroxyethylmethacrylamide, methacryloylmorpholine, methoxymethylmethacrylate, Hydroxyethyl methacrylate and acrylonitrile Is preferably at least one selected from the group consisting of.

The fluorine-containing urethane (meth) acrylate monomer preferably has a fluoroalkyl ether group.

（式（１）中、Ｘは、同一又は異なって、ウレタン（メタ）アクリレート基を表す。ｐ、ｑは、同一又は異なって、１以上の整数を表す。） The fluorine-containing urethane (meth) acrylate monomer is preferably represented by the following formula (1).

(In formula (1), X is the same or different and represents a urethane (meth) acrylate group. P and q are the same or different and each represents an integer of 1 or more.)

The fluorine-containing (meth) acrylate monomer preferably has a polyfunctional (meth) acrylate group.
The fluorine-containing (meth) acrylate monomer preferably has 2 to 4 functional (meth) acrylate groups.

The non-functional, fluorine-containing urethane (meth) acrylate monomer (liquid) or a solution thereof contains a polymerization inhibitor and is preferably polymerized in the presence of the polymerization inhibitor. Here, the polymerization inhibitor is preferably 4-methylphenol.

It is preferable that the total polymer chain length including the non-functional polymer chain and the fluorine-containing urethane (meth) acrylate polymer chain is 10 to 50000 nm.
The length ratio of the non-functional polymer chain and the fluorine-containing urethane (meth) acrylate polymer chain is preferably 50:50 to 99.9: 0.1.

The present invention relates to a surface-modified elastic body obtained by the surface modification method.
The present invention relates to a surface-modified elastic body that is required to have slidability, low friction or low water resistance in the presence of water or in a dry state obtained by the surface modification method.

The present invention relates to a surface-modified elastic body in which at least a part of a three-dimensional solid surface is modified by the surface modification method.
The surface-modified elastic body is preferably a polymer brush.

The present invention relates to a syringe gasket having at least a part of the surface modified by the surface modification method.

The present invention relates to a syringe for a syringe having at least a part of the surface modified by the surface modification method.

The present invention relates to a tire having at least a part of a groove surface and / or a sidewall surface of the tire modified by the surface modification method.

According to the present invention, vulcanized rubber or a thermoplastic elastomer is used as a modification target, and a process 1 for forming a polymerization start point A on the surface of the modification target and a non-function starting from the polymerization start point A Surface modification comprising the step 2 of radically polymerizing a functional monomer to grow a non-functional polymer chain, and further radically polymerizing a fluorine-containing urethane (meth) acrylate monomer to grow a fluorine-containing urethane (meth) acrylate polymer chain Since it is a method, the polymer layer which consists of a fluorine-containing urethane (meth) acrylate polymer chain is formed in the outermost surface of a polymer chain, and functions, such as slidability, can be provided by this. Moreover, since the other part of a polymer chain is formed with the polymer layer which consists of a non-functional polymer chain, it is economically advantageous.

It is an example of the side view of embodiment of the gasket for syringes. It is an example of the expanded view of the tread part of a pneumatic tire (whole figure not shown). It is an example of A1-A1 sectional drawing of FIG.

The present invention is a surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification target, the step 1 of forming a polymerization start point A on the surface of the modification target, and the polymerization start point A Step 2 is a process of growing a non-functional polymer chain by radical polymerization of a non-functional monomer starting from the above, and further growing a fluorine-containing urethane (meth) acrylate polymer chain by radical polymerization of a fluorine-containing urethane (meth) acrylate monomer. Including.

In general, in order to impart functionality by forming a polymer chain on the surface of vulcanized rubber or thermoplastic elastomer with large irregularities, a functional chain is formed by forming a polymer chain of a certain height (length) from the surface. Although it is necessary to bring the chain to the surface, functional monomers are usually very expensive, so it is economically disadvantageous if the amount of the polymer chain is not limited to the minimum necessary to demonstrate the functionality. . On the other hand, in the present invention, first, a polymer chain is formed by inexpensive non-functional monomers on the surface of the object to be modified, and a certain degree of scaffolding is built, and then a fluorine-containing urethane (meth) acrylate monomer is polymerized thereon. This is a surface modification method for forming a functional polymer layer on the outermost surface by building a minimum functional polymer chain. Therefore, it is possible to provide a surface-modified elastic body imparted with desired functionality such as slidability very economically.

Furthermore, since the fluorine-containing urethane (meth) acrylate monomer used in the present invention has a low surface free energy, a functional polymer chain is formed on the outermost surface using the monomer to form a surface having a remarkably high slidability. Can be made.

In step 1, a polymerization start point A is formed on the surface of the rubber after vulcanization molding or the thermoplastic elastomer after molding (subject to be modified).
As the vulcanized rubber and the thermoplastic elastomer, those having a carbon atom adjacent to the double bond (allylic carbon atom) are preferably used.

Examples of rubbers to be modified include diene rubbers such as styrene butadiene rubber, butadiene rubber, isoprene rubber, natural rubber, and deproteinized natural rubber, and butyl rubber and halogenated butyl rubber containing isoprene units as a degree of unsaturation. Is mentioned. In the case of butyl rubber and halogenated butyl rubber, a crosslinked rubber made of triazine is preferred because the extract from the vulcanized rubber is reduced. In this case, an acid acceptor may be included, and suitable acid acceptors include hydrotalcite and magnesium carbonate.

In the case of other rubbers, sulfur vulcanization is preferred. In that case, you may add compounding agents, such as a vulcanization accelerator generally used by sulfur vulcanization, a zinc oxide, a filler, and a silane coupling agent. As the filler, carbon black, silica, clay, talc, calcium carbonate and the like can be suitably used.

The rubber vulcanization conditions may be set as appropriate, and the rubber vulcanization temperature is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and still more preferably 175 ° C. or higher.

As the thermoplastic elastomer, for example, a polymer compound having a rubber elasticity at normal temperature (thermoplastic elastomer (TPE) such as a styrene-butadiene styrene copolymer) by a collection of plastic components (hard segments) serving as a crosslinking point Etc .; a high molecular compound having rubber elasticity in which a thermoplastic component and a rubber component are mixed and dynamically crosslinked by a crosslinking agent (including a styrene block copolymer or an olefin resin and a crosslinked rubber component) And thermoplastic elastomers (TPV) such as polymer alloys).

Other suitable thermoplastic elastomers include nylon, polyester, urethane, polypropylene, and their dynamically crosslinked thermoplastic elastomers. In the case of a dynamically crosslinked thermoplastic elastomer, a material obtained by dynamically crosslinking a halogenated butyl rubber in a thermoplastic elastomer is preferable. In this case, the thermoplastic elastomer is preferably nylon, urethane, polypropylene, SIBS (styrene-isobutylene-styrene block copolymer) or the like.

The polymerization start point A is formed by, for example, adsorbing the photopolymerization initiator A on the surface of the modification target. Examples of the photopolymerization initiator A include carbonyl compounds, organic sulfur compounds such as tetraethylthiuram disulfide, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreducible dyes, among others. A carbonyl compound is preferred.

As the carbonyl compound as the photopolymerization initiator A, benzophenone and its derivatives are preferable. For example, a benzophenone compound represented by the following formula can be suitably used.

(Wherein R ^{1 to} R ⁵ and R ¹ ′ to R ⁵ ′ are the same or different and represent a hydrogen atom, an alkyl group, a halogen (fluorine, chlorine, bromine, iodine), a hydroxyl group, a primary to tertiary amino group, It represents a mercapto group or a hydrocarbon group that may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and any two adjacent groups may be linked together to form a ring structure together with the carbon atoms to which they are bonded. )

Specific examples of benzophenone compounds include benzophenone, xanthone, 9-fluorenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis ( And diethylamino) benzophenone. Among these, benzophenone, xanthone, and 9-fluorenone are particularly preferable because a polymer brush can be obtained satisfactorily.

As the benzophenone compound, a fluorobenzophenone compound can also be suitably used, and examples thereof include 2,3,4,5,6-pentafluorobenzophenone and decafluorobenzophenone represented by the following formula.

（式中、Ｒ^１１〜Ｒ^１４及びＲ^１１′〜Ｒ^１４′は、同一若しくは異なって、水素原子、ハロゲン原子、アルキル基、環状アルキル基、アリール基、アルケニル基、アルコキシ基、又はアリールオキシ基を表す。） As the photopolymerization initiator A, a thioxanthone compound can also be suitably used because it has a high polymerization rate and easily adsorbs and / or reacts with rubber or the like. For example, a compound represented by the following formula can be preferably used.

(In the formula, R ^{11 to} R ¹⁴ and R ¹¹ ′ to R ¹⁴ ′ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group, an alkenyl group, an alkoxy group, or an aryloxy group. Represents.)

Examples of the thioxanthone compound represented by the above formula include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-methoxythioxanthone, 1 -Chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-cyclohexylthioxanthone, 2-vinylthioxanthone, 2,4-divinylthioxanthone, 2,4-diphenylthioxanthone, 2-butenyl-4-phenylthioxanthone, 2-methoxythioxanthone , 2-p-octyloxyphenyl-4-ethylthioxanthone and the like. Among ^them, one or two of R 11 ^{to R 14} and ^R 11 ^{'~R 14',} is preferably one in particular two are substituted by an alkyl group, 2,4-Diethylthioxanthone (2,4- diethyl Thioxanthone) is more preferred.

As a method for adsorbing the photopolymerization initiator A such as a benzophenone compound or a thioxanthone compound on the surface of the object to be modified, a known method may be used. For example, for benzophenone compounds and thioxanthone compounds, the surface portion of the object to be modified is adsorbed on the surface by treatment with a solution obtained by dissolving benzophenone compounds and thioxanthone compounds in an organic solvent, The polymerization starting point A is formed by evaporating the organic solvent by drying as necessary. The surface treatment method is not particularly limited as long as the benzophenone compound solution and the thioxanthone compound solution can be brought into contact with the surface of the object to be modified. For example, the benzophenone compound solution and the thioxanthone compound Application, spraying, immersion in the solution, and the like are preferable. Further, when the surface modification is necessary only on a part of the surface, the photopolymerization initiator A may be adsorbed only on the part of the necessary surface. In this case, for example, the application of the solution, the solution Is suitable. As the solvent, methanol, ethanol, acetone, benzene, toluene, methyl ethyl ketone, ethyl acetate, THF, and the like can be used. Acetone is preferable because it does not swell the object to be modified, and is quick to dry and evaporate.

Further, after surface treatment with the benzophenone-based compound solution and the thioxanthone-based compound solution is performed on the site to be modified to adsorb the photopolymerization initiator A, it is further irradiated with light to be chemically bonded to the surface of the material to be modified. It is preferable to make it. For example, the benzophenone compound and the thioxanthone compound can be immobilized on the surface by irradiation with ultraviolet rays having a wavelength of 300 to 450 nm (preferably 300 to 400 nm, more preferably 350 to 400 nm). In the step 1 and the immobilization, as shown in the following formula, hydrogen on the rubber surface is extracted, and at the same time a covalent bond is formed between C═O carbon of benzophenone and carbon on the rubber surface. Hydrogen bonds to C = O oxygen to form C-O-H. Further, since this hydrogen abstraction reaction is selectively performed with hydrogen at the allylic position of the reforming target, it is preferable that the rubber contains butadiene and isoprene units having allyl hydrogen.

Among them, by treating the surface of the modification target with the photopolymerization initiator A to adsorb the photopolymerization initiator A on the surface, and then irradiating the treated surface with 300 to 450 nm LED light. The polymerization initiation point A is preferably formed. In particular, the surface of the modification target is subjected to a surface treatment with a benzophenone compound solution or a thioxanthone compound solution to adsorb the photopolymerization initiator A, and then further treated. It is preferable that the adsorbed photopolymerization initiator A is chemically bonded to the surface by irradiating the surface with 300 to 450 nm of LED light. If the wavelength is less than 300 nm, there is a possibility of damaging the molecule of the modification target, so that light of 300 nm or more is preferable, and from the viewpoint that the damage of the modification target is very small, it is 355 nm or more. More preferred is light. On the other hand, with light exceeding 450 nm, the polymerization initiator is difficult to activate and the polymerization reaction does not proceed easily, so light with a wavelength of 450 nm or less is preferable, and light with a wavelength of 400 nm or less is more preferable from the viewpoint of further activating the polymerization initiator. The wavelength of the LED light is particularly preferably 355 to 380 nm. LED light is suitable because it has a narrow wavelength and does not emit a wavelength other than the center wavelength. Even if a mercury lamp or the like is used to cut light of less than 300 nm using a filter, the same effect as LED light can be obtained. It is also possible.

In step 2, the non-functional monomer is radically polymerized starting from the polymerization start point A to grow a non-functional polymer chain, and the fluorine-containing urethane (meth) acrylate monomer is further radically polymerized to form a fluorine-containing urethane (meta ) Acrylate polymer chain is grown, preferably, the non-functional monomer is radically polymerized starting from the polymerization start point A to grow a non-functional polymer chain, and then the polymerization start point on the surface of the non-functional polymer chain B is formed, and a fluorine-containing urethane (meth) acrylate polymer chain is grown by radical polymerization of the fluorine-containing urethane (meth) acrylate monomer starting from the polymerization initiation point B. Specifically, first, a non-functional monomer is radically polymerized from the polymerization initiation point A formed in Step 1 to produce a non-functional polymer chain, and then the obtained non-functional polymer chain is If necessary, the polymerization start point B is formed on the surface of the non-functional polymer chain, and the polymer chain is extended by radical polymerization of the fluorine-containing urethane (meth) acrylate monomer starting from the polymerization start point B. By producing a fluorine-containing urethane (meth) acrylate polymer chain, a surface-modified elastic body having a fluorine-containing urethane (meth) acrylate polymer layer formed on the outermost surface can be produced.

The non-functional monomer in step 2 is a monomer that produces a non-functional polymer chain that does not have a function that is appropriately set according to the application. For example, when a function such as slidability is imparted to an object to be modified, a monomer that does not impart these functions is applicable, and may be appropriately selected from the viewpoint of economy. On the other hand, performance such as slidability can be imparted by polymerizing a fluorine-containing urethane (meth) acrylate monomer to produce a fluorine-containing urethane (meth) acrylate polymer chain.

The non-functional monomer may be appropriately selected from the above viewpoints. For example, acrylic acid, acrylic ester (methyl acrylate, ethyl acrylate, etc.), alkali metal acrylate (sodium acrylate, potassium acrylate, etc.) , Amine acrylate, acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, acryloylmorpholine, methoxymethyl acrylate, hydroxyethyl acrylate, methacrylic acid, methacrylic acid ester (methyl methacrylate, ethyl methacrylate, etc.), methacrylic Acid alkali metal salts (sodium methacrylate, potassium methacrylate, etc.), methacrylic acid amine salts, methacrylamide, dimethylmethacrylamide, die Le methacrylamide, isopropyl methacrylamide, hydroxyethyl methacrylamide, methacryloyl morpholine, methoxymethyl methacrylate, hydroxyethyl methacrylate, acrylonitrile and the like can be used. These may be used alone or in combination of two or more.

The fluorine-containing urethane (meth) acrylate monomer can be used without particular limitation as long as it is a fluorine-containing monomer having a urethane bond and a (meth) acrylate structure in the molecule. The number of (meth) acrylate groups in the monomer is preferably a compound having a polyfunctional (meth) acrylate group from the viewpoint of slidability and the like, and in particular, a compound having a bifunctional to tetrafunctional (meth) acrylate group. Is preferred.

Examples of the fluorine-containing urethane (meth) acrylate monomer include a fluorine-containing polyol, diisocyanate, and a compound obtained by reacting a hydroxyl group, a carboxyl group, or an amine group-containing (meth) acrylate. It is prepared by reacting with a hydroxyl group of a polyol and a hydroxyl group of a hydroxyl group, a carboxyl group or an amine group-containing (meth) acrylate, respectively, by a known method.

As a fluorine-containing polyol used here, a well-known polyfunctional polyol (2-4 functionalities etc.) etc. can be used, Specifically, the perfluoro polyether represented by a following formula is mentioned.
Z-CF ₂ - _{[(OCF 2 CF 2) m -} (OCF 2) n ] _-O-CF 2 -Z
(Wherein Z is the same or different and represents —CH ₂ (OCH ₂ CH ₂ ) _k OH (k is 0 to 10, preferably 1 to 7). M and n are the same or different. And represents an integer of 1 or more (preferably, m is 1 to 40, and n is 1 to 70).

The diisocyanate is not particularly limited, and hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H12-MDI), cyclohexyl-1,4-diisocyanate, 4,4′-methylenebis (phenylisocyanate) (MDI) or its isomer, toluene 2,4-diisocyanate (TDI) or its isomer, xylylene diisocyanate, naphthalene-1,5-diisocyanate, p-phenylene-diisocyanate, etc. And known compounds. The hydroxyl group, carboxyl group or amine group-containing (meth) acrylate is not particularly limited, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylamide And known compounds such as (meth) acrylic acid.

（式（１）中、Ｘは、同一又は異なって、ウレタン（メタ）アクリレート基を表す。ｐ、ｑは、同一又は異なって、１以上の整数を表す。） Examples of the structure of the fluorine-containing urethane (meth) acrylate monomer include a monomer having a fluoroalkyl ether group represented by the following formula (1).

(In formula (1), X is the same or different and represents a urethane (meth) acrylate group. P and q are the same or different and each represents an integer of 1 or more.)

The urethane (meth) acrylate group represented by X is not particularly limited as long as it is a group having a urethane bond and a (meth) acrylate structure, and may be appropriately selected from the viewpoint of slidability and the like. p is preferably 1 to 40, and q is preferably 1 to 70.

Moreover, the following compounds etc. are mentioned as a specific example of a fluorine-containing urethane (meth) acrylate monomer.

（式中、Ｙは、下記式（ａ）で示される繰り返し構造単位１及び下記式（ｂ）で示される繰り返し構造単位２の少なくとも一方を表す。該繰り返し構造単位１の繰り返し数ｒ及び該繰り返し構造単位２の繰り返し数ｓは、それぞれ独立に、０≦ｒ≦５０、０≦ｓ≦５０であり、かつｒ＋ｓ≧１である。）

(In the formula, Y represents at least one of the repeating structural unit 1 represented by the following formula (a) and the repeating structural unit 2 represented by the following formula (b). The repeating number r of the repeating structural unit 1 and the repeating unit The repeating number s of the structural unit 2 is independently 0 ≦ r ≦ 50, 0 ≦ s ≦ 50, and r + s ≧ 1.)

In the above formula, when both of the repeating structural units 1 and 2 are included, these may be either a block copolymer structure or a random copolymer structure. The number average molecular weight of the perfluoropolyether (PFPE) structure represented by the formulas (a) and (b) is preferably 100 to 20,000, more preferably 380 to 20,000.

As a method of radical polymerization of each of the non-functional monomer and the fluorine-containing urethane (meth) acrylate monomer in Step 2, the surface or non-functionality of the modification target to which a benzophenone compound, a thioxanthone compound or the like is adsorbed or covalently bonded A non-functional monomer or a fluorine-containing urethane (meth) acrylate monomer (liquid) or a solution thereof is applied (sprayed) to a modification target in which a polymer chain is formed, or the modification target or non-function Each of the radical polymerizations by irradiating light such as ultraviolet rays by immersing the modification target in which the functional polymer chain is formed in a non-functional monomer or fluorine-containing urethane (meth) acrylate monomer (liquid) or a solution thereof. Photoradical polymerization) proceeds to the surface of the object to be modified. It can be grown Tan a (meth) acrylate polymer chain in this order. Furthermore, after the coating, the surface is covered with transparent glass, PET, polycarbonate or the like, and each radical polymerization (photo radical polymerization) is advanced by irradiating light such as ultraviolet rays on the surface, so that the surface of the object to be modified On the other hand, a non-functional polymer chain and a fluorine-containing urethane (meth) acrylate polymer chain can be grown in this order.

Further, the amount of each monomer used may be appropriately set depending on the length of the polymer chain to be formed, the performance exhibited by the chain, and the like.

Conventionally known materials and methods can be applied to the coating (spraying) solvent, the coating (spraying) method, the dipping method, the irradiation conditions, and the like. As the monomer solution, an aqueous solution or a solution obtained by dissolving a used photopolymerization initiator (benzophenone compound, thioxanthone compound, etc.) in an organic solvent that does not dissolve is used. Moreover, what contains well-known polymerization inhibitors, such as 4-methylphenol, can also be used as a monomer (liquid) and its solution.

In the present invention, after application of the monomer (liquid) or a solution thereof or after immersion in the monomer or the solution thereof, the respective radical polymerization of the non-functional monomer and the fluorine-containing urethane (meth) acrylate monomer proceeds by light irradiation. However, a UV irradiation light source such as a high-pressure mercury lamp, a metal halide lamp, or an LED lamp having a light emission wavelength mainly in ultraviolet light can be preferably used. The amount of irradiation light may be appropriately set in consideration of the polymerization time and the uniformity of the progress of the reaction. In order to prevent polymerization inhibition due to active gas such as oxygen in the reaction vessel, it is preferable to remove oxygen in the reaction vessel or in the reaction solution at the time of light irradiation or before light irradiation. Therefore, introducing an inert gas such as nitrogen gas or argon gas into the reaction vessel or in the reaction liquid and discharging the active gas such as oxygen out of the reaction system, and replacing the inside of the reaction system with an inert gas atmosphere, The inside of the reaction vessel is evacuated and oxygen is degassed as appropriate. Furthermore, in order to prevent reaction inhibition such as oxygen, a UV irradiation light source is installed at a position where an air layer (oxygen content of 15% or more) does not enter between a reaction vessel such as glass or plastic and a reaction solution or a modification target. A device such as the above is also appropriately performed.

When irradiating with ultraviolet rays, the wavelength is preferably 300 to 450 nm, more preferably 300 to 400 nm. Thereby, a polymer chain can be favorably formed on the surface of the object to be modified. As the light source, a high-pressure mercury lamp, an LED having a central wavelength of 365 nm, an LED having a central wavelength of 375 nm, or the like can be used. Especially, it is preferable to irradiate 300-400 nm LED light, and it is more preferable to irradiate 355-380 nm LED light. In particular, an LED having a center wavelength of 365 nm close to the excitation wavelength of benzophenone of 366 nm is preferable from the viewpoint of efficiency.

In Step 2, the non-functional monomer is radically polymerized starting from the polymerization start point A to grow a non-functional polymer chain, and then the polymerization start point B is formed on the surface of the non-functional polymer chain. When the fluorine-containing urethane (meth) acrylate monomer is radically polymerized from the polymerization initiation point B as a starting point to grow a fluorine-containing urethane (meth) acrylate polymer chain, the formation of the polymerization initiation point B is the obtained non-functionality. It can be carried out by applying the same method as in Step 1 such as newly adsorbing the photopolymerization initiator B to the surface of the polymer chain, and further chemically bonding as necessary. Here, the photopolymerization initiator B can be the same as the photopolymerization initiator A.

The present invention is also a surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification target, wherein a non-functional monomer is radicalized on the surface of the modification target in the presence of a photopolymerization initiator A. A step I of growing a non-functional polymer chain by polymerization and further radically polymerizing a fluorine-containing urethane (meth) acrylate monomer in the presence of the photopolymerization initiator B to grow a fluorine-containing urethane (meth) acrylate polymer chain. Including. Specifically, a non-functional monomer is radically polymerized using a photopolymerization initiator A as an initiator to produce a non-functional polymer chain, and then a photopolymerization initiator B is further added to the obtained non-functional polymer chain. A fluorine-containing urethane (meth) acrylate polymer layer is formed on the outermost surface by radically polymerizing a fluorine-containing urethane (meth) acrylate monomer as an initiator to extend the polymer chain to produce a fluorine-containing urethane (meth) acrylate polymer chain. The formed surface-modified elastic body can be manufactured.

In step I, the non-functional monomer is radically polymerized from the polymerization initiation point A formed from the photopolymerization initiator A on the surface of the modification target to grow a non-functional polymer chain, and then the non-functional polymer It is preferable to grow a fluorine-containing urethane (meth) acrylate polymer chain by radical polymerization of a fluorine-containing urethane (meth) acrylate monomer starting from a polymerization initiation point B formed from the photopolymerization initiator B on the surface of the chain. For example, in the step I, after the photopolymerization initiator A and the non-functional monomer are brought into contact with the surface of the modification target, the polymerization is started from the photopolymerization initiator A by irradiating LED light of 300 to 450 nm. A point A is generated, and a non-functional monomer is radically polymerized starting from the polymerization start point A to grow a non-functional polymer chain, and then a photopolymerization initiator B and fluorine are formed on the surface of the non-functional polymer chain. After bringing the urethane (meth) acrylate monomer into contact, irradiation with LED light of 300 to 450 nm causes the polymerization initiation point B to be generated from the photopolymerization initiator B, and fluorine starting from the polymerization initiation point B. Can be carried out by radically polymerizing the containing urethane (meth) acrylate monomer to grow the fluorine-containing urethane (meth) acrylate polymer chain

As a method of radical polymerization of each of the non-functional monomer and the fluorine-containing urethane (meth) acrylate monomer in Step I, the surface of the modification object or the modification object on which the non-functional polymer chain is formed may be benzophenone-based. Non-functional monomer or fluorine-containing urethane (meth) acrylate monomer (liquid) containing a photopolymerization initiator A or B such as a compound or a thioxanthone compound, or a solution thereof (spray), or a modification target Alternatively, the modification target in which the non-functional polymer chain is formed is immersed in a non-functional monomer containing the photopolymerization initiator A or B, a fluorine-containing urethane (meth) acrylate monomer (liquid) or a solution thereof, and ultraviolet rays, etc. Each radical polymerization (photoradical polymerization) proceeds by irradiating the light, and the surface of the object to be modified Capacity polymer chain, a fluorine-containing urethane (meth) acrylate polymer chains can be grown in this order. Furthermore, a method of covering with the above-mentioned transparent glass, PET, polycarbonate, etc. and irradiating light such as ultraviolet rays from the top can be adopted. The same materials and methods as described above can be applied to the coating (spraying) solvent, the coating (spraying) method, the dipping method, and the irradiation conditions.

In Step 2 and Step I, by forming a polymer chain containing a fluorine-containing urethane (meth) acrylate polymer chain, excellent slidability and durability can be obtained, and good sealing performance can be maintained. The degree of polymerization of the formed polymer chain is preferably 20 to 200000, more preferably 350 to 50000.

The length of the total polymer chain including the non-functional polymer chain formed in Step 2 and Step I and the fluorine-containing urethane (meth) acrylate polymer chain is preferably 10 to 50000 nm, more preferably 100 to 50000 nm. If it is less than 10 nm, there is a tendency that good slidability cannot be obtained. If it exceeds 50000 nm, further improvement in slidability cannot be expected, and the cost of raw materials tends to increase due to the use of expensive monomers, and the surface pattern by surface treatment becomes visible to the naked eye. There is a tendency to deteriorate the sealing performance.

The ratio of the lengths of the non-functional polymer chain and the fluorine-containing urethane (meth) acrylate polymer chain in all the polymer chains formed in Step 2 and Step I (length of the non-functional polymer chain: fluorine-containing urethane (meth)) The length of the acrylate polymer chain is preferably 50:50 to 99.9: 0.1, more preferably 90:10 to 99.5: 0.5. If the length of the fluorine-containing urethane (meth) acrylate polymer chain is less than 0.1%, the desired function may not be imparted, and if it exceeds 50%, it tends to be economically disadvantageous.

In step 2 and step I, two or more types of non-functional monomers may be radically polymerized starting from the polymerization starting point A, and two or more fluorine-containing urethanes starting from the polymerization starting point B. The (meth) acrylate monomer may be radically polymerized simultaneously. Further, the non-functional, fluorine-containing urethane (meth) acrylate polymer chain may be a laminate of two or more layers. Furthermore, a plurality of polymer chains may be grown on the surface of the modification target. The surface modification method of the present invention may crosslink between polymer chains. In this case, ionic crosslinking, crosslinking with a hydrophilic group having an oxygen atom, and crosslinking with a halogen group such as iodine may be formed between the polymer chains.

By applying the surface modification method to vulcanized rubber or thermoplastic elastomer, a surface modified elastic body can be obtained. For example, a surface-modified elastic body excellent in slidability in the presence of water or in a dry state is obtained, which is excellent in that it has low friction and low water resistance. Further, by applying the method to at least a part of a three-dimensional solid (such as an elastic body), a modified surface-modified elastic body can be obtained. Furthermore, a polymer brush (polymer brush) is mentioned as a preferable example of the surface modified elastic body. Here, the polymer brush means a grafting graft polymer by surface-initiated living radical polymerization. In addition, the graft chain is preferably oriented in the substantially vertical direction from the surface of the modification target because the entropy is reduced and the molecular motion of the graft chain is lowered, so that the slidability is obtained. Furthermore, as the brush density, a quasi-density and a density brush that are 0.01 chains / nm ² or more are preferable.

Further, by applying the surface modification method to vulcanized rubber or thermoplastic elastomer, it is possible to produce a syringe gasket and a syringe syringe having at least a part of the modified surface. The modification is preferably performed at least on the sliding portion of the gasket or syringe surface, and may be performed on the entire surface.

FIG. 1 is an example of a side view of an embodiment of a syringe gasket. The gasket 1 shown in FIG. 1 has three annular protrusions 11a, 11b, and 11c that continuously protrude in the circumferential direction on the outer peripheral surface that contacts the inner peripheral surface of the syringe barrel of the syringe. In the gasket 1, the surface modification is applied to (1) the surface of the protruding portion in contact with the syringe such as the annular protruding portions 11 a, 11 b, 11 c, and (2) the side surface including the annular protruding portions 11 a, 11 b, 11 c. The entire surface includes (3) the entire surface of the side surface and the surface 13 of the bottom surface portion.

Furthermore, by applying the surface modification method to a groove formed in a tread of a tire used in a vehicle such as a passenger car and generating a polymer brush in the groove, the fluid resistance of the groove surface on a wet or snowy road surface is reduced. Or the contact angle with water is increased, water and snow can be eliminated and brushed, and the grip can be improved.

FIG. 2 shows an example of a development view of the tread portion 2 of the pneumatic tire (not shown), and FIG. 3 shows an example of the A1-A1 cross-sectional view of FIG.
2 to 3, the central vertical groove 3 a (groove depth D <b> 1) and the shoulder vertical groove 3 b (groove depth D <b> 2) are constituted by straight grooves extending linearly in the tire circumferential direction. Such straight grooves can reduce drainage resistance and exhibit high drainage performance when traveling straight ahead.

The pneumatic tire has a narrow groove 5 (groove depth D3) extending in the tire circumferential direction on the shoulder longitudinal groove 3b side, and an intermediate inclined groove 6 (groove) extending from the narrow groove 5 toward the central longitudinal groove 3a. Depth D4), joint groove 7 (groove depth D5) that is located on the inner side in the tire axial direction than the narrow groove 5 and that connects between the intermediate inclined grooves 6 and 6 adjacent in the tire circumferential direction, and from the shoulder vertical groove 3b to the tire Shoulder lateral grooves 8, 8 a, 8 b (groove depth D 6) and the like that extend to the outside are arranged, and drainage performance can be exhibited even with such grooves. And the above-mentioned effect is exhibited by applying the method to these grooves. Moreover, the effect which suppresses adhesion of dust and dust by applying the said method to the sidewall surface is also expected.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these.

Example 1
A vulcanized rubber gasket (vulcanized at 180 ° C. for 10 minutes) obtained by crosslinking chlorobutyl rubber containing an isoprene unit (unsaturation: 1 to 2%) with triazine is immersed in a 1 wt% acetone solution of benzophenone to vulcanize rubber surface Was adsorbed with benzophenone and dried.
The dried vulcanized rubber gasket was immersed in a glass reaction vessel containing a mixed aqueous solution of acrylic acid / acrylamide (2.5 M: 1.8 g of acrylic acid and 16.1 g of acrylamide dissolved in 100 mL of water). Radiation polymerization was carried out by irradiating LED-UV light having a wavelength for 80 minutes to grow a non-functional polymer chain on the rubber surface. Thereafter, the surface was washed with water and dried.
Next, the dried vulcanized rubber gasket was immersed in a 1 wt% acetone solution of benzophenone so that benzophenone was adsorbed on the surface of the non-functional polymer chain and dried. Further, vulcanized rubber gasket in which fluorine-containing urethane (meth) acrylate monomer (Solvay Specialty Polymers Japan Fomblin MT70: 4-functional urethane methacrylate) is diluted to 20 wt% with MEK and benzophenone is adsorbed on the surface of the non-functional polymer chain. It is applied to the surface and irradiated with LED-UV light having a wavelength of 365 nm for 90 minutes in an argon gas atmosphere to perform radical polymerization, and further grow a fluorine-containing urethane (meth) acrylate polymer chain on the non-functional polymer chain. I let you. As a result, a surface-modified elastic body (laminated polymer brush) was obtained.

(Example 2)
A surface-modified elastic body (laminated polymer brush) was obtained in the same manner as in Example 1 except that the polymerization time of the fluorine-containing urethane (meth) acrylate monomer (LED-UV light irradiation time) was changed to 120 minutes. .

(Example 3)
Surface modified elastic body as in Example 1 except that Fluorolink MD700 (bifunctional urethane methacrylate) of Solvay Specialty Polymers Japan Co., Ltd. was diluted to 20 wt% with MEK as the fluorine-containing urethane (meth) acrylate monomer (Laminated polymer brush) was obtained.

Example 4
Surface-modified elastic body as in Example 1 except that Fluorolink AD1700 (tetrafunctional urethane acrylate) from Solvay Specialty Polymers Japan was diluted to 20 wt% with MEK as the fluorine-containing urethane (meth) acrylate monomer (Laminated polymer brush) was obtained.

(Example 5)
Surface-modified elastic body as in Example 1 except that Fomblin AD40 (bifunctional urethane methacrylate) from Solvay Specialty Polymers Japan was diluted to 20 wt% with MEK as the fluorine-containing urethane (meth) acrylate monomer (Laminated polymer brush) was obtained.

(Comparative Example 1)
A vulcanized rubber (vulcanized at 180 ° C. for 10 minutes) itself obtained by crosslinking chlorobutyl rubber containing an isoprene unit (unsaturation degree: 1 to 2%) with triazine was used.

(Comparative Example 2)
Fluorine-containing urethane (meth) acrylate monomer diluted to 20 wt% with MEK is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10 A surface-modified elastic body (laminated polymer brush) was obtained in the same manner as in Example 1 except that it was changed to -Heptadecafluordecyl acrylate.

The surface-modified elastic bodies produced in Examples and Comparative Examples were evaluated by the following methods.
(Polymer chain length)
The length of the polymer chain formed on the surface of the vulcanized rubber was measured using an SEM at an acceleration voltage of 15 kV and 1000 times the cross section of the modified rubber on which the polymer chain was formed. The film thickness of the polymer layer was taken as the length of the polymer chain.

(Friction resistance)
In order to measure the frictional resistance force on the surface of the surface-modified elastic body, the vulcanized rubber gaskets prepared in Examples and Comparative Examples were set in a COP resin syringe of a syringe and pushed in using a tensile tester. Friction resistance was measured (pushing speed: 30 mm / min). The friction resistance force of Comparative Example 1 was set to 100, and the following formula was used, and each example was shown as a friction resistance index. A smaller index indicates a lower frictional resistance. When the frictional resistance index is 2.5 or less, it feels relatively light when the plunger of the syringe is pushed, which is good.
(Friction resistance index) = Friction resistance of each Example / Friction resistance of Comparative Example 1 × 100

From Table 1, it was revealed that the surface-modified elastic body surface of the example has a significantly reduced frictional resistance and good slidability. Moreover, since only the surface was modified, the sealing performance was equivalent to that of Comparative Example 1.

Therefore, when it is used as a gasket for a plunger of a syringe, the frictional force of the plunger against the syringe is reduced with a sufficient sealing property, and the treatment with the syringe can be performed easily and accurately. Further, since the difference between the static friction coefficient and the dynamic friction coefficient is small, the start of pushing the plunger and the subsequent plunger approaching operation can be performed smoothly without pulsating. Further, when a syringe syringe is made of a thermoplastic elastomer and a polymer chain is formed on the inner surface thereof, prescription by a syringe can be easily performed as described above.

In addition, by forming polymer chains on the surface of grooves, sidewalls, diaphragms, skis and snowboard boards, swimming swimsuits, road signs, signboards, etc. formed on the tread of tires used in passenger cars etc. Can also be expected.

DESCRIPTION OF SYMBOLS 1 Gasket 11a, 11b, 11c Annular projection part 13 Surface 2 of a bottom part 2 Tread part 3a Center vertical groove 3b Shoulder vertical groove 5 Narrow groove 6 Intermediate inclination groove 7 Joint groove 8, 8a, 8b Shoulder horizontal groove

Claims (24)

A surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification object,
Forming a polymerization initiation point A on the surface of the modification target; and
A non-functional monomer is radically polymerized starting from the polymerization starting point A to grow a non-functional polymer chain, and a fluorine-containing urethane (meth) acrylate monomer is further radically polymerized on the non-functional polymer chain. And a step 2 of growing a fluorine-containing urethane (meth) acrylate polymer chain. In the step 1, the photopolymerization initiator A is adsorbed on the surface of the modification target to form a polymerization start point A, or the photopolymerization initiator A is adsorbed on the surface of the modification target. The surface modification method according to claim 1, further comprising irradiating LED light of 300 to 400 nm to form a polymerization initiation point A from a photopolymerization initiator A on the surface. In the step 2, the non-functional monomer is radically polymerized by irradiation with LED light of 300 to 450 nm starting from the polymerization start point A to grow a non-functional polymer chain, and further a fluorine-containing urethane (meth) acrylate monomer The surface modification method according to claim 1 or 2, wherein a fluorine-containing urethane (meth) acrylate polymer chain is grown by radical polymerization by irradiation with LED light of 300 to 450 nm. In the step 2, the non-functional monomer is radically polymerized by irradiation with 300 to 450 nm LED light starting from the polymerization start point A to grow a non-functional polymer chain, and then the surface of the non-functional polymer chain is formed. After the photopolymerization initiator B is adsorbed to form the polymerization start point B, the fluorine-containing urethane (meth) acrylate monomer is radically polymerized by irradiation with LED light of 300 to 450 nm from the polymerization start point B as a starting point. One that grows a urethane (meth) acrylate polymer chain, or a radically polymerized non-functional monomer by irradiation with LED light of 300 to 450 nm starting from the polymerization initiation point A, to grow a non-functional polymer chain, Next, the photopolymerization initiator B is adsorbed on the surface of the non-functional polymer chain to further emit LED light of 300 to 400 nm. After the polymerization initiation point B is formed from the photopolymerization initiator B on the surface, radical polymerization is performed by irradiating the fluorine-containing urethane (meth) acrylate monomer from the polymerization initiation point B with LED light of 300 to 450 nm. The surface modification method according to any one of claims 1 to 3, wherein a fluorine-containing urethane (meth) acrylate polymer chain is grown . A surface modification method using a vulcanized rubber or a thermoplastic elastomer as a modification object,
Non-functional monomers are radically polymerized on the surface of the modification target in the presence of photopolymerization initiator A to grow a non-functional polymer chain, and fluorine-containing urethane (meta ) A surface modification method comprising the step I of growing a fluorine-containing urethane (meth) acrylate polymer chain by radical polymerization of an acrylate monomer on the non-functional polymer chain . The surface modification method according to claim 1, wherein the vulcanized rubber or the thermoplastic elastomer has an allylic carbon atom that is a carbon atom adjacent to a double bond. The surface modification method according to claim 1, wherein the photopolymerization initiators A and B are the same or different and are benzophenone compounds and / or thioxanthone compounds. The surface modification method according to claim 1, wherein the polymerization is performed in an inert gas atmosphere. The surface modification method according to claim 1, wherein polymerization is performed under vacuum degassing conditions. The non-functional monomer includes acrylic acid, acrylic ester, acrylamide, alkali metal acrylate, amine acrylate, methacrylic acid, methacrylic ester, methacrylamide, alkali metal methacrylate, amine methacrylate, dimethylacrylamide , Diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, methoxymethylacrylamide, acryloylmorpholine, methoxymethyl acrylate, hydroxyethyl acrylate, dimethylmethacrylamide, diethylmethacrylamide, isopropylmethacrylamide, hydroxyethylmethacrylamide, methacryloylmorpholine, methoxymethylmethacrylate, Hydroxyethyl methacrylate and acrylonitrile Surface modification method according to claim 1 is at least one selected from the group consisting of. The surface modification method according to claim 1, wherein the fluorine-containing urethane (meth) acrylate monomer has a fluoroalkyl ether group. The surface modification method according to claim 1, wherein the fluorine-containing urethane (meth) acrylate monomer is represented by the following formula (1).

(In formula (1), X is the same or different and represents a urethane (meth) acrylate group. P and q are the same or different and each represents an integer of 1 or more.) The surface modification method according to any one of claims 1 to 12, wherein the fluorine-containing (meth) acrylate monomer has a polyfunctional (meth) acrylate group. The surface modification method according to any one of claims 1 to 13, wherein the fluorine-containing (meth) acrylate monomer has 2 to 4 functional (meth) acrylate groups. The non-functional, fluorine-containing urethane (meth) acrylate monomer (liquid) or a solution thereof contains a polymerization inhibitor and is polymerized in the presence of the polymerization inhibitor. Surface modification method. The surface modification method according to claim 15, wherein the polymerization inhibitor is 4-methylphenol. The surface modification method according to any one of claims 1 to 16, wherein a length of all polymer chains including the non-functional polymer chain and the fluorine-containing urethane (meth) acrylate polymer chain is 10 to 50000 nm. The surface modification according to any one of claims 1 to 17, wherein a ratio of lengths of the non-functional polymer chain and the fluorine-containing urethane (meth) acrylate polymer chain is 50:50 to 99.9: 0.1. Quality method. A method for producing a gasket for a syringe having a vulcanized rubber or a thermoplastic elastomer as a modification target,
Forming a polymerization initiation point A on the surface of the modification target; and
A non-functional monomer is radically polymerized starting from the polymerization starting point A to grow a non-functional polymer chain, and a fluorine-containing urethane (meth) acrylate monomer is further radically polymerized on the non-functional polymer chain. And a step 2 for growing a fluorine-containing urethane (meth) acrylate polymer chain. A method for producing a gasket for a syringe having a vulcanized rubber or a thermoplastic elastomer as a modification target,
Non-functional monomers are radically polymerized on the surface of the modification target in the presence of photopolymerization initiator A to grow a non-functional polymer chain, and fluorine-containing urethane (meta ) A method for producing a gasket for a syringe, comprising the step I of radically polymerizing an acrylate monomer on the non-functional polymer chain to grow a fluorine-containing urethane (meth) acrylate polymer chain. A method for producing a syringe for a syringe having a vulcanized rubber or a thermoplastic elastomer as a modification target,
Forming a polymerization initiation point A on the surface of the modification target; and
A non-functional monomer is radically polymerized starting from the polymerization starting point A to grow a non-functional polymer chain, and a fluorine-containing urethane (meth) acrylate monomer is further radically polymerized on the non-functional polymer chain. The manufacturing method of the syringe for syringes including the process 2 which grows a fluorine-containing urethane (meth) acrylate polymer chain. A method for producing a syringe for a syringe having a vulcanized rubber or a thermoplastic elastomer as a modification target,
Non-functional monomers are radically polymerized on the surface of the modification target in the presence of photopolymerization initiator A to grow a non-functional polymer chain, and fluorine-containing urethane (meta ) A method for producing a syringe for a syringe, which comprises the step I of radically polymerizing an acrylate monomer on the non-functional polymer chain to grow a fluorine-containing urethane (meth) acrylate polymer chain. A method for manufacturing a tire using a vulcanized rubber or a thermoplastic elastomer as a modification object,
Forming a polymerization initiation point A on the surface of the modification target; and
A non-functional monomer is radically polymerized starting from the polymerization starting point A to grow a non-functional polymer chain, and a fluorine-containing urethane (meth) acrylate monomer is further radically polymerized on the non-functional polymer chain. And a step 2 of growing a fluorine-containing urethane (meth) acrylate polymer chain. A method for manufacturing a tire using a vulcanized rubber or a thermoplastic elastomer as a modification object,
Non-functional monomers are radically polymerized on the surface of the modification target in the presence of photopolymerization initiator A to grow a non-functional polymer chain, and fluorine-containing urethane (meta ) A tire manufacturing method comprising a step I in which an acrylate monomer is radically polymerized on the non-functional polymer chain to grow a fluorine-containing urethane (meth) acrylate polymer chain.

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