JP2007217516A - Fluoroalkyl group-containing chain high polymer and dental composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new type chain high polymer containing a phosphorylcholine type chemical structure, effectively exhibiting functions derived from the chemical structure and having improved peel resistance and to provide uses in which performances of the high polymer are effectively exhibited. <P>SOLUTION: The chain high polymer has a main chain containing a monomer unit represented by general formula (1) (wherein, R<SP>1</SP>represents a hydrogen atom or a methyl group; R<SP>2</SP>represents a 2-12C alkylene group; and R<SP>3</SP>represents a 1-6C alkyl group, with the proviso that 3 R<SP>3</SP>in the formula may each be mutually different). Furthermore, both terminals of the main chain have terminal groups containing a fluoroalkyl group, respectively. A dental composition comprises the chain high polymer. A dental polymerizable composition comprises the chain high polymer and a polymerizable monomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a chain polymer compound having a fluoroalkyl group in a terminal group and a dental composition containing the chain polymer compound. The chain polymer compound of the present invention includes, for example, dental materials, coating agents, conductivity-imparting agents, surfactants, adhesives, thickeners, cleaning agents, moisturizers, antithrombogenic materials, resins, metals, and glasses. It is useful for surface modifiers of fillers, antiviral agents, cosmetics, etc., and particularly useful as a compounding component of dental compositions.

  Methacryloyloxyethyl phosphorylcholine (hereinafter referred to as MPC), which is a polymerizable monomer having a phosphorylcholine group, is widely known as an antithrombotic material. Since the phosphorylcholine group has the effect of suppressing the adsorption of cells and proteins, the polymer in which MPC is incorporated has antithrombogenicity to artificial blood vessels, artificial hearts, subcutaneously implanted sensors, hemodialysis membranes, contact lenses, etc. Application as a material is expected (see Non-Patent Document 1).

  Patent Document 1 discloses a technique in which a copolymer film of MPC and (meth) acrylic acid ester is used as a coating material for a dental prosthesis to make it difficult for the biofilm to adhere to the surface of the prosthesis in the oral cavity. Is disclosed (see Patent Document 1).

On the other hand, among hydrophilic polymers in which monomers having hydrophilic groups are polymerized, hydrophilic polymers containing fluoroalkyl groups in which both ends are blocked with fluoroalkyl groups are obtained from their unique surface activity. Many applications have been studied (for example, see Patent Document 2).
Polymers Vol. 53, March, 2004 (pp. 164-165) JP 2004-194874 A JP-A-10-245419

  With current technology that attempts to immobilize phosphorylcholine groups on the surface of the substrate using MPC, surface treatment can be performed by graft polymerizing MPC on the surface of the substrate or adsorbing the polymer of MPC onto the surface of the substrate. However, since it is difficult to orient the phosphorylcholine group precisely, the basic functions of phosphorylcholine are not fully demonstrated, and problems such as easy peeling from the surface of the substrate are also pointed out. Has been.

  The present invention has been made to meet the above-mentioned demands, and one of the problems is to include a phosphorylcholine type chemical structure and to effectively exhibit functions derived from the chemical structure. It is possible to provide a new type of polymer compound that is capable of improving the peel resistance. Moreover, the other subject of this invention is providing the use from which the performance of this high molecular compound is exhibited effectively.

（式中、Ｒ^１は水素原子またはメチル基を示し、Ｒ^２は炭素数２〜１２のアルキレン基を示し、Ｒ^３は炭素数１〜６のアルキル基を示す。ただし、式中の３個のＲ^３は相異なっていてもよい。）
で表される単量体単位を含む主鎖を有し、かつ、該主鎖の両末端がそれぞれフルオロアルキル基を含む末端基を有する鎖状高分子化合物、
〔２〕〔１〕に記載の鎖状高分子化合物を含有する歯科用組成物（さらに重合性単量体を含有する歯科用重合性組成物を包含する）、
に関する。 The present invention
[1] The following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms. R ³ may be different from each other.)
A chain polymer compound having a main chain containing a monomer unit represented by formula (1) and having both end groups each containing a fluoroalkyl group,
[2] A dental composition containing the chain polymer compound according to [1] (including a dental polymerizable composition further containing a polymerizable monomer),
About.

  The chain polymer compound of the present invention has a chemical structure in that a phosphorylcholine group or a similar group is branched from a molecular main chain, and both ends of the main chain have terminal groups each containing a fluoroalkyl group. There are the above features.

  The chain polymer compound of the present invention is excellent in adsorption suppression performance for cells, proteins, biofilms, plaques, and the like, and in coating durability performance when a coating is formed on the substrate surface. The chain polymer compound of the present invention has an action of suppressing the adsorption of cells, proteins, biofilms, plaques, etc. by a phosphorylcholine group or a similar group, but has a unique property due to the fluoroalkyl groups present at both ends of the main chain. Due to the surface active action, phosphorylcholine groups or similar groups are more effectively oriented on the surface of the coated substrate, so that the adsorption suppressing action is remarkably enhanced, and at the same time, the film durability is greatly increased. It is estimated that it will be improved.

  Furthermore, the chain polymer compound of the present invention is not only used for biomaterials, but also has a highly oriented phosphorylcholine group or similar group on the surface in addition to the difficulty of soiling due to the water and oil repellency of fluorine. By doing so, an excellent antifouling property that oil-based dirt is difficult to adhere is also expressed.

で表される単量体単位を主鎖中に有する。一般式（１）中のＲ^１は水素原子またはメチル基である。Ｒ^２は炭素数２〜１２のアルキレン基であるが、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、デカメチレン基、ドデカメチレン基等の炭素数２〜１２の直鎖状アルキレン基が好ましく、エチレン基が特に好ましい。Ｒ^３は、メチル基、エチル基、イソプロピル基、ｎ−ブチル基、ｎ−ヘキシル基等の炭素数１〜６のアルキル基であり、一般式（１）中に含まれる３個のＲ^３は同一のアルキル基であっても、相違していてもよい。ただし、３個のＲ^３は、それぞれメチル基またはエチル基であることが好ましく、いずれもメチル基であることがより好ましい。 The chain polymer compound of the present invention is
General formula (1):

In the main chain. R ¹ in the general formula (1) is a hydrogen atom or a methyl group. R ² is an alkylene group having 2 to 12 carbon atoms, preferably a linear alkylene group having 2 to 12 carbon atoms such as ethylene group, trimethylene group, tetramethylene group, hexamethylene group, decamethylene group, dodecamethylene group and the like. An ethylene group is particularly preferred. R ³ is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and an n-hexyl group, and the three R ³ contained in the general formula (1) are Even if it is the same alkyl group, they may differ. However, it is preferable that ^three R <3> is respectively a methyl group or an ethyl group, and it is more preferable that all are methyl groups.

  The monomer unit represented by the general formula (1) constituting the chain polymer compound of the present invention may be one type or two or more types.

The chain polymer compound of the present invention has the same or different terminal groups at both ends of the main chain, and the terminal groups must contain a fluoroalkyl group therein. Examples of the fluoroalkyl group include a fluoroalkyl group having 1 to 12 carbon atoms and a fluorocycloalkyl group having 4 to 6 carbon atoms. The fluoroalkyl group may have a hydrogen atom, but a perfluoroalkyl group having a structure in which all hydrogen atoms are substituted with fluorine atoms is preferable. A particularly preferred fluoroalkyl group is a linear perfluoroalkyl group having 1 to 12 carbon atoms represented by the formula — (CF ₂ ) _p F (p represents an integer of 1 to 12).

で表される炭素数１〜１０の分岐状フルオロアルキレン基が挙げられる。フルオロアルキル基がオキサフルオロアルキル基中に含まれる場合、該オキサフルオロアルキル基の全炭素数は３〜１８であることが好ましい。 The fluoroalkyl group may be present in the terminal group as part of the oxafluoroalkyl group. An oxafluoroalkyl group is defined as a group in which at least one carbon atom in the carbon atom chain of a fluoroalkyl group is replaced with an oxygen atom. In the oxafluoroalkyl group, one or two or more oxygen atoms interposed between carbon atoms may be present, but it is preferable that two or more carbon atoms exist on both sides of the oxygen atom. Of course, a fluorine atom and a hydrogen atom may coexist in the oxafluoroalkyl group, but in general, it is preferable that all of the hydrogen atoms are substituted with fluorine atoms, that is, an oxaperfluoroalkyl group. . The fluoroalkylene group that may be contained in the oxafluoroalkyl group having two or more oxygen atoms is a carbon number represented by the formula — (CF ₂ ) _q — (q represents an integer of 1 to 12). 1-12 linear fluoroalkylene groups; any of the following formulae:

The C1-C10 branched fluoroalkylene group represented by these is mentioned. When the fluoroalkyl group is contained in the oxafluoroalkyl group, the total number of carbon atoms of the oxafluoroalkyl group is preferably 3-18.

  Examples of the terminal group containing a fluoroalkyl group include the above-mentioned fluoroalkyl group having 1 to 12 carbon atoms, fluorocycloalkyl group having 4 to 6 carbon atoms, oxafluoroalkyl group having 3 to 18 carbon atoms, Examples include a group having a structure in which a linking group such as an oxygen atom, a sulfur atom, a —COO— group, a —CO— group, and a —NH— group is bonded to the terminal of any group.

（式中、ｎは０〜６の整数を示す）
で表されるオキサフルオロアルキル基が、本発明の鎖状高分子化合物における所期の効果の高さ、鎖状高分子化合物の合成の容易さ（鎖状高分子化合物への導入の容易さ）、鎖状高分子化合物に導入するための原料（重合開始剤等）の入手し易さ、鎖状高分子化合物の性状の用途適合性（溶剤や重合性単量体への溶解性が高いことなど）などの点から特に好ましい。 As the terminal group, a fluoroalkyl group represented by the formula — (CF ₂ ) _e F (e represents an integer of 1 to 12), the following general formula (2):

(In the formula, n represents an integer of 0 to 6)
The oxafluoroalkyl group represented by the formula is highly effective in the chain polymer compound of the present invention, and is easy to synthesize the chain polymer compound (easy to introduce into the chain polymer compound). , Availability of raw materials (polymerization initiators, etc.) for introduction into the chain polymer compound, suitability for use of properties of the chain polymer compound (high solubility in solvents and polymerizable monomers) Etc.) is particularly preferable.

Specific examples of these preferable end groups include those having the following structures.
- _{(CF 2)} 3 F
_{-CF (CF 3) O- (CF} 2) 3 F
_{-CF (CF 3) O-CF} 2 CF (CF 3) O- (CF 2) 3 F
_{-CF (CF 3) O- (CF} 2 CF (CF 3) O) 2 - (CF 2) 3 F
_{-CF (CF 3) O- (CF} 2 CF (CF 3) O) 3 - (CF 2) 3 F
_{-CF (CF 3) O- (CF} 2 CF (CF 3) O) 6 - (CF 2) 3 F

  The chain polymer compound of the present invention includes a monomer represented by the general formula (1) in addition to a polymer having only a monomer unit represented by the general formula (1). Copolymers containing both units and other monomer units are also included. In such a case, in the chain polymer compound of the present invention, the ratio of the monomer unit represented by the general formula (1) and the monomer unit other than the monomer unit represented by the general formula (1) Is preferably in the range of 100: 0 to 1:99 in the former: latter molar ratio. As described above, by incorporating the monomer unit represented by the general formula (1) and the other monomer unit in combination, the solubility of the chain polymer compound of the present invention can be appropriately adjusted, When the chain polymer compound of the invention is blended in the molding material, it is difficult to elute the chain polymer compound, or when the chain polymer compound of the present invention is used as a coating material, It may be possible to improve adhesion. However, in the case of a chain polymer compound, when importance is attached to the effects of contamination resistance, plaque adhesion prevention, bacteria and protein adhesion prevention, the monomer unit represented by the general formula (1) and the general formula The ratio of monomer units other than the monomer unit represented by (1) is preferably in the range of 100: 0 to 5:95 in the former: the latter molar ratio, and 100: 0 to 10: A range of 90 is particularly preferred.

  Examples of monomer units other than the monomer unit represented by the general formula (1) that the chain polymer compound of the present invention may have are derived from the monomer (C) described later by addition polymerization. Monomer units to be used.

  In the main chain of the chain polymer compound of the present invention, when two or more types of monomer units represented by the general formula (1) are present, or a single unit represented by the general formula (1) When both the body unit and the other monomer unit are present, the arrangement of these plural types of monomer units is not particularly limited, and may be any of random, block, and tapered block. There may be.

  The number average molecular weight of the chain polymer compound of the present invention is not particularly limited, but is preferably in the range of 1000 to 1000000, and more preferably in the range of 2000 to 20000. When the number average molecular weight of the chain polymer compound is 1000 or more, particularly when it is 2000 or more, the antifouling property and the durability of the film are particularly easily expressed, and the number average molecular weight of the chain polymer compound is 1000000. In the following cases, more preferably in the case of 20000 or less, particularly in the case of 15000 or less, the production of the chain polymer compound is generally easy. The number average molecular weight can be measured by GPC (gel permeation chromatography) method.

  Among the chain polymer compounds of the present invention, the chain polymer compound in which the portions other than both ends of the main chain are substantially composed only of the monomer unit represented by the general formula (1) 1 type of (meth) acrylic acid ester derivative (hereinafter referred to as monomer (A)) having a chemical structure similar to phosphorylcholine group or phosphorylcholine group represented by the following general formula (3) The above can be synthesized by polymerization using a polymerization initiator represented by the following general formula (4) (hereinafter referred to as peroxide (B)). In the present specification, the notation “(meth) acryl” is used to mean both “methacryl” and “acryl”. Similarly, the notation “(meth) acryloyl” is used to mean both “methacryloyl” and “acryloyl”, and the notation “(meth) acrylate” means both “methacrylate” and “acrylate”. Used.

（式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ前記定義のとおりである）

一般式（４）：
Ｒｆ^１−Ｃ（＝Ｏ）−Ｏ−Ｏ−Ｃ（＝Ｏ）−Ｒｆ^２
（Ｒｆ^１およびＲｆ^２は、それぞれ独立に、フルオロアルキル基を含む有機基を示し、通常は、所望の末端基と同じ化学構造を有する基である）
The following general formula (3):

(Wherein R ¹ , R ² and R ³ are each as defined above)

General formula (4):
Rf ¹ —C (═O) —O—O—C (═O) —Rf ²
(Rf ¹ and Rf ² each independently represents an organic group containing a fluoroalkyl group and is usually a group having the same chemical structure as the desired end group)

  Of the chain polymer compound of the present invention, the portion other than both terminal portions of the main chain is a monomer unit represented by the general formula (1) and a monomer unit represented by the general formula (1). The chain polymer compound composed of both monomer units is a monomer other than the monomer (A) copolymerizable with the monomer (A) when the monomer (A) is polymerized. It can manufacture by taking the method of copolymerizing 1 or more types of a monomer (henceforth a monomer (C)).

  As the monomer (C), any known monomer can be used as long as it is copolymerizable with the monomer (A). For example, α-cyanoacrylic acid, (meth) acrylic can be used. Unsaturated carboxylic acids such as acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid; esters of the carboxylic acid; (meth) acrylamide or derivatives thereof; vinyl esters; vinyl ethers Examples thereof include styrenes, among which (meth) acrylic acid, esters thereof or amides thereof are preferably used.

〔式中、Ｒ^４は水素原子またはメチル基を示し、Ｘ^１は水素原子、メチル基、または、式：−Ｒ^ａ−Ｙ^１で表される基（式中、Ｒ^ａは炭素数２〜２０の炭化水素基を示し、Ｙ^１は、水素原子、水酸基、−ＣＯＯＨ基、リン酸基、ホスホン酸基、アミノ基、四級アンモニウム塩基、アルコキシシリル基、または炭素数１〜２０のアルコキシル基を示す）を示す〕
で表される（メタ）アクリル酸またはそのエステル類、および、
下記一般式：

〔式中、Ｒ^５は水素原子またはメチル基を示し、Ｘ^２およびＸ^３はそれぞれ独立に水素原子、メチル基、または、式：−Ｒ^ｂ−Ｙ^２で表される基（式中、Ｒ^ｂは炭素数２〜２０の炭化水素基、Ｙ^２は、水素原子、水酸基、−ＣＯＯＨ基、リン酸基、ホスホン酸基、アミノ基、四級アンモニウム塩基、アルコキシシリル基、または炭素数１〜２０のアルコキシル基を示す）を示す〕
で表される（メタ）アクリル酸アミド類が挙げられる。 Preferred examples of (meth) acrylic acid, esters thereof or amides thereof include, for example, the following general formula:

[In the formula, R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents a hydrogen atom, a methyl group, or a group represented by the formula: —R ^a —Y ¹ (wherein R ^a has 2 to 2 carbon atoms, 20 represents a hydrocarbon group, and Y ¹ represents a hydrogen atom, a hydroxyl group, a —COOH group, a phosphoric acid group, a phosphonic acid group, an amino group, a quaternary ammonium base, an alkoxysilyl group, or an alkoxyl group having 1 to 20 carbon atoms. Show)
(Meth) acrylic acid or its esters represented by:
The following general formula:

[Wherein, R ⁵ represents a hydrogen atom or a methyl group, and X ² and X ³ each independently represent a hydrogen atom, a methyl group, or a group represented by the formula: —R ^b —Y ² (wherein R ^b is a hydrocarbon group having 2 to 20 carbon atoms, Y ² is a hydrogen atom, a hydroxyl group, a —COOH group, a phosphoric acid group, a phosphonic acid group, an amino group, a quaternary ammonium base, an alkoxysilyl group, or a carbon number of 1 to 20 represents an alkoxyl group)]
(Meth) acrylic acid amides represented by the formula:

  Specific examples of such (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, and lauryl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 2 -Hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono ( Acrylate), (meth) acryloyl oxide decylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol mono (meth) acrylate, 2-butoxyethyl (Meth) acrylate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyl Oxydecyl dihydrogen phosphate, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 10- (meth) acryloyloxy-1, - decanedicarboxylic acid and the like. Specific examples of (meth) acrylic acid amides include N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, isopropyl (meth) acrylamide, and (meth) acryloyl. And morpholine.

  The peroxide (B) represented by the general formula (4) is used as a polymerization initiator to polymerize one or more monomers (A) represented by the general formula (3), or The method for producing the chain polymer compound of the present invention by polymerizing one or more of the monomer (A) and one or more of the monomer (C) is a known method using a peroxide as a polymerization initiator. This can be carried out according to the polymerization method. For example, the polymerization reaction can be performed in an inert solvent such as a halogenated aliphatic hydrocarbon at a normal pressure in the range of 0 ° C to 150 ° C. The polymerization reaction using such a peroxide having a fluoroalkyl group is described, for example, in a document by Sawada, one of the present inventors (Chemical Reviews Vol. 96, No. 5 (1996), pp. 1779-1808). It can also be done with reference.

  For example, polymerization can be carried out by mixing the peroxide (B) of the general formula (4) and the monomer (A) together with the monomer (C) as necessary and heating. At this time, the charge molar ratio of the peroxide (B) and all the monomers (when the monomer (C) is used in combination, the monomer (A) and the whole of the monomer (C)) is usually 1: 0.1 to 1: 100, particularly preferably 1: 0.5 to 1:20. The charged molar ratio of the monomer (A) to the monomer (C) can be any ratio, but is preferably in the range of 1: 0 to 1: 100, particularly preferably 1: It is in the range of 0 to 1:20, more preferably 1: 0 to 1: 5.

  Usually, the number average molecular weight of the obtained chain polymer compound can be adjusted by adjusting the charged molar ratio of the peroxide (B). That is, if the charge molar ratio of the peroxide (B) is set high with respect to all monomers, a polymer having a low number average molecular weight tends to be obtained. If the charge molar ratio is set low, the number average There is a tendency that a polymer having a high molecular weight can be obtained. Furthermore, the said polymerization reaction can be performed at a normal pressure, and reaction temperature is -20-150 degreeC normally, Preferably it is the range of 0-100 degreeC. The reaction time tends to be shortened by setting the reaction temperature to −20 ° C. or higher, and the reaction operation is facilitated by setting the reaction temperature to 150 ° C. or lower. Furthermore, although reaction time can be suitably selected in the range of 30 minutes-20 hours normally, it is desirable to set conditions so that it may become 1 to 10 hours practically.

  Moreover, in order to perform a polymerization reaction more smoothly, it may be preferable to use a solvent. Such a solvent is preferably a halogenated aliphatic hydrocarbon solvent or a halogenated aromatic hydrocarbon solvent. Specifically, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2- Trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3 -Trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1,2,2- Pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3- Chloropropane, benzotrifluoride, hexafluoroxylene, can be used pentafluoro benzene. Particularly industrially, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, etc. These solvents are used alone or in a mixed ratio [for example, AK-225 manufactured by Asahi Glass Co., Ltd. (1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1 , 3-dichloro-1,2,2,3,3-pentafluoropropane 1: 1.35 mixed solvent)]. When these solvents are used, it is usually desirable that the concentration of the peroxide (B) in the solvent is about 0.1 to 30% by weight.

  In order to perform the polymerization reaction more efficiently, it is desirable to add 1 to 90 parts by weight of water with respect to 100 parts by weight of the total monomers and dissolve the monomers to perform polymerization. It may be preferable in that the yield of the chain polymer compound can be increased and the time required for the polymerization reaction can be shortened. In the polymerization reaction, additives such as a known dispersant may be added to the reaction system at an appropriate ratio.

  The chain polymer compound of the present invention obtained by the above method can be purified by a known method such as a reprecipitation method, column chromatography, or dialysis.

Specific examples of the chain polymer compound of the present invention obtained by such a method include compounds represented by the following formulas. In the formula, x, y and z each represent the degree of polymerization of the corresponding monomer unit, but x / (x + y + z) is preferably from 0.01 to 1. In the present specification, unless otherwise specified, “C ₃ F ₇ ” represents a perfluoro n-propyl group. Furthermore, when multiple types of monomer units are contained in the same formula, the arrangement of these monomer units is not limited.

（式中、c-C₆F₁₁はペルフルオロシクロヘキシル基を示す）

(Where cC ₆ F ₁₁ represents a perfluorocyclohexyl group)

  The chain polymer compound of the present invention can be used, for example, as a coating material after being dissolved in a solvent, and is used as a polymerizable composition together with a polymerizable monomer. Moreover, it is used for various uses as an additive to molding materials, such as plastics, surfactant, a fiber treatment agent, and a dental material.

  A preferred use of the chain polymer compound of the present invention is a dental composition. The dental composition containing the chain polymer compound of the present invention includes a non-polymerizable dental composition obtained by dissolving one or more of the chain polymer compounds of the present invention in a suitable solvent. It can be used as a dental coating material or a dental primer. Another preferred type of dental composition is a dental polymerizable composition containing the chain polymer compound (a) of the present invention and a polymerizable monomer (b). Hereinafter, the dental polymerizable composition containing the chain polymer compound (a) and the polymerizable monomer (b) will be described in detail.

  In the dental polymerizable composition, one or more chain polymer compounds (a) can be used. The amount of the chain polymer compound (a) is based on 100 parts by weight of the polymerizable monomer (b) from the viewpoint of antifouling property, anti-adhesion effect such as plaque, the strength of the cured product and wear resistance. It is preferable that it is 0.001-30 weight part, More preferably, it is 0.01-10 weight part.

  The type of the polymerizable monomer (b) used in the dental polymerizable composition is not particularly limited, and those used in known dental polymerizable compositions can be used as well. Specifically, it is roughly classified into a radical polymerizable monomer and a cationic polymerizable monomer.

  Specific examples of the radical polymerizable monomer in the polymerizable monomer (b) include α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid. Examples thereof include unsaturated carboxylic acids such as acids and itaconic acids or esters derived therefrom; (meth) acrylamides; (meth) acrylamide derivatives; vinyl esters; vinyl ethers; styrenes. Of these, (meth) acrylic acid esters are preferred.

Examples of (meth) acrylic acid ester-based polymerizable monomers are shown below.
(1) monofunctional (meth) acrylate methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (Meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-bis (hydroxyethyl) (meth) acrylamide, (Meta) acrylic Oxy dodecyl pyridinium bromide, (meth) acryloyloxy-dodecyl pyridinium chloride, (meth) acryloyloxydodecyl pyridinium bromide, and the like (meth) acryloyloxy hexadecyl pyridinium chloride.

(2) Bifunctional (meth) acrylates Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate (commonly known as BisGMA), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2, 2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3 -(Meth) acryloyloxy-2-hydroxypropoxy] ethane Pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [N, N ′-(2,2,4-trimethylhexamethylene) bis (2-carbamoyloxyethyl) )] Dimethacrylate and the like.

(3) Trifunctional or higher (meth) acrylates Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, [N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarbonyloxy) propane-1,3-diol]] tetramethacrylate, 1,7-diacryloyl Examples include oxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane.

  The polymerizable monomers (b) can be used alone or in admixture of two or more.

  In addition, when improving the adhesiveness with respect to base materials, such as a tooth substance, a metal, and a ceramic, the functional monomer which improves the adhesiveness with respect to these base materials is made into a polymerizable monomer (b ) May be preferably contained as part of the above.

  Examples of the functional monomer include phosphoric acid such as 2- (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate Monomers having a carboxylic acid group such as 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, etc. It is preferable at the point which exhibits the outstanding adhesiveness.

  Examples of the functional monomer include 10-mercaptodecyl (meth) acrylate, 6- [3- (4-vinylbenzyl) propylamino] -1,3,5-triazine-2,4-dithione, A thiouracil derivative described in Japanese Patent No. 1473 and a compound having a sulfur atom described in Japanese Patent Application Laid-Open No. 11-92461 are preferable in that they exhibit excellent adhesion to noble metals.

  Furthermore, as the functional monomer, for example, a silane coupling agent such as 3-methacryloyloxypropyltrimethoxysilane is preferable because it is effective for adhesion to ceramics, porcelain, and dental composite resins.

  The amount of the functional monomer is preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the total polymerizable monomer (b) from the viewpoints of adhesive strength to the substrate and adhesion durability.

  It is preferable to add a polymerization initiator (c) in advance to the dental polymerizable composition to facilitate polymerization and curing.

  As the polymerization initiator (c) used in combination with the above radical polymerizable monomer, known radical polymerization initiators such as a heat polymerization initiator, a room temperature polymerization initiator, and a photopolymerization initiator can be used. .

  Examples of the heat polymerization initiator include polymerization initiators such as peroxides and azo compounds having a use temperature range of 40 to 100 ° C. Examples of heat polymerization initiators include organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides.

  Examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, and the like.

  Examples of peroxyesters include t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy- Examples include 2-ethylhexanoate and t-butyl peroxyisopropyl carbonate.

  Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like.

  Examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane.

  Examples of ketone peroxides include methyl ethyl ketone peroxide.

  Examples of hydroperoxides include t-butyl hydroperoxide.

  As the room temperature polymerization initiator, for example, a redox polymerization initiator system composed of an oxidizing agent (polymerization initiator) and a reducing agent (accelerator) can be suitably used. In this case, for example, benzoyl peroxide can be used as a polymerization initiator, and an aromatic tertiary amine such as diethanol toluidine, an aromatic sulfinate, or the like can be used as an accelerator.

  When a redox polymerization initiator is used, the dental polymerizable composition preferably takes a two-part or more packaging form. Examples of the oxidizing agent in the redox polymerization initiator system include organic peroxidation such as the diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, hydroperoxides, and the like. Things are preferred.

  As the reducing agent, for example, aromatic tertiary amine, aliphatic tertiary amine and sulfinic acid or a salt thereof are preferable.

  Examples of the aromatic tertiary amine include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N- Dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N -Screw ( -Hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 2-butoxyethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, and the like. These can be used alone or in admixture of two or more.

  Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, etc. may be mentioned. These may be used alone or in combination of two or more. Can be used.

  Examples of the sulfinic acid or a salt thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, toluenesulfine. Acid calcium, lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethyl Calcium benzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 2,4,6-triethylbenzenes Sodium finate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfine Examples thereof include sodium acid, potassium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, and the like. These may be used alone or in combination of two or more. it can.

  As the photopolymerization initiator, a special light irradiation device (for example, an ultraviolet irradiation device) is not required, and a light irradiation device in the visible light region that has been widely used in the past can be used. A photopolymerization initiator excited by light of ˜700 nm is preferred.

  Examples of the photopolymerization initiator excited by light having a wavelength of 350 to 700 nm include α-diketones, ketals, thioxanthones, acylphosphine oxides, coumarins, halomethyl group-substituted s-triazine derivatives, and the like. .

  Examples of the α-diketones include camphorquinone, benzyl, 2,3-pentanedione and the like.

  Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  Examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6- Tetramethylbenzoyldiphenylphosphine oxide, benzoylbis (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and water-soluble acylphosphine oxide disclosed in JP-B-3-57916 Compound etc. are mentioned.

  Examples of the coumarins are described in JP-A-10-245525 such as 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, and 3-thienoylcoumarin. Compounds.

  Examples of the halomethyl group-substituted s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl Examples thereof include compounds described in JP-A-10-245525 such as -4,6-bis (trichloromethyl) -s-triazine.

  Any of the photopolymerization initiators can be used alone or in admixture of two or more.

  The amount of the radical polymerization initiator is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0. 0 parts by weight with respect to 100 parts by weight of the polymerizable monomer (b). 1 to 3 parts by weight.

  In addition, when using a photoinitiator, in order to promote photocurability, it is preferable to use a photoinitiator and a reducing agent together.

  Examples of the reducing agent mainly include tertiary amines, aldehydes, and compounds having a thiol group, and these may be used alone or in combination of two or more.

  Examples of tertiary amines include 2-dimethylaminoethyl (meth) acrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl 4-dimethylaminobenzoate, 4-dimethyl Examples include butyl aminobenzoate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, and 4-dimethylaminobenzophenone.

  Examples of aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.

  Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.

  The amount of the reducing agent is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable monomer (b). Part.

  The dental polymerizable composition can be a radical polymerizable composition containing a radical polymerizable monomer as described above (preferably further containing a radical polymerization initiator). A cationically polymerizable composition containing a cationic polymerizable monomer as b) (preferably further containing a cationic polymerization initiator as a polymerization initiator (c)) may be used. Examples of such cationic polymerizable monomers include cationic polymerizable vinyl compounds, lactones, and cyclic ethers.

  Examples of the cationic polymerizable vinyl compound include vinyl ethers such as ethylene glycol divinyl ether, glycerol trivinyl ether, trimethylolpropane trivinyl ether, 4-vinyl ether styrene, and allyl vinyl ether, and styrenes.

  Examples of lactones include lactones such as γ-propiolactone and ε-caprolactone.

  Examples of cyclic ethers include alicyclic epoxy compounds, oxetane compounds, spiroorthoesters, bicycloorthoesters, and cyclic carbonates. Of these, alicyclic epoxy compounds and oxetane compounds are preferred.

  Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate [trade name: UVR6105 (low viscosity product) and UVR6110 (low viscosity product, manufactured by Union Carbide). ), Manufactured by Daicel Chemical Industries, Ltd., trade name: CELLOXIDE 2021, etc.], bis (3,4-epoxycyclohexylmethyl) adipate (trade name: UVR6128, manufactured by Union Carbide), vinyl cyclohexene monoepoxide [Daicel Chemical Co., Ltd. Manufactured, trade name: CELOXIDE 2000], ε-caprolactone-modified 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate [manufactured by Daicel Chemical Industries, trade name: CELOXIDE 2081], 1-methyl-4- ( 2-methyloxy Yl) -7-oxabicyclo [4.1.0] heptane [Daicel Chemical Industries Co., Ltd. under the trade name: CELOXIDE3000] and the like.

  Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxymethyl) oxetane. And oxetanes such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. These compounds can be easily obtained from, for example, Toagosei Chemical Co., Ltd. In addition, when an oxetane compound is used together with the alicyclic epoxy compound, the curability may be further improved.

  As the cationic polymerization initiator, a photocationic polymerization initiator is suitable. Examples of the photocationic polymerization initiator include known sulfonium salts and ammonium salts, and diaryliodonium salts and triarylsulfonium salts. JP-A-6-298912, JP-A-8-143806 and It can be used by appropriately selecting from those described in JP-A-8-283320.

  Moreover, a commercial item can also be used as it is as a photocationic polymerization initiator. Representative examples of commercially available products include Nippon Soda Co., Ltd., trade names: CI-1370, CI-2064, CI-2397, CI-2624, CI-2539, CI-2734, CI-2758, CI-2823, CI-2855, CI-5102, etc., Rhodia Co., Ltd., trade name: PHOTOINITIATOR 2047, etc., Union Carbide Corp., trade names: UVI-6974, UVI-6990, etc. Absent.

  The amount of the cationic polymerization initiator used varies depending on the type, the type and amount ratio of the cationic polymerizable monomer used, the usage conditions, etc., but from the viewpoint of improving curability and enhancing storage stability, The amount is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

  In addition, as the dental polymerizable composition, epoxy compounds, hydroxyl group-containing compounds, and iodonium salts described in JP-T-10-5008067, JP-A 2001-520758, JP-A 2001-520759, and the like ( A system in which a cationic polymerizable composition containing a photopolymerization catalyst comprising a polymerization initiator) and a visible light sensitizer (accelerator) is combined with the chain polymer compound (a) of the present invention is also included.

  A more preferred embodiment of the dental polymerizable composition is a composition obtained by further adding a solvent (d) to the chain polymer compound (a), the polymerizable monomer (b) and the polymerization initiator (c). It is.

  The solvent (d) referred to in the present specification is a liquid having a boiling point in the range of 40 to 180 ° C. at normal pressure, such as water, methanol, ethanol, isopropanol, n-propanol, butanol, cyclohexanol and the like. Alcohols such as chloroform, methylene chloride, chlorobenzene, etc .; hydrocarbons such as hexane, cyclohexane, toluene, xylene; ketones such as acetone, methyl ethyl ketone, cyclohexanone; esters such as ethyl acetate and butyl acetate An ether type may be mentioned, but it is not limited to such examples.

  The advantages of using the solvent (d) in this way in the dental polymerizable composition are to improve the solubility of the chain polymer compound (a) in the dental polymerizable composition, and further After the dental polymerizable composition is applied to the base material, the chain polymer compound (a) can be localized on the surface (gas-liquid interface) of the concentrate in the process of evaporation of the solvent. After the curing, the layer of the chain polymer compound (a) is densely formed on the surface of the cured product, and the surface has higher antifouling property. From these viewpoints, preferred are solvents such as water, methanol, ethanol, propanol, butanol, and acetone, which have good compatibility with the chain polymer compound (a) and can be evaporated relatively easily after coating.

  The amount of the solvent (d) is usually 30 to 1000 parts by weight, preferably 50 to 500 parts by weight, and more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the polymerizable monomer (b).

  Moreover, when it shows collectively about the suitable composition ratio of each component (a)-(d) in a dental polymerizable composition, with respect to 100 weight part of polymerizable monomers (b), a chain polymer compound ( The amount of a) is 0.001 to 30 parts by weight (more preferably 0.01 to 10 parts by weight), and the amount of the polymerization initiator (c) is 0.05 to 10 parts by weight (more preferably 0.1 to 5 parts). Parts by weight) and the amount of the solvent (d) is 30 to 1000 parts by weight (more preferably 50 to 500 parts by weight).

  When components that interact with each other in a dissolved state are used in the dental polymerizable composition, the components that interact with each other are divided in advance in order to increase the storage stability near room temperature. Then, it can be packaged, and a method of mixing and polymerizing them immediately before use can be employed. In particular, when using a redox polymerization catalyst consisting of a peroxide and a reducing agent as the polymerization initiator system, the peroxide and the reducing agent are packaged separately, and both are measured and mixed immediately before use. It is preferable to polymerize and cure.

  On the other hand, when using a photopolymerization initiator as a polymerization initiator, storage stability can be improved by storing the dental polymerizable composition containing the same in a sufficiently light-shielded container. It can be supplied to the user in a liquid state in which all components are dissolved (so-called “one-pack type” state). And since the user can apply the composition in a container directly to a tooth | gear or a restoration material, there exists an advantage that the operation is simple. As a usage form taking advantage of this advantage, for example, a one-pack type dental coating material in which a dental polymerizable composition is packaged in one package can be mentioned.

  As described above, when the solvent (d) is used as one component of the dental polymerizable composition, from the viewpoint of localizing the chain polymer compound (a) on the surface of the cured product, the polymerizable monomer ( As b), a polymerizable monomer that does not dissolve the chain polymer compound (a) is selected, and polymerization is performed so that the chain polymer compound (a) is uniformly dissolved in the state where the solvent (d) is blended. It is preferable to adjust the types and amounts of the polymerizable monomer (b) and the solvent (d). By selecting such a combination, as the solvent evaporates after the coating material is applied, the chain polymer compound (a) is added to the surface portion of the concentrate derived from the polymerizable composition. A dense chain polymer compound (a) layer can be formed on the surface of the cured product.

  As a method of forming a dense chain polymer compound (a) layer on the surface of the cured product in this way, for example, a dental polymerizable composition containing the chain polymer compound (a) of the present invention is used. A method of applying to the surface of a tooth or a dental restorative material, evaporating the solvent contained in the polymerizable composition, and then polymerizing and curing the concentrate derived from the polymerizable composition is included. From this viewpoint, polymerization curing by light irradiation is preferred.

  Specific examples of the use of such a dental polymerizable composition include dental composite filling materials, crown materials, fitting materials, artificial teeth, implant materials, denture base resins, fisher sealants, tooth surfaces and dental prostheses. Coating materials, surface lubricants, surface stains, dental nail polish and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this Example. In addition, the number average molecular weight of the obtained chain polymer compound was calculated based on a calibration curve of standard polystyrene by performing GPC analysis using tetrahydrofuran as a developing solvent. In the GPC analysis, trade names “Shodex GPC KF-802.5”, “Shodex RI-71”, and “Shodex DS-4” manufactured by Showa Denko KK were used as columns, detectors, and pumps, respectively.

数平均分子量（ＧＰＣ）：２８００
ＩＲ： ν(ｃｍ^-1)：１６３５（Ｃ＝Ｏ），１３２５（ＣＦ_３），１２３０（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．１〜１．７２（ＣＨ_２），δ１．６０（ＣＨ_３），δ３．２８（ＮＣＨ_３），δ３．５２（ＮＣＨ_２），δ４．０〜４．４（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．０〜−１０．５ｐｐｍ（１６Ｆ），
δ−５４．４ｐｐｍ（６Ｆ） Example 1
AK-225 (manufactured by Asahi Glass Co.) containing perfluoro-2-methyl-3-oxahexanoyl peroxide (2.2 mmol; 1.45 g) [1: 1 of CF ₃ CF ₂ CHCl ₂ and CHFClCF ₂ CF ₂ Cl An aqueous solution prepared by dissolving methacryloyloxyethyl phosphorylcholine (MPC) (6.5 mmol; 1.92 g) in water (1.8 g) was added to 34 g of the mixed solvent. This mixture was stirred at 45 ° C. for 6 hours under a nitrogen stream to conduct a polymerization reaction. After the reaction, the solvent was distilled off under reduced pressure, methanol was added to the remaining residue, and insolubles were removed by filtration. Hexane was added to the filtrate for reprecipitation, and the precipitated solid was collected. By washing and purifying the obtained solid (powder) with hexane, 0.35 g of the following compound (Chemical Formula 1 (where x represents the degree of polymerization of MPC-derived monomer units)), which is the target product, is obtained. It was.

Number average molecular weight (GPC): 2800
IR: ν (cm ⁻¹ ): 1635 (C═O), 1325 (CF ₃ ), 1230 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.1 to 1.72 (CH ₂ ), δ 1.60 (CH ₃ ), δ 3.28 (NCH ₃ ), δ 3.52 (NCH ₂ ), δ 4.0 to 4.4 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.0 to −10.5 ppm (16F),
δ-54.4 ppm (6F)

数平均分子量（ＧＰＣ）：３２００
ＩＲ： ν(ｃｍ^-1)：１６４０（Ｃ＝Ｏ），１３２２（ＣＦ_３），１２３６（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．０５〜１．７１（ＣＨ_２），δ１．６１（ＣＨ_３），δ３．３０（ＮＣＨ_３），δ３．５１（ＮＣＨ_２），δ４．０〜４．５（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．２〜−８．８ｐｐｍ（２６Ｆ），
δ−５４．９ｐｐｍ（６Ｆ），δ−７０．７ｐｐｍ（２Ｆ） Example 2
In Example 1, instead of perfluoro-2-methyl-3-oxahexanoyl peroxide as the peroxide, perfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide (2.2 mmol; Except for using 2.2 g), operations such as polymerization and reprecipitation were carried out in the same manner as in Example 1, and the following compound (chemical formula 2 (x represents the degree of polymerization of monomer units derived from MPC)): ) Was obtained in a yield of 0.33 g.

Number average molecular weight (GPC): 3200
IR: ν (cm ⁻¹ ): 1640 (C═O), 1322 (CF ₃ ), 1236 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.05 to 1.71 (CH ₂ ), δ 1.61 (CH ₃ ), δ 3.30 (NCH ₃ ), δ 3.51 (NCH ₂ ), δ 4.0 to 4.5 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.2 to −8.8 ppm (26 F),
δ-54.9 ppm (6F), δ-70.7 ppm (2F)

数平均分子量（ＧＰＣ）：４８００
ＩＲ： ν(ｃｍ^-1)：１６３７（Ｃ＝Ｏ），１３５０（ＣＦ_３），１２５８（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．０１〜１．７４（ＣＨ_２），δ１．５８（ＣＨ３），δ３．２７（ＮＣＨ_３），δ３．４８（ＮＣＨ_２），δ４．０〜４．５（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．５〜−９．８ｐｐｍ（３６Ｆ），
δ−５９．０ｐｐｍ（６Ｆ），δ−７１．１ｐｐｍ（４Ｆ） Example 3
In Example 1, instead of perfluoro-2-methyl-3-oxahexanoyl peroxide as a peroxide, perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide ( When operations such as polymerization and reprecipitation were carried out in the same manner as in Example 1 except that 2.2 mmol; 2.9 g) was used, the following compound (formula 3 (x represents polymerization of monomer units derived from MPC) was obtained. Degree)) was obtained in a yield of 0.4 g.

Number average molecular weight (GPC): 4800
IR: ν (cm ⁻¹ ): 1637 (C═O), 1350 (CF ₃ ), 1258 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.01-1.74 (CH ₂ ), δ 1.58 (CH ₃ ), δ 3.27 (NCH ₃ ), δ 3.48 (NCH ₂ ), δ 4.0-4 .5 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.5 to −9.8 ppm (36 F),
δ-59.0 ppm (6F), δ-71.1 ppm (4F)

数平均分子量（ＧＰＣ）：３８００
ＩＲ： ν(ｃｍ^-1)：１６５０（Ｃ＝Ｏ），１３４２（ＣＦ_３），１２４２（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．１３〜１．７３（ＣＨ_２），δ１．５９（ＣＨ_３），δ３．２９（ＮＣＨ_３），δ３．５（ＮＣＨ_２），δ４．０〜４．４（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−４．４〜−９．９ｐｐｍ（４６Ｆ），
δ−５３．６ｐｐｍ（６Ｆ），δ−７０．５ｐｐｍ（６Ｆ） Example 4
In Example 1, as the peroxide, perfluoro-2,5,8,11-tetramethyl-3,6,9,12-peroxide instead of perfluoro-2-methyl-3-oxahexanoyl peroxide was used. Except for using tetraoxapentadecanoyl (2.2 mmol; 3.6 g), operations such as polymerization and reprecipitation were carried out in the same manner as in Example 1. As a result, the following compound (wherein x is derived from MPC) Indicating the degree of polymerization of the monomer units)) was obtained in a yield of 0.44 g.

Number average molecular weight (GPC): 3800
IR: ν (cm ⁻¹ ): 1650 (C═O), 1342 (CF ₃ ), 1242 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.13 to 1.73 (CH ₂ ), δ 1.59 (CH ₃ ), δ 3.29 (NCH ₃ ), δ 3.5 (NCH ₂ ), δ 4.0 to 4.4 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-4.4 to −9.9 ppm (46 F),
δ-53.6 ppm (6F), δ-70.5 ppm (6F)

数平均分子量（ＧＰＣ）： ５６００
ＩＲ： ν(ｃｍ^-1)：１６８０（Ｃ＝Ｏ），１３３２（ＣＦ_３），１２４８（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．１３〜１．７３（ＣＨ_２），δ１．６０（ＣＨ_３），δ３．２８（ＮＣＨ_３），δ３．４８（ＮＣＨ_２），δ４．０５〜４．５（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．５〜−１０．５ｐｐｍ（３８Ｆ），
δ−５６．６ｐｐｍ（６Ｆ），δ−７１．５ｐｐｍ（２Ｆ） Example 5
In Example 1, instead of perfluoro-2-methyl-3-oxahexanoyl peroxide as a peroxide, perfluoro-2,5-dimethyl-3,6-dioxadodecanoyl peroxide (2.2 mmol; 2.8 g) was used, and operations such as polymerization and reprecipitation were carried out in the same manner as in Example 1. The following compound (x 5 indicates the degree of polymerization of monomer units derived from MPC): ) Was obtained in a yield of 0.3 g.

Number average molecular weight (GPC): 5600
IR: ν (cm ⁻¹ ): 1680 (C═O), 1332 (CF ₃ ), 1248 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.13 to 1.73 (CH ₂ ), δ 1.60 (CH ₃ ), δ 3.28 (NCH ₃ ), δ 3.48 (NCH ₂ ), δ 4.05 4.5 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.5 to -10.5 ppm (38 F),
δ-56.6 ppm (6F), δ-71.5 ppm (2F)

数平均分子量（ＧＰＣ）： ５９００
ＩＲ： ν(ｃｍ^-1)：１７００（Ｃ＝Ｏ），１３２０（ＣＦ_３），１２４０（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．０５〜１．７３（ＣＨ_２），δ１．５８（ＣＨ_３），δ２．１（ＣＨ），δ２．８〜３．１（ＮＣＨ_３），δ３．３０（ＮＣＨ_３），δ３．４５（ＮＣＨ_２），δ４．０〜４．４５（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．５〜−１１．５ｐｐｍ（１６Ｆ），
δ−５４．１ｐｐｍ（６Ｆ） Example 6
AK-225 (manufactured by Asahi Glass Co.) containing perfluoro-2-methyl-3-oxahexanoyl peroxide (2.2 mmol; 1.45 g) [1: 1 of CF ₃ CF ₂ CHCl ₂ and CHFClCF ₂ CF ₂ Cl Mixed solution] In 34 g of methacryloyloxyethyl phosphorylcholine (MPC) (6.5 mmol; 1.92 g) dissolved in water (1.8 g), dimethylacrylamide (10.8 mmol; 1.07) added. 50 g of AK-225 was further added to this mixed solution, and the polymerization reaction was carried out by stirring in a nitrogen stream at 45 ° C. for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, methanol was added to the remaining residue, and the insoluble material was removed by filtration. Hexane was added to the filtrate for reprecipitation, and the precipitated solid was collected. The obtained solid (powder) was purified by washing with hexane. Furthermore, when the obtained purified product was dried at 50 ° C. under vacuum for 2 days, the following compound (Chemical Formula 7) was obtained in a yield of 0.7 g. As a result of ¹ H-NMR analysis, it was x: y = 38: 62 (molar ratio).

Number average molecular weight (GPC): 5900
^{IR: ν (cm -1):} 1700 (C = O), 1320 (CF 3), 1240 (CF 2)
¹ H-NMR (D ₂ O): δ 1.05 to 1.73 (CH ₂ ), δ 1.58 (CH ₃ ), δ 2.1 (CH), δ 2.8 to 3.1 (NCH ₃ ), δ ₃ .30 (NCH ₃ ), δ 3.45 (NCH ₂ ), δ 4.0 to 4.45 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.5 to −11.5 ppm (16F),
δ-54.1 ppm (6F)

数平均分子量（ＧＰＣ）： ７８００
ＩＲ： ν(ｃｍ^-1)：１７０５（Ｃ＝Ｏ），１３３５（ＣＦ_３），１２５５（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．０〜１．７５（ＣＨ_２），δ１．５９（ＣＨ_３），δ２．１（ＣＨ），δ３．３１（ＮＣＨ_３），δ３．４４（ＮＣＨ_２），δ４．０〜４．４４（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．５〜−９．６ｐｐｍ（１６Ｆ），
δ−５５．２ｐｐｍ（６Ｆ） Example 7
Methacryloyloxyethyl phosphorylcholine (MPC) (6.5 mmol; 1.92 g), acrylic acid (15 mmol; 1.08 g), water (1.8 g) and AK-225 (Asahi Glass Co., Ltd.) [CF ₃ CF ₂ CHCl ₂ AK-225 containing perfluoro-2-methyl-3-oxahexanoyl peroxide (2.2 mmol; 1.45 g) in 25 g of a mixed solution added to a 1: 1 mixed solvent of CHFCClCF ₂ CF ₂ Cl] 40 g of the solution was added, and a polymerization reaction was performed at 45 ° C. for 5 hours under a nitrogen stream. After the reaction, the white powder in the obtained reaction mixture was collected by suction filtration, and the recovered product was sufficiently washed with hexane for purification. Furthermore, when the obtained purified product was dried at 50 ° C. under vacuum for 2 days, the following compound (Chemical Formula 8) was obtained in a yield of 0.5 g. As a result of ¹ H-NMR analysis, it was x: y = 20: 80 (molar ratio).

Number average molecular weight (GPC): 7800
^{IR: ν (cm -1):} 1705 (C = O), 1335 (CF 3), 1255 (CF 2)
¹ H-NMR (D ₂ O): δ 1.0 to 1.75 (CH ₂ ), δ 1.59 (CH ₃ ), δ 2.1 (CH), δ 3.31 (NCH ₃ ), δ 3.44 (NCH ₂ ), δ 4.0-4.44 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.5 to −9.6 ppm (16 F),
δ-55.2 ppm (6F)

数平均分子量（ＧＰＣ）： ４５００
ＩＲ： ν(ｃｍ^-1)：１６８５（Ｃ＝Ｏ），１３５０（ＣＦ_３），１２３６（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．０〜１．８（ＣＨ_２），δ１．３５（ＣＨ_３），δ１．５９（ＣＨ_３），δ２．１（ＣＨ），δ３．３１（ＮＣＨ_３），δ３．４４（ＮＣＨ_２），δ４．０〜４．４４（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−４．９〜−８．６ｐｐｍ（１６Ｆ），
δ−５４．５ｐｐｍ（６Ｆ） Example 8
Methacryloyloxyethyl phosphorylcholine (MPC) (6.5 mmol; 1.92 g), n-butyl acrylate (20 mmol; 2.56 g), water (1.8 g) and AK-225 (manufactured by Asahi Glass Co., Ltd.) [CF ₃ CF ₂ CHCl AK-225 containing perfluoro-2-methyl-3-oxahexanoyl peroxide (2.2 mmol; 1.45 g) in 25 g of a mixed solution composed of 1: 1 mixed solvent of ₂ and CHFCClCF ₂ CF ₂ Cl] 40 g of the solution was added, and a polymerization reaction was performed at 45 ° C. for 5 hours under a nitrogen stream. After the reaction, the white powder in the obtained reaction mixture was collected by suction filtration, and the recovered product was sufficiently washed with hexane for purification. Furthermore, when the obtained purified product was dried at 50 ° C. under vacuum for 2 days, the following compound (Chemical Formula 9) was obtained in a yield of 0.45 g. As a result of ¹ H-NMR analysis, it was x: y = 27: 73 (molar ratio).

Number average molecular weight (GPC): 4500
IR: ν (cm ⁻¹ ): 1685 (C═O), 1350 (CF ₃ ), 1236 (CF ₂ )
_{^{1 H-NMR (D 2 O}} ): δ1.0~1.8 (CH 2), δ1.35 (CH 3), δ1.59 (CH 3), δ2.1 (CH), δ3.31 (NCH ₃ ), δ 3.44 (NCH ₂ ), δ 4.0 to 4.44 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-4.9 to −8.6 ppm (16 F),
δ-54.5ppm (6F)

数平均分子量（ＧＰＣ）： ９１００
ＩＲ： ν(ｃｍ^-1)：１７００（Ｃ＝Ｏ），１３４０（ＣＦ_３），１２３２（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ１．２〜２．１（ＣＨ_２），δ１．５９（ＣＨ_３），δ２．４（ＣＨ），δ３．２７（ＮＣＨ_３），δ３．４０（ＮＣＨ_２），δ４．０３〜４．４１（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ５．７〜−７．９８（２Ｆ），−４０〜４４．７（４Ｆ），−４６．０〜−５１．１（６Ｆ），−５６．５〜６０．１（４Ｆ），−６２〜７１．７（６Ｆ），−１０７．２〜１１２（２Ｆ） Example 9
In Example 7, in place of perfluoro-2-methyl-3-oxahexanoyl peroxide, bis (perfluorocyclohexanecarbonyl) peroxide was used in the same manner as in Example 7 except for polymerization reaction, filtration, purification, etc. As a result of the operation, the following compound (Chemical Formula 14) was obtained. As a result of ¹ H-NMR analysis, it was x: y = 17: 83.

Number average molecular weight (GPC): 9100
IR: ν (cm ⁻¹ ): 1700 (C═O), 1340 (CF ₃ ), 1232 (CF ₂ )
¹ H-NMR (D ₂ O): δ 1.2 to 2.1 (CH ₂ ), δ 1.59 (CH ₃ ), δ 2.4 (CH), δ 3.27 (NCH ₃ ), δ 3.40 (NCH _{2), δ4.03~4.41 (OCH 2)}
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ5.7 to −7.98 (2F), −40 to 44.7 (4F), −46.0 to −51.1 (6F) ), −56.5 to 60.1 (4F), −62 to 71.7 (6F), −107.2 to 112 (2F)

Examples 10-11
In Example 8, the usage ratio of MPC and n-butyl acrylate was changed from 6.5 mmol and 20 mmol to 13.5 mmol and 14.5 mmol (Example 10), or 1.5 mmol and 25 mmol (Example 11). Except for the above, operations such as polymerization, filtration and purification were carried out in the same manner as in Example 8. As a result, compounds having the same end groups and monomer units as those obtained in Example 8 (Chemical Formula 9) were obtained. 0.42 g (Example 10) or 0.38 g (Example 11) was obtained. However, the content ratio and number average molecular weight of the two types of monomer units are different from those of Example 8, and the compound obtained in Example 10 is represented by x in the compound formula shown in Example 8. : Y = 50: 50 (molar ratio), and the number average molecular weight was 3,700. Moreover, the compound obtained in Example 11 was x: y = 5: 95 (molar ratio) in the formula of the compound shown in Example 8, and the number average molecular weight was 5800.

数平均分子量（ＧＰＣ）： ４４００
ＩＲ： ν(ｃｍ^-1)：１７１０（Ｃ＝Ｏ），１３３７（ＣＦ_３），１２５８（ＣＦ_２）
^１Ｈ−ＮＭＲ(Ｄ_２Ｏ)：δ０．９０〜１．９７（ＣＨ_２），δ１．６１（ＣＨ_３），δ２．１（ＣＨ），δ２．５〜２．８（ＣＨ_２），δ３．３３（ＮＣＨ_３），δ３．４１（ＮＣＨ_２），δ４．１〜４．５１（ＯＣＨ_２）
^１９Ｆ−ＮＭＲ（Ｄ_２Ｏ溶媒、ＣＦ_３ＣＯＯＨ内部標準）：δ−５．４５〜−９．３５ｐｐｍ（１６Ｆ），δ−５５．０ｐｐｍ（６Ｆ） Example 12
In Example 7, a polymerization reaction, filtration, purification and the like were performed in the same manner as in Example 7 except that 10-methacryloyloxydecylphosphorylcholine (6.5 mmol) was used instead of MPC. 0.34 g of (Chemical Formula 16) was obtained. The results of the analysis of ¹ H-NMR, x: was 77: y = 23.

Number average molecular weight (GPC): 4400
IR: ν (cm ⁻¹ ): 1710 (C═O), 1337 (CF ₃ ), 1258 (CF ₂ )
¹ H-NMR (D ₂ O): δ 0.90 to 1.97 (CH ₂ ), δ 1.61 (CH ₃ ), δ 2.1 (CH), δ 2.5 to 2.8 (CH ₂ ), δ ₃ .33 (NCH ₃ ), δ 3.41 (NCH ₂ ), δ 4.1 to 4.51 (OCH ₂ )
¹⁹ F-NMR (D ₂ O solvent, CF ₃ COOH internal standard): δ-5.45 to −9.35 ppm (16F), δ-55.0 ppm (6F)

Example 13
As an application example of the chain polymer compound obtained in Example 8, a dental photopolymerizable coating composition having the following composition was prepared. That is, 35 parts by weight of dipentaerythritol hexaacrylate (trade name DPE-6A, manufactured by Kyoeisha Chemical Co., hereinafter abbreviated as DPA6) and 15 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) are used as polymerizable monomers. These were uniformly dissolved using 1 part by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as TMDPO) as a polymerization initiator. 0.2 parts by weight of the chain polymer obtained in Example 8 was mixed with 50 parts by weight of ethanol (99%) as a solvent and dissolved uniformly. A dental photopolymerizable coating composition was obtained by mixing 50 parts by weight of the polymerizable monomer-containing solution and 50 parts by weight of a chain polymer compound-containing ethanol solution. The obtained dental photopolymerizable coating composition was applied onto a substrate by the method described below, then polymerized and cured, and then the stain resistance of the coating surface was evaluated.

Contamination resistance test A glass flat plate was used as a substrate, and a coloring test using a turmeric dye was performed. This method is an evaluation method published in Japan Prosthodontic Society Journal, Vol. 35 (1991), pages 542-555, as a means for simply and simply evaluating the contamination resistance of dental materials in the oral cavity. Is a reference.

  The surface of a glass plate having a thickness of 1 mm and a size of 20 mm × 15 mm is polished smoothly with # 1000 silicon carbide paper, and the photopolymerizable coating composition is applied to the surface to slowly evaporate volatile components. Then, using a dental light irradiator (trade name “JETLITE 3000” manufactured by Morita Co., Ltd.), light irradiation was performed until the unpolymerized layer on the surface disappeared, and polymerization was cured.

  In order to evaluate the antifouling property of the coating layer after polymerization and curing, a colorability test using a turmeric edible dye was performed. That is, the prepared test piece was placed in an aqueous suspension containing 1% by weight of turmeric dye, with the coating surface facing upward, and stored at 37 ° C. in a dark place. One week later, the test piece was taken out, washed with water, and the chromaticity of the test piece was measured with a color difference meter (Nippon Denshoku Σ90 type, C light source, colorimetric field of view 2 °). As for the degree of color change, the chromaticity of the test piece before immersion was compared with the chromaticity after immersion, and the difference in chromaticity was expressed as ΔE *. The value of ΔE * was 15.6. A smaller value of ΔE * means less coloring and better resistance to contamination.

Comparative Example 1
A coating composition was prepared in the same manner as in Example 13 except that the chain polymer compound obtained in Example 8 was omitted. Furthermore, when the obtained coating composition was evaluated for the stain resistance of the coating film on the glass substrate in the same manner as in Example 13, the value of ΔE * was 68.4, which was obtained in Example 13. It was found that the stain resistance was inferior compared to the coating composition.

Comparative Example 2
Instead of the chain polymer obtained in Example 8, a 75:25 (molar ratio) copolymer of n-butyl acrylate and MPC but having no fluoroalkyl group in the main chain end group Coating composition in the same manner as in Example 13 except that a polymer compound (synthesized by polymerizing a mixture of n-butyl acrylate and MPC in a molar ratio of 75:25 using benzoyl peroxide as a polymerization initiator) was blended A product was prepared. Furthermore, when the resulting composition was evaluated for stain resistance of the coating film on the glass substrate in the same manner as in Example 13, the value of ΔE * was 59.7, and the coating obtained in Example 13 was used. It was found that the stain resistance was inferior compared to the composition.

Comparative Example 3
Instead of the chain polymer obtained in Example 8, a 75:25 (molar ratio) copolymer of n-butyl acrylate and acrylic acid has no fluoroalkyl group in the main chain end group. Except that a chain polymer compound (a mixture obtained by polymerizing a mixture of n-butyl acrylate and acrylic acid in a molar ratio of 75:25 using benzoyl peroxide as a polymerization initiator) was blended, the same manner as in Example 13 was carried out. A coating composition was prepared. Furthermore, when the obtained composition was evaluated for stain resistance of the coating film on the glass substrate in the same manner as in Example 13, the value of ΔE * was 57.0, and the coating obtained in Example 13 was used. It was found that the stain resistance was inferior compared to the composition.

Comparative Example 4
Instead of the chain polymer obtained in Example 8, it is a 75:25 (molar ratio) copolymer of n-butyl acrylate and 2-methacryloyloxyethyltrimethylammonium chloride, but in the main chain end group. Implemented except blending a chain polymer without fluoroalkyl group (synthesized by polymerizing a mixture of n-butyl acrylate and 2-methacryloyloxyethyltrimethylammonium chloride using benzoyl peroxide as a polymerization initiator) A coating composition was prepared as in Example 13. Furthermore, the contamination resistance of the coating film on the glass substrate was evaluated for the obtained composition in the same manner as in Example 13. As a result, the value of ΔE * was 55.1, and the coating obtained in Example 13 was used. It was found that the stain resistance was inferior compared to the composition.

Examples 14-20
Example 13 except that the chain polymer compound obtained in Example 10, 11, 1, 7, 2, 6 or 12 was added instead of the chain polymer compound obtained in Example 8 Similarly, dental photopolymerizable coating compositions were prepared (Examples 14 to 20 in order).

Reference Example About the dental photopolymerizable coating compositions obtained in the above Examples 13 to 20, the plaque adhesion prevention performance after polymerization and curing was evaluated by the following test.

Plaque adhesion test Hard resin for dental crown “Epricord” (manufactured by Kuraray Medical Co., Ltd.) is filled into a stainless steel mold (4 × 4 × 2 mm), polymerized and cured by light irradiation, and 4 × 4 × 2 mm. A test piece was prepared. One surface of the test piece was polished by # 1000, and the dental photopolymerizable coating composition obtained in each of Examples 13 to 20 was applied to this surface, and the same method as in Example 13 was applied. A test piece having a cured coating surface was produced by polymerization and curing by light irradiation. When the coating surface was cured, the chromaticity of the coating surface was measured in the same manner as in Example 13 using a color difference meter. This test piece was worn in the oral cavity of a healthy person for 8 hours to evaluate plaque adhesion.

  That is, the test piece was affixed on the buccal side of the upper first molar of a healthy person with the coating surface of the test piece as the front. After mounting in the oral cavity for 8 hours, the test piece was peeled off and taken out from the oral cavity, and lightly washed in running tap water. The test piece was immersed in a plaque tester (plaque staining solution, manufactured by Lion Corporation) for 3 minutes to stain the adhered plaque. The chromaticity of the coated surface was measured again, compared with the chromaticity before installation in the oral cavity (at the end of coating surface curing), and the color difference was recorded. Three test pieces were prepared for each coating composition, three plaque adhesion tests were performed, and the average value of the color differences obtained in the three tests was expressed as ΔE *. The obtained results are shown in Table 1. A smaller value of ΔE * indicates that there is less plaque adhesion (higher adhesion prevention performance to plaque).

  In Table 1, in addition to ΔE * in the dental photopolymerizable coating compositions obtained in Examples 13 to 20 above, as a comparative example thereto, in place of the chain polymer compound of the present invention, The ΔE * values in the coating compositions (Comparative Examples 5 to 7) prepared in the same manner as in Example 13 except that the above polymer compound was used are also shown.

  As is apparent from Table 1, the chain polymer compound of the present invention containing a fluoroalkyl group in the terminal group and a monomer unit having a phosphorylcholine-type branched chain in the main chain is used for dental use. When used as a polymerizable composition (Examples 13 to 20), it exhibits a markedly superior plaque adhesion preventing effect as compared with other chain polymer compounds (Comparative Examples 5 to 7).

  The chain polymer of the present invention is a coating agent, conductivity-imparting agent, surfactant, antithrombotic material, adhesive, thickener, cleaning agent, moisturizer, resin, metal, glass and filler surface modification. It is useful for quality agents, antiviral agents, cosmetics, fiber treatment agents, dental materials and the like.

In particular, the chain polymer compound of the present invention is used as a component of a dental polymerizable composition in the field of dental materials, so that dental composite filling materials, dental crown materials, fitting materials, etc. Composite resins, orthodontic adhesives, adhesives for cavity application and dental fissure sealing materials, denture base materials, denture base mucous membrane conditioners, fisher sealants, tooth surfaces and dental use It is advantageously used as a coating material for a prosthesis or a surface lubricant. Among these, when used as a coating material for various coatings, for example, as a sealant for a tooth surface or dental prosthesis, as a surface stain or surface lubricant, as a material for suppressing hypersensitivity, or as a dental nail polish, The feature of the chain polymer compound of the present invention is exhibited to the maximum that the surface formed from the chain polymer compound of the present invention prevents the adhesion of biofilms and plaques in the oral cavity.

Claims (5)

The following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms. R ³ may be different from each other.)
A chain polymer compound having a main chain containing a monomer unit represented by formula (1) and having both end groups each containing a fluoroalkyl group. The end group is represented by the following general formula (2):

(In the formula, n represents an integer of 0 to 6)
The chain polymer compound according to claim 1, represented by:   The chain polymer compound according to claim 1 or 2, having a number average molecular weight of 1,000 to 100,000.   A dental composition containing the chain polymer compound according to claim 1. A dental polymerizable composition comprising the chain polymer compound according to any one of claims 1 to 3 and a polymerizable monomer.