JP2015025110A - (meth)acrylate compound, production method of the same, and polymeric compound having microbial adhesion preventing function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel (meth)acrylate compound that can impart a microbial adhesion preventing function to a radical polymer of the compound, and to provide an easy production method of the above compound with high yield.SOLUTION: The (meth)acrylate compound is expressed by formula (1) below, and a polymeric compound is obtained by polymerizing a monomer comprising the above compound. In formula (1), R1 represents a hydrogen atom or a methyl group; R2 represents -R3NHCOO- or a single bond, where R3 represents a divalent linear hydrocarbon group which may have an oxygen atom (provided that oxygen atoms are not continuous and that no oxygen atom is located at either end of R3); R4 represents a fluorophenylene group in which 1 to 4 fluorine atoms are bonded, or a divalent hydrocarbon group having a fluorophenylene group in which 1 to 4 fluorine atoms are bonded and optionally having an oxygen atom; and R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Description

  The present invention relates to a novel (meth) acrylate compound, a production method thereof, and a polymer compound having a function of preventing microbial adhesion. More specifically, the present invention relates to a novel compound such as (meth) acrylate having a fluorophenylene group, a production method thereof, and a polymer compound having a function of preventing microbial adhesion obtained by using it as a raw material. According to the production method of the present invention, a novel compound such as (meth) acrylate having a fluorophenylene group can be obtained with high purity and high yield by a simple method. In addition, by using the polymer compound of the present invention, microorganisms can be prevented from adhering to the inner surface of a water pipe or drain pipe in a water treatment facility or factory, the inner surface of a circulation pipe provided in a bathroom or air conditioning equipment, etc. And can significantly reduce maintenance costs.

  A radically polymerizable compound having a phenolic hydroxyl group in a molecule represented by hydroxystyrene and a phenol compound having a (meth) acryloyl group imparts alkali solubility to a polymer obtained by radical copolymerization of the compound. Since it can be used, it has been preferably used in the field of photoresist. In addition, since the phenolic hydroxyl group can be used as a crosslinking point, it is not limited to a photoresist, and can be used as a raw material monomer for other coating material resins.

  Patent Document 1 describes a (meth) acrylate compound having a phenolic hydroxyl group, but this compound cannot provide sufficient functions such as heat resistance, chemical resistance, and weather resistance.

  Patent Document 2 describes a method for producing a hydroxyphenyl (meth) acrylate having a phenolic hydroxyl group. In this method, phenylene di (meth) acrylate is by-produced, and therefore hydroxyphenyl (meta) ) The by-product phenylene di (meth) acrylate contained in the crude crystal cannot be removed unless the crude crystal containing acrylate is washed several times with a poor solvent, and the phenylene di (meth) acrylate is gelled. It causes quality degradation.

  There are bacteria, fungi, filamentous fungi, algae, etc. in structures that contact water such as the inner surface of water pipes or drainage pipes in water treatment facilities, factories, etc., the inner surface of circulation pipes provided in bathrooms and air conditioning equipment, etc. Species microorganisms adhere to the surface of the substrate (carrier) to form colonies. When a certain number of cells are reached, organic substances such as polysaccharides and glycoproteins are produced and secreted to biofilms (biofilms). Form. As a result of the formation of biofilms, these structures may induce a decrease in thermal efficiency, a decrease in flow rate, blockage of tubes, and the like. Biofilms are also formed in areas where condensation is likely to occur, such as inside and outside buildings, water facilities, refrigeration / refrigeration facilities, and air conditioners, causing deterioration of materials, loss of aesthetics, and deterioration of the health of surrounding people. Sometimes.

  Thus, the formation of a biofilm is remarkably recognized in a member in which part or all of the biofilm is in contact with moisture. As a method for preventing problems caused by adhesion of microorganisms or the like, there is a method of applying or impregnating a base material with a drug such as an antifouling agent or an antibacterial agent. However, the drug applied by application or impregnation in this way is gradually released into the environment and may adversely affect surrounding organisms. Further, microorganisms having resistance to the drug may appear in the vicinity while being exposed to the continuously released drug. Therefore, as an environmentally friendly method, for example, in Patent Document 3, a coating film is formed by applying a dispersion containing a biodegradable resin or the like to a base material to prevent adhesion of aquatic organisms and adhesion. A technique for facilitating removal of living organisms is disclosed.

Patent Document 4 and the like disclose a technique for imparting antifouling property by kneading titanium oxide as a photocatalyst into a base material.
As other techniques, Patent Document 5 and the like disclose a technique for preventing adhesion of organisms to a structure (base material) that contacts seawater using an electric current.

JP 2006-111803 A JP 2007-204448 A JP 2005-132924 A JP 2003-231814 A JP 2003-013264 A

The present invention provides a novel (meth) acrylate compound that can impart functions such as alkali solubility, crosslinkability, heat resistance, chemical resistance, and weather resistance to the radical polymer of the compound and the compound in a simple manner. An object of the present invention is to provide a method that can be produced with high purity and high yield.
Another object of the present invention is to provide a polymer compound having a function of preventing microbial adhesion obtained by using a novel (meth) acrylate compound as a raw material.

  A dihydroxy compound having a fluorophenylene group, such as 2,3,5,6-tetrafluoro-p-phenylenedimethanol (hereinafter abbreviated as “TFDM”) has two hydroxyl groups in the molecule. However, there is a feature that the acidity of the hydroxyl group is high due to the fluorine atom in the molecule. In addition, because of the high C—F bond energy, heat resistance, chemical resistance, weather resistance, etc. can be imparted to the polymer, and at the same time, the fluorine atoms reduce the refractive index and dielectric constant of the polymer. In addition, low surface tension and water repellency can be imparted.

  Further, the present inventors have found that a polymer compound having a fluorophenylene group has a high antimicrobial adhesion function. However, when TFDM is used as a raw material as it is, a condensed type or an addition type using the hydroxyl group is used. Since only the reaction can be used, the degree of freedom in designing the resin structure is poor, and there are particularly large restrictions in terms of synthesis and control of physical properties of solvent-soluble coating type polymer compounds.

  Therefore, the present inventors introduced a (meth) acryloyl group, which is a radical polymerizable functional group, while leaving one hydroxyl group of a dihydroxy compound having a fluorophenylene group, thereby allowing a radical having a reactive hydroxyl group in the molecule. A polymerizable monomer was used. In particular, TFDM and tetrafluorohydroquinone can impart alkali developability due to the high acidity of the hydroxyl group, and these (meth) acrylate compounds impart new functions to the photoresist material due to the above-mentioned characteristics resulting from the C—F bond. It is expected to be developed, and development to the application can be expected.

  In addition, by radical copolymerization of a (meth) acrylate compound having a fluorophenylene group and another monomer, a polymer compound having a function of preventing microbial adhesion can be obtained, and water pipes such as water treatment facilities and factories can be obtained. Development of coating materials for structures that come into contact with water, such as the inner surface of drain pipes, the inner surface of circulation pipes provided in bathrooms and air conditioning equipment, can be expected.

  A compound in which a (meth) acryloyl group which is a polymerizable functional group is introduced while leaving one hydroxyl group of a dihydroxy compound having a fluorophenylene group, and a fluorophenylene group and a (meth) acryloyl group which is a polymerizable functional group The specific compound has been found for the first time by the present inventors.

  In addition, the present inventors selectively react one of two hydroxyl groups of a dihydroxy compound having a fluorophenylene group using dihydropyran, thereby producing a tetrahydropyranyl group and a fluorophenylene group. Or a hydroxy compound having various kinds of (meth) acryloyl-containing compounds, and the tetrahydropyranyl group of the resulting compound is deprotected to form a hydroxyl group, or of the two hydroxyl groups. A novel (meth) acrylate compound can be easily produced with high purity and high yield by reacting a hydroxy compound in which one hydrogen is substituted with an alkyl group and various (meth) acryloyl-containing compounds. I found out that I can do it. The present invention has been completed based on these findings.

  Further, the inventors of the present invention have a high antimicrobial adhesion function by radical polymerization of the above-described novel (meth) acrylate compound having a fluorophenylene group with other radical polymerizable monomers as necessary. It has been found that molecular compounds can be obtained.

That is, the present invention relates to the following (1) to [23] novel (meth) acrylate compounds, production methods thereof, and polymer compounds having a function of preventing microbial adhesion.
[1] A (meth) acrylate compound represented by the following formula (1).
Formula (1)

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain which may have oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group in which 1 to 4 fluorine atoms are bonded, or fluorine (It represents a divalent hydrocarbon group optionally having oxygen having a fluorophenylene group having 1 to 4 atoms bonded thereto, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[2] The (meth) acrylate compound according to [1], wherein R ⁴ is a 2,3,5,6-tetrafluoro-p-xylylene group.

[3] The (meth) acrylate compound of [1] or [2], wherein R ² is a single bond or —R ³ NHCOO—, and R ³ is — (CH ₂ ) ₂ —.

[4] The (meth) acrylate compound of [1], which is a compound represented by the following formula (2).
Formula (2)

[5] The (meth) acrylate compound of [1], which is a compound represented by the following formula (3).
Formula (3)

[6] The (meth) acrylate compound of [1], which is a compound represented by the following formula (4).
Formula (4)

[7] The (meth) acrylate compound of [1], which is a compound represented by the following formula (5).
Formula (5)

[8] The (meth) acrylate compound of [1], which is a compound represented by the following formula (6).
Formula (6)

[9] The (meth) acrylate compound of [1], which is a compound represented by the following formula (7).
Formula (7)

[10] The (meth) acrylate compound of [1], which is a compound represented by the following formula (8).
Formula (8)

[11] The (meth) acrylate compound of [1], which is a compound represented by the following formula (9).
Formula (9)

[12] After reacting the hydroxy compound represented by the following formula (10) with the (meth) acryloyl group-containing compound represented by the formula (11), the tetrahydropyranyl group is deprotected from the compound obtained by the reaction. The manufacturing method of the (meth) acrylate compound in any one of [1]-[7].
Formula (10)

(In the formula (10), R ⁴ is a divalent hydrocarbon which may have oxygen having a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto or a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto. Represents a group.)
Formula (11)

(In Formula (11), R ¹ represents a hydrogen atom or a methyl group, X represents a halogen atom, —OCOC (R ¹ ) ═CH ₂ , —OR ⁵ or —OR ³ NCO, and R ³ represents oxygen. Represents a divalent linear hydrocarbon group which may have (provided that oxygen atoms are not continuous and oxygen atoms are not present at both ends of R ³ ), and R ⁵ is a hydrogen atom Or represents a C1-C4 alkyl group.)

  [13] A polymer compound obtained by polymerizing the (meth) acrylate compound according to any one of [1] to [11] alone.

  [14] A polymer compound obtained by polymerizing a monomer containing the (meth) acrylate compound according to any one of [1] to [11].

[15] The polymer compound according to [14] obtained by copolymerizing the following (A), (B) and (C).
(A) (Meth) acrylate compound represented by the following formula (1) (1)

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain which may have oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group or fluorine atom having 1 to 4 fluorine atoms bonded thereto Represents a divalent hydrocarbon group which may have oxygen having 1 to 4 bonded fluorophenylene groups, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
(B) Radical polymerizable monomer having an organic group having a cyclic ether structure of 4 or more members (C) Radical polymerizable monomer having a carboxyl group

  [16] When the mass sum of (A), (B) and (C) is 100, the mass ratio of (A) :( B) :( C) is 30-80: 10-40: 5-20. [15] The polymer compound according to [15].

[17] The polymer compound according to [15] or [16], wherein the radical polymerizable monomer (B) is represented by the following formula (12):
Formula (12)

(In formula (12), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a monovalent organic group having a cyclic ether structure of four or more members.)

[18] The polymer compound according to any one of [15] to [17], wherein the radically polymerizable monomer (C) is represented by the following formula (13).
Formula (13)

(In formula (13), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a divalent organic group having 2 to 6 carbon atoms, and R ¹¹ represents a divalent organic group having 2 to 8 carbon atoms)

  [19] A coating composition in which the polymer compound according to any one of [13] to [18] is dissolved or dispersed in a solvent.

  [20] The coating composition according to [19], further comprising a curing agent.

  [21] A microorganism adhesion preventing material obtained by applying the coating composition of [19] to a substrate and drying the solvent.

  [22] A microorganism adhesion preventing material obtained by applying the coating composition according to [20] to a substrate, drying the solvent, and further curing.

  According to the present invention, a (meth) acrylate compound capable of imparting functions such as alkali solubility, crosslinkability, heat resistance and weather resistance to the radical polymer of the compound is easily produced in high purity and high yield. it can. Moreover, the novel polymer compound which has a microorganisms adhesion prevention function can be obtained by performing radical polymerization with the said (meth) acrylate compound and another radically polymerizable monomer as needed.

FIG. 1 shows a chart of the compound (2) of Example 1 measured by ¹ H-NMR. FIG. 2 shows a chart of the compound (4) of Example 2 measured by ¹ H-NMR. FIG. 3 shows a chart of the compound (6) of Example 3 measured by ¹ H-NMR. FIG. 4 shows a chart of the compound (8) of Example 4 measured by ¹ H-NMR. FIG. 5 is a graph showing the amount of bacteria attached to the test piece as a relative value of fluorescence intensity in Examples 6-1 to 10-1, Comparative Example 1-1, and Comparative Example 2.

  Hereinafter, the present invention will be described in detail. In the present specification, the expression “(meth) acrylate compound” means an acrylate compound and / or a methacrylate compound.

1. (Meth) acrylate compound The (meth) acrylate compound according to the present invention is represented by the following formula (1). Hereinafter, it is referred to as “(meth) acrylate compound (1)”.
Formula (1)

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain which may have oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group or fluorine atom having 1 to 4 fluorine atoms bonded thereto Represents a divalent hydrocarbon group optionally having 1 to 4 bonded fluorophenylene groups, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When R ¹ is a hydrogen atom, the radical polymerization rate is fast. On the other hand, when R ¹ is a methyl group, the stability of the compound is increased compared to the case of a hydrogen atom, and handling is facilitated. Among these, one in which R ¹ is a methyl group is a preferred embodiment.

R ² represents —R ³ NHCOO— or a single bond. R ³ represents a divalent linear hydrocarbon group which may have oxygen. However, in R ³ , oxygen atoms are not continuously bonded, and oxygen atoms are not attached to both ends of R ³ . Examples of R ³ include an alkylene group having 2 to 12 carbon atoms, an oxyalkylene group having 2 to 12 carbon atoms, and an arylene group having 6 to 12 carbon atoms.

Specific examples of the alkylene group having 2 to 12 carbon atoms include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ — and —CH— ( CH ₃ ) CH ₂ — and the like.
Specific examples of the oxyalkylene group having 2 to 12 carbon atoms include, for example, —CH ₂ CH ₂ OCH ₂ CH ₂ —, — (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ O ) ₃ CH ₂ CH _2- , -CH ₂ CH- (CH ₃ ) OCH ₂ CH- (CH ₃ )-,-(CH ₂ CH- (CH ₃ ) O) ₂ CH ₂ CH- (CH ₃ )-, -(CH ₂ CH- (CH ₃ ) O) ₃ CH ₂ CH- (CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ -,-(CH ₂ CH ₂ CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and — (CH ₂ CH ₂ CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ CH ₂ CH ₂ — and the like.

Specific examples of the arylene group having 6 to 12 carbon atoms include a p-phenylene group and an m-phenylene group. Among these, R ³ is preferably — (CH ₂ ) ₂ —, and R ² is a single bond or — (CH ₂ ) ₂ —NHCOO—, in order not to reduce the above-described characteristics of R ^{4 due} to fluorine. It is preferable that

R ⁴ represents a divalent hydrocarbon group which may have oxygen having a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto or a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto.

Specific examples of the fluorophenylene group include —C ₆ F ₄ —, —C ₆ F ₃ H—, —C ₆ F ₂ H ₂ —, and —C ₆ FH ₃ —, and the fluorine atom is 1 Specific examples of the divalent hydrocarbon group which may have oxygen having -4 bonded fluorophenylene groups include —CH ₂ C ₆ F ₄ CH ₂ —, —CH ₂ C ₆ F ₃ HCH ₂ -, --CH ₂ C ₆ F ₂ H ₂ CH _2- , --CH ₂ C ₆ FH ₃ CH _2- , --CH ₂ CH ₂ C ₆ F ₄ CH ₂ CH _2- , --CH ₂ CH ₂ C ₆ F ₃ HCH ₂ CH _2- , --CH ₂ CH ₂ C ₆ F ₂ H ₂ CH ₂ CH _2- , --CH ₂ CH ₂ C ₆ FH ₃ CH ₂ CH _2- , --C ₆ F ₄ --O-C ₆ F _{4 -, - CH 2 C 6 F} 4 CH 2 -O-CH 2 C 6 F 4 CH 2 - and the like. Among these, -C ₆ F ₄ -and -CH ₂ C ₆ F ₄ CH ₂ -are particularly preferable from the viewpoints of availability, economy, and fluorine content, and in particular, (2,3,5,6-tetrafluoro-p -Phenylene group) and (2,3,5,6-tetrafluoro-p-xylylene group) are more preferable.

R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. R ⁶ is preferably a hydrogen atom when imparting alkali developability, and is preferably a hydrogen atom or a methyl group when importance is attached to the function of preventing microbial adhesion.

Among the compounds contained in the (meth) acrylate compound (1), from the viewpoint of availability of raw materials, economy, and the above-described properties of R ⁴ fluorine are not reduced, preferred compounds are those represented by formula (2) and formula (3). , Formula (4), formula (5), formula (6), formula (7), formula (8), and compounds represented by formula (9). The compounds represented by formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), formula (8) and formula (9) are hereinafter referred to as compounds ( 2), compound (3), compound (4), compound (5), compound (6), compound (7), compound (8) and compound (9).

2. 2. Method for producing (meth) acrylate compound (1) 2-1. (Meth) acrylate compound (1): When R ⁶ is a hydrogen atom (Meth) acrylate compound (1), when R ⁶ is a hydrogen atom,
(I) a hydroxy compound having a tetrahydropyranyl group and a fluorophenylene group represented by formula (10) (hereinafter referred to as “hydroxy compound (10)”), and a (meth) acryloyl group-containing compound represented by formula (11) ( Hereinafter, a method obtained by reacting a “(meth) acryloyl group-containing compound (11)” and then deprotecting a tetrahydropyranyl group as a protecting group (formula (a) of the following [Chemical Formula 24]) , See formula (b), formula (c)),
(Ii) A method in which a (meth) acryl group-containing compound is directly reacted with one hydroxyl group of a dihydroxy compound having a fluorophenylene group (hereinafter referred to as “dihydroxy compound (14)”). )), But the production method (i) is higher in the yield and purity of the (meth) acrylate compound (1) than the production method (ii). Since it is obtained, it is preferable.

  2-1-1. Process for producing by reacting a hydroxy compound (10) with a (meth) acryloyl group-containing compound (11) and then deprotecting a tetrahydropyranyl group as a protecting group

[1] Hydroxy compound (10)
The hydroxy compound (10) used in this production method has a tetrahydropyranyl group as a protecting group by selectively reacting one hydroxyl group of the dihydroxy compound (14) with dihydropyran (DHP) as in the above formula (a). Is obtained. Usually, it is difficult to protect only one hydroxyl group, but the hydroxy compound (10) is preferentially produced.

Here, R ⁴ is identical to R ⁴ of formula (1), have an oxygen having 1-4 bound fluorophenylene group 1-4 bonded fluorophenylene group or a fluorine atom a fluorine atom The divalent hydrocarbon group which may be sufficient.

[2] Dihydroxy compound having fluorophenylene group The dihydroxy compound having a fluorophenylene structure and / or oxyfluorophenylene structure group used in the present invention is:
Formula (14)

R ⁴ is the same as R ⁴ in formula (1) and has an oxygen having a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto or a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto. It represents a divalent hydrocarbon group which may be present.

A tetrahydropyranyl group is abbreviated as THP, and specific examples of the compound represented by the formula (15) are shown below. Specific examples of the hydroxy compound (15) include HOC ₆ F ₄ OTHP, HOC ₆ F ₃ HOTHP, HOC ₆ F ₂ H ₂ OTHP, HOC ₆ FH ₃ OTHP, HOCH ₂ C ₆ F ₄ CH ₂ OTHP, and HOCH ₂ C. ₆ F ₃ HCH ₂ OTHP, HOCH ₂ C ₆ F ₂ H ₂ CH ₂ OTHP, HOCH ₂ C ₆ FH ₃ CH ₂ OTHP, HOCH ₂ CH ₂ C ₆ F ₄ CH ₂ CH ₂ OTHP, HOCH ₂ CH ₂ C ₆ F ₃ HCH ₂ CH ₂ OTHP, HOCH ₂ CH ₂ C ₆ F ₂ H ₂ CH ₂ CH ₂ OTHP, HOCH ₂ CH ₂ C ₆ FH ₃ CH ₂ CH ₂ OTHP, HOC ₆ F ₄ OC ₆ F ₄ OTHP and HOCH ₂ C ₆ F ₄ CH ₂ OCH ₂ C ₆ F ₄ CH ₂ OTHP is exemplified. The phenylene group contained in the hydroxy compound (14) shown above is preferably a p-phenylene group, and the xylylene group contained in the compound (14) shown above is preferably a p-xylylene group.

Among these, HOC ₆ F ₄ OTHP and HOCH ₂ C ₆ F ₄ CH ₂ OTHP are from the viewpoint of not reducing the fluorine content of the (meth) acrylate compound (1) in terms of availability of raw materials and having a fluorophenylene group. preferable.

  [3] (Meth) acryloyl group-containing compound (11)

The (meth) acryloyl group-containing compound used in the present invention is represented by the formula (11). R ¹ represents a hydrogen atom or a methyl group, X represents a halogen atom, —OCOC (R ¹ ) ═CH ₂ , —OR ³ NCO, or —OR ⁵ , preferably a halogen atom or —O (CH ₂ ) ₂ -NCO. R ³ represents a divalent linear hydrocarbon group which may have oxygen (however, oxygen atoms are not continuous, and oxygen atoms are not attached to both ends of R ³ . ), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  Specific examples of the (meth) acryloyl group-containing compound (11) include (meth) acrylic anhydride, (meth) acryloyl chloride, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid n-. Propyl, n-butyl (meth) acrylate, 1- (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate 6- (meth) acryloyloxyhexyl isocyanate, 10- (meth) acryloyloxydecyl isocyanate, 2- (meth) acryloyloxy-2-methyl-ethyl isocyanate, 2- (meth) acryloyloxy-1-methyl-ethyliso Aneto, 2- (meth) acryloyloxy-1,1-dimethyl - ethyl isocyanate, 4- (meth) acryloyloxy phenyl isocyanate, 3- (meth) acryloyloxy phenyl isocyanate, and (meth) acryloyl isocyanate and the like.

[4] Method for Producing Hydroxy Compound (10) The hydroxy compound (10) is obtained by reacting a dihydroxy compound (14) having a fluorophenylene group with dihydropyran (DHP).

  A known acidic catalyst can be used as a catalyst for the reaction. Specific examples include sodium hydrogen sulfate, sodium dihydrogen phosphate, p-toluenesulfonic acid and the like, and sodium hydrogen sulfate is particularly preferable.

  A nonpolar solvent can be used as a solvent for the reaction. Specific examples include hexane, heptane, cyclohexane, benzene, toluene, xylene, dibutyl ether, diethyl ether and the like.

As reaction temperature, 0-100 degreeC is preferable and 0-40 degreeC is more preferable. If it is less than 0 ° C., the reaction is slow, and if it exceeds 100 ° C., the two-sided protectors increase, such being undesirable.
The molar ratio during the reaction is dihydroxy compound (14): dihydropyran = 1: 1.0 to 10.0, more preferably 1: 1.0 to 4.0. If the molar ratio of dihydropyran to dihydro compound (14) is less than 1.0, the dihydroxy compound having a fluorophenylene group remains excessively, and if it exceeds 10.0, the dihydropyran excessively remains, which is not economical. It is not preferable.

[5] Method for producing (meth) acrylate compound (1) when R ⁶ is a hydrogen atom (meth) acrylate compound (1) is obtained by reacting hydroxy compound (10) with (meth) acryloyl group-containing compound (11). It is obtained by further deprotecting the compound of formula (15) obtained by the reaction.

  As a reaction catalyst of the hydroxy compound (10) and the (meth) acryloyl group-containing compound (11), when the compound represented by the formula (11) is other than isocyanate, a known basic catalyst is used as a reaction catalyst. Can be used. When the compound represented by the formula (11) is an isocyanate, a basic catalyst or a urethane bond forming catalyst can be used as a reaction catalyst.

  Examples of the basic catalyst include tertiary amines such as potassium carbonate, sodium carbonate, t-butoxypotassium, sodium hydride, triethylamine, triethylenediamine, DBU, pyridine, N, N-dimethyl-4-aminopyridine, and the like. It is done.

Examples of the urethane bond forming catalyst include organotin compounds such as dibutyltin dilaurate and tin octylate.
Examples of the reaction solvent include hexane, heptane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, dibutyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N-methylpyrrolidone, and the like. be able to.

As reaction temperature, 0-120 degreeC is preferable. If it is less than 0 ° C, the reaction is slow, and if it exceeds 120 ° C, polymerization is caused, which is not preferable.
The molar ratio during the reaction is hydroxy compound (10) :( meth) acryloyl group-containing compound (11) = 1: 0.90 to 5.0, more preferably 1: 1.0 to 3.0. is there. When the molar ratio of the (meth) acryloyl group-containing compound (11) to the hydroxy compound (10) is less than 0.9, the hydroxy compound (10) remains excessively. Since it lowers, it is not preferable. On the other hand, when the molar ratio of the (meth) acryloyl group-containing compound (11) exceeds 5.0, the (meth) acryloyl group-containing compound (11) remains and post-treatment becomes difficult, which is not preferable.

  The reaction time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If it is 1 hour or longer, no unreacted substance remains, and if it is 20 hours or shorter, the reaction time is short, which is economical. The reaction solution after the reaction is washed with deionized water, the organic solvent layer is dried, and the crude solvent containing the compound (15) represented by the formula (15) is removed by using an evaporator, a vacuum pump or the like to remove the reaction solvent and the reaction catalyst. You can get things. The (meth) acrylate compound (1) can be obtained by dissolving the obtained crude product in methanol and adding hydrochloric acid for deprotection.

  Formula (15)

(R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear hydrocarbon group which may have oxygen ( However, oxygen atoms are not continuous, and oxygen atoms are not attached to both ends of R ^3. ), R ⁴ is a fluorophenylene group having 1 to 4 fluorine atoms bonded or 1 to 4 fluorine atoms bonded Represents a divalent hydrocarbon group optionally having oxygen having a fluorophenylene group.)

  The equivalent of methanol is preferably 1.0 to 10 equivalents, more preferably 3.0 to 5.0 equivalents, relative to 1.0 equivalent of the above compound (15). The hydrochloric acid is preferably 0.1N to 12N. The reaction time is preferably 1 to 10 hours, more preferably 2 to 8 hours.

2-1-2. Method of directly reacting (meth) acryl group-containing compound (11) with one hydroxyl group of dihydroxy compound (14) (Meth) acrylate compound (1) is a dihydroxy compound having a fluorophenylene group as shown in formula (d) It can also be obtained by reacting (14) with a (meth) acryloyl group-containing compound (11).

Specific examples of the dihydroxy compound represented by the formula (14) include HOC ₆ F ₄ OH, HOC ₆ F ₃ HOH, HOC ₆ F ₂ H ₂ OH, HOC ₆ FH ₃ OH, and HOCH ₂ C ₆ F ₄ CH ₂ OH. , HOCH ₂ C ₆ F ₃ HCH ₂ OH, HOCH ₂ C ₆ F ₂ H ₂ CH ₂ OH, HOCH ₂ C ₆ FH ₃ CH ₂ OH, HOCH ₂ CH ₂ C ₆ F ₄ CH ₂ CH ₂ OH, HOCH ₂ CH ₂ C ₆ F ₃ HCH ₂ CH ₂ OH, HOCH ₂ CH ₂ C ₆ F ₂ H ₂ CH ₂ CH ₂ OH, HOCH ₂ CH ₂ C ₆ FH ₃ CH ₂ CH ₂ OH, HOC ₆ F ₄ OC ₆ F ₄ OH HOCH ₂ C ₆ F ₄ CH ₂ OCH ₂ C ₆ F ₄ CH ₂ OH is exemplified. Among these, HOC ₆ F ₄ OH and HOCH ₂ C ₆ F ₄ CH ₂ OH are particularly preferable from the viewpoint of availability of raw materials and a decrease in fluorine content of the (meth) acrylate compound (1).

  When the compound represented by the formula (11) is other than an isocyanato group-containing compound, a known acidic catalyst or basic catalyst can be used as a reaction catalyst. When the compound represented by the formula (11) is an isocyanato group-containing compound, a basic catalyst or a urethane bond forming catalyst can be used as a reaction catalyst.

Examples of the acidic catalyst include sulfonic acids such as p-toluenesulfonic acid, sulfuric acid, and the like.
Examples of the basic catalyst include tertiary amines such as potassium carbonate, sodium carbonate, t-butoxypotassium, sodium hydride, triethylamine, triethylenediamine, DBU, pyridine, N, N-dimethyl-4-aminopyridine, and the like. It is done.

Examples of the urethane bond forming catalyst include organotin compounds such as dibutyltin dilaurate and tin octylate.
As the reaction solvent, any solvent can be used as long as it is an inert solvent for both (meth) acrylic acid or compound (11) and compound (14). Specific examples include hexane, heptane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, dibutyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N-methylpyrrolidone, and the like. Can do.

As reaction temperature, 0-120 degreeC is preferable. If it is less than 0 ° C, the reaction is slow, and if it exceeds 120 ° C, polymerization is caused, which is not preferable.
As a molar ratio during the reaction, the dihydroxy compound (14) :( meth) acryloyl group-containing compound (11) is preferably 1: 0.40 to 2.0, more preferably 1: 0.45 to 1. .0. When the molar ratio of the (meth) acryloyl group-containing compound (11) to the dihydroxy compound (14) is less than 0.40, the dihydroxy compound (14) having a fluorophenylene group remains excessively, which is not economical. On the other hand, when the molar ratio of the (meth) acryloyl group-containing compound (11) exceeds 2.0, a large amount of bifunctional monomers in which the hydroxyl groups at both ends are (meth) acrylates are generated, such being undesirable.

  The reaction time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If it is 1 hour or longer, no unreacted substance remains, and if it is 20 hours or shorter, the reaction time is short, which is economical.

  The reaction solution after the reaction is washed with deionized water, the organic solvent layer is dried, the organic solvent is removed using an evaporator, a vacuum pump or the like to obtain a crude product containing compound (1), and if necessary, silica gel column chromatography. Compound (1) can be purified by a conventional method such as chromatography.

2-2. (Meth) acrylate compound (1): If R ⁶ where R ⁶ is an alkyl group having 1 to 4 carbon atoms (meth) acrylate compound (1) is an alkyl group having 1 to 4 carbon atoms, said 2-1 The method -2 can be applied as it is. In that case, a hydroxy compound having a fluorophenylene group of the following formula (17) is used instead of the dihydroxy compound of the formula (14).

(In the formula (17), R ⁴ is a divalent hydrocarbon which may have oxygen having a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto or a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto. And R ⁶ represents an alkyl group having 1 to 4 carbon atoms.)

Specific examples of the hydroxy compound represented by the formula (17) include HOC ₆ F ₄ OCH ₃ , HOC ₆ F ₃ HOCH ₃ , HOC ₆ F ₂ H ₂ OCH ₃ , HOC ₆ FH ₃ OCH ₃ , and HOCH ₂ C ₆ F. ₄ CH ₂ OCH ₃ , HOCH ₂ C ₆ F ₄ CH ₂ OC ₂ H ₅ , HOCH ₂ C ₆ F ₄ CH ₂ OC ₃ H ₇ , HOCH ₂ C ₆ F ₄ CH ₂ OC ₄ H ₉ , HOCH ₂ C ₆ F ₃ HCH ₂ OCH ₃ , HOCH ₂ C ₆ F ₂ H ₂ CH ₂ OCH ₃ , HOCH ₂ C ₆ FH ₃ CH ₂ OCH ₃ , HOCH ₂ CH ₂ C ₆ F ₃ HCH ₂ CH ₂ OCH ₃ , HOC ₆ F ₄ OC Examples are ₆ F ₄ OCH ₃ and HOCH ₂ C ₆ F ₄ CH ₂ OCH ₂ C ₆ F ₄ CH ₂ OCH ₃ . Among these, HOC ₆ F ₄ OCH ₃ and HOCH ₂ C ₆ F ₄ CH ₂ OCH ₃ are particularly preferable from the viewpoint of reducing the availability of raw materials and the fluorine content of the (meth) acrylate compound (1).

3. Polymerization of (meth) acrylate compound (1) The (meth) acrylate compound (1) is solid at room temperature and is relatively stable against heat and light, but the polymerization property is general (meta). ) Equivalent to acrylic ester.

  When the polymer is synthesized by copolymerizing the (meth) acrylate compound (1) alone or with other monomers, alkali solubility, crosslinkability, heat resistance, chemical resistance, weather resistance, low refractive index, low dielectric constant, low Functions such as surface tension and water repellency can be imparted. Therefore, it can be applied to an alkali development type photoresist used for semiconductor production, display members, printing plate making materials, and the like, and a protective film that requires heat discoloration. It can also be used as a raw material monomer for various coating materials, antifouling materials, and graft polymerization.

  In particular, when used as a raw material for a positive alkali development type photoresist resin used for semiconductor manufacturing, display members, printing plate making materials, etc., the hydroxyl group of the (meth) acrylate compound (1) is desorbed with an acid. In this case, examples of the protecting group include a t-butoxycarbonyl group, a t-butyl group, a 1-ethoxyethyl group, and a tetrahydropyranyl group. The (meth) acrylate compound (1) having a protective group introduced is further copolymerized with another radical polymerizable monomer to obtain a photoresist resin.

The polymer compound having a fluorophenylene group has a function of preventing microbial adhesion, and (A) a (meth) acrylate compound formula (1) represented by the following formula (1):

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain optionally having oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group or fluorine atom having 1 to 4 fluorine atoms bonded thereto Represents a divalent hydrocarbon group optionally having 1 to 4 bonded fluorophenylene groups, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(B) A radically polymerizable monomer having a cyclic ether structure of 4 or more members (C) A polymer compound obtained by radical copolymerization of a monomer composition containing a radically polymerizable monomer having a carboxyl group has a function of preventing microbial adhesion Is particularly good.

Here, as the radically polymerizable monomer (B) having a cyclic ether structure having four or more members, a compound represented by the following formula (12) is preferable.
Formula (12)

(In formula (12), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a monovalent organic group having a cyclic ether structure of four or more members.)

Here, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ represents a monovalent organic group having a cyclic ether structure of 4 or more members, and specific examples include an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxanyl group, and a dioxolanyl group. .

  Specific examples of such compounds include tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) (meth) Acrylate, [cyclohexanespiro-2- (1,3-dioxolan-4-yl)] methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and in particular tetrahydrofur Furyl (meth) acrylate is preferred.

Examples of the radical polymerizable monomer (C) having a carboxyl group include (meth) acrylic acid, crotonic acid, citraconic acid, itaconic acid, vinyl benzoic acid, and ω-carboxypolycaprolactone mono (meth) acrylate. Particularly preferred is a compound represented by the following formula (13).
Formula (13)

(In formula (13), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a divalent organic group having 2 to 6 carbon atoms, and R ¹¹ represents a divalent organic group having 2 to 8 carbon atoms)

Specific examples of R ¹⁰ include-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -and -CH- (CH ₃ ) CH _2-. Etc. Further, as R ¹¹ , specifically, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, —CH— (CH ₃ ) CH ₂ -, Phenylene group, cyclohexanylene group, cyclohexenylene group, methylcyclohexanylene group and the like.

  Specific examples of such a compound represented by the formula (13) include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropyl. Examples include phthalic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth) acryloyloxyethyl succinic acid is particularly preferable.

The microbial adhesion preventing function is expressed even in a polymer compound obtained by polymerizing the (meth) acrylate compound (1) represented by the formula (1) alone, but in order to develop a higher microbial adhesion preventing function,
(A) a (meth) acrylate compound represented by formula (1),
(B) a radically polymerizable monomer having an organic group having a cyclic ether structure of 4 or more members,
(C) A polymer compound obtained by copolymerizing a radically polymerizable monomer having a carboxyl group is particularly preferred.

  When the mass sum of the above (A), (B) and (C) is 100, the copolymerization ratio (mass ratio) is preferably (A) :( B) :( C) = 30-80: 10 It is the range of -40: 5-20, More preferably, it is (A) :( B) :( C) = 35-75: 15-35: 8-15. (A): (B): (C) = When it is out of the range of 30-80: 10-40: 5-20, the microorganisms adhesion prevention function falls.

  In addition, the polymer compound of the present invention is a radical polymerizable monomer (D) other than the above (A) to (C) and a radical for the purpose of imparting curability or adjusting the physical properties of other coating films. It may be copolymerized.

  (A) Specific examples of the radical polymerizable monomer copolymerized with the (meth) acrylate compound (1) include, for example, the above-mentioned radical polymerizable monomers (B) and (meth) having a cyclic ether structure having four or more members. Acrylic acid, crotonic acid, citraconic acid, itaconic acid, vinylbenzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypoly In addition to radically polymerizable monomers (C) having a carboxyl group such as caprolactone mono (meth) acrylate, citraconic anhydride, itaconic anhydride, tricyclodecane (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, phenyl (meth) Acrylate, benzyl (meth) acrylate, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxys (A) such as tylene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, trifluoromethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (B ) And (C) other than the radical polymerizable monomer (D).

  The density | concentration in the solvent at the time of superposition | polymerization of the whole radically polymerizable monomer of (A)-(D) is 10-70 mass% with respect to the whole reaction liquid to superpose | polymerize, Preferably it is 20-60 mass%. If it is less than 10% by mass, the polymerization reaction is not completed, or the molecular weight becomes too small. When it exceeds 70% by mass, the amount of heat generated during the polymerization reaction is large, and it becomes difficult to control the polymerization reaction.

[1] Radical polymerization initiator During polymerization, azobisisobutyronitrile, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane- 1-carbonitrile), azo initiators typified by 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, tert-amylperoxy- 2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate Thermal radical polymerization initiators such as representative organic peroxides can be used.

  Although the usage-amount of a thermal radical polymerization initiator is not specifically limited, Preferably it is 0.5-10 mass% with respect to all the radically polymerizable monomers, More preferably, it is 1-5 mass%. If it is less than 0.5% by mass, the unreacted residual monomer tends to increase, such being undesirable. If it exceeds 10% by mass, the reaction proceeds rapidly and it may be difficult to keep the temperature constant.

[2] Polymerization solvent During polymerization, 1-propanol, isopropyl alcohol, butanol, ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3- Methoxy pig Nord, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethyl lactate and the like.

[3] Chain Transfer Agent Specific examples of such chain transfer agents to which a chain transfer agent can be added for the purpose of adjusting the molecular weight of the polymer compound of the present invention during polymerization include 1-dodecanethiol, 1-decane Mention may be made of thiol compounds such as thiol and mercaptopropionic acid.

  The number average molecular weight of the polymer compound of the present invention is preferably 3000 to 200000, particularly preferably 5000 to 100,000. Here, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography. When the number average molecular weight is less than 3000, the strength of the coating film is lowered. If it exceeds 200,000, the solubility in a solvent will be low, and the viscosity will become too high even if it is dissolved.

4). Method of Use The polymer compound of the present invention can be used by, for example, applying a composition dissolved or dispersed in a solvent or the like to a substrate and then removing the solvent by heating or the like. The solvent used in the composition is not particularly limited as long as it can dissolve or disperse the polymer compound of the present invention. For example, the solvent used as the polymerization solvent of the present invention can be used as it is.

[1] Curing Agent / Curing Accelerator In order to increase the strength of the coating film or increase the hardness, a curing agent may be further added to the composition. Examples of the curing agent include polyepoxy compounds and polyisocyanate compounds. The polyepoxy compound reacts with the carboxyl group of the polymer compound of the present invention to be crosslinked and cured, and the polyisocyanate compound reacts with the hydroxyl group or carboxyl group of the polymer compound of the present invention to be crosslinked and cured. it can.

  Polyepoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, biphenyl. Aralkyl-type epoxy resins, naphthalene-type epoxy resins, naphthalene-aralkyl-type epoxy resins, triphenylmethane-type epoxy resins, trimethylolpropane triglycidyl ether and pentaerythritol polyglycidyl ether and other glycidyl ether-type epoxy resins, hexahydrophthalic acid glycidyl ester , Dimer acid glycidyl ester, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, etc. Examples include linear aliphatic epoxy resins such as glycidylamine epoxy resins, epoxidized polybutadiene and epoxidized soybean oil, and (co) polymers of radical polymerizable monomers having an epoxy group such as glycidyl (meth) acrylate. be able to. The said polyepoxy compound can be used individually or in mixture of 2 or more types. As for the compounding quantity of the said polyepoxy compound, 5-100 mass parts is preferable with respect to 100 mass parts of resin components total in a composition.

  If a compound having an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate is used as a radical polymerizable monomer of the polymer compound of the present invention, a polyepoxy is used as a curing agent. It is not necessary to use a compound.

  When using a polyepoxy compound as a curing agent, a curing accelerator may be used. Specific examples of the curing accelerator include imidazoles, tertiary amines, phenols, Lewis acid salts and the like, and one or more of these can be used. As for the compounding quantity of the said hardening accelerator, 0.01-5.0 mass parts is preferable with respect to 100 mass parts of resin components in a composition total. If the amount is less than 0.01 parts by mass, the effect of adding a curing accelerator may not be obtained. If the amount exceeds 5.0 parts by mass, gelation occurs or the curing accelerator remains unreacted. As a result, there are concerns about performance degradation such as coloring.

  Specific examples of the polyisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 4-trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate, (o, m, or p) -xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 3, Diisocyanate compounds such as 3′-methyleneditolylene-4,4′-diisocyanate and 4,4′-diphenyl ether diisocyanate and their isocyanurs Over door body and the bullet body, and the like. These polyisocyanate compounds can be used alone or in combination of two or more. As for the compounding quantity of the said polyisocyanate compound, 3-50 mass parts is preferable with respect to the resin component total 100 mass parts in a composition.

  When a polyisocyanate compound is used as a curing agent, no catalyst may be used, but a curing accelerator may be added. Examples of such a curing catalyst include organic tin compounds such as dibutyltin dilaurate and tin octylate, and the blending amount is 0.001 to 1 part by mass with respect to 100 parts by mass of the resin component. If it is less than 0.001 part by mass, curing does not proceed, and if it exceeds 1 part by mass, the pot life is insufficient.

[2] Additives In the composition containing the polymer compound of the present invention, various additives such as plasticizers, fillers, pigments, deterioration inhibitors, ultraviolet absorbers, repellents, etc. Additives may be included.

[3] Curing method A composition comprising the polymer compound of the present invention, a curing agent, and a curing accelerator is applied to a substrate, and after the solvent is removed by heating or the like, the composition is cured at room temperature or by heating to toughness It can be set as a simple coating film. The preferred temperature range for heat curing is 40 to 180 ° C, more preferably 60 to 150 ° C. If it is lower than 40 ° C., curing takes too much time. If it exceeds 180 ° C, the coating film may be colored. In addition, as said base material, various base materials, such as an inorganic base material and an organic base material, can be used. The composition containing the polymer compound of the present invention can be suitably used, for example, as a paint.

5. In addition, the polymer compound thus obtained by radical polymerization is blended with a photoacid generator and other necessary additives, then applied to a substrate, dried in a solvent, and then in an ultraviolet region such as an excimer laser. Pattern exposure is performed with the light. When the acid is generated in the exposed portion, the protective group bonded to the hydroxyl group of the (meth) acrylate compound (1) unit contained in the resin is eliminated, and alkali developability is exhibited. Examples of the alkaline developer to be used include aqueous solutions of sodium carbonate, sodium hydroxide, potassium hydroxide, etc., but in the case of photoresist applications, alkali metal ions or alkaline earth metal ions such as tetramethylammonium hydroxide are used. An alkaline developer not contained is preferred.

  In addition, in order to utilize the microbe adhesion prevention function, which is another important function of the polymer compound of the present invention, it was provided in the inner surface of water pipes and drain pipes in treatment facilities, factories, bathrooms, and air conditioning equipment. This is achieved by forming a coating / coating on members / parts / structures that tend to cause condensation such as the inner surface of the circulation pipe, the interior / exterior of the building, the water supply facility, the refrigeration / refrigeration facility, and the air conditioner.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[Analysis method]
(1) Measurement of molecular weight of polymer The measurement conditions of GPC are as follows.
Device name: Shodex GPC-101
Column: Shodex KF-802, KF-803, KF-805
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min
Detector: Shodex RI-71
Temperature: 40 ° C
Under the above measurement conditions, the weight average molecular weight was calculated using a calibration curve prepared using a polystyrene standard.

(2) GC (gas chromatography): The column was “InertCap 1” manufactured by GL Sciences Inc., and measurement was performed under the following conditions.
Column temperature and rate of temperature rise: held at 100 ° C. for 0 minute, heated at 20 ° C./minute and held at 300 ° C. for 5 minutes Detector: FID
Detector temperature: 330 ° C
Inlet temperature: 330 ° C

(3) ¹ H-NMR: Measured using “JNM-AL400” manufactured by JEOL Ltd. using tetramethylsilane as an internal standard substance.

(4) HPLC (High Performance Liquid Chromatography): The column was measured using the “Shodex 5C8 4E” manufactured by Showa Denko KK under the following conditions.
Column temperature: 40 ° C. Mobile phase: Acetonitrile / water = 2/1 (volume ratio), 2 mmol / liter tetra-n-butylammonium perchlorate elution rate: 1 ml / min Detection wavelength: 254 nm

(5) Acid value: measured in accordance with JIS K0070.
[Synthesis of Compound (2)]

Production Example 1 (Synthesis of Compound (10) -1)
In a 2000 mL separable flask equipped with a nitrogen gas inlet tube and a stirring blade, 157.5 g of TFDM (2,3,5,6-tetrafluoro-p-phenylenedimethanol, manufactured by SHANG YU FINECHEM CHEMICAL Co., Ltd.) 0.750 mol), toluene 500 ml, dimethyl sulfoxide 20 ml, 3,4-dihydro-2H-pyran 140 g (1.658 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 5M sodium hydrogensulfate aqueous solution 150 ml was added, and under a nitrogen stream The reaction was allowed to proceed for 5 hours at room temperature with stirring. After the reaction, the reaction solution was diluted with toluene, the organic layer was washed with deionized water, a 5% aqueous sodium hydroxide solution, and deionized water in this order, and the organic layer was dried over magnesium sulfate. Furthermore, toluene was removed using an evaporator and a vacuum pump to obtain a crude product of compound (10) -1 having a GC purity of 69.4%. The obtained crude product of compound (10) -1 was used in the next reaction without purification.

Example 1 (Synthesis of Compound (2))
In a 2000 mL separable flask equipped with a nitrogen gas introduction tube and a stirring blade, 150.0 g (0.354 mol, GC purity: 69.4%) of the compound (10) -1 synthesized as described above, 750 ml of toluene, A 48% aqueous sodium hydroxide solution (85 g) was added, and the mixture was stirred for 15 minutes. Next, 81.0 g of methacrylic acid chloride (0.775 mol, Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at room temperature for 3 hours. Further, 10.8 g (0.103 mol) of methacrylic acid chloride was added and stirred at room temperature for 3 hours. After the reaction, the reaction mixture was diluted with toluene, and the organic layer was washed 3 times with water and dried over magnesium sulfate. 0.075 g of hydroquinone was added, and toluene was removed using an evaporator and a vacuum pump to obtain a crude product of compound (15) -1 having a GC purity of 73.5%.

To the crude product of compound (15) -1, 250 ml of methanol and 20 ml of concentrated hydrochloric acid were added and stirred at room temperature for 5 hours using a magnetic stirrer. After the reaction, the reaction mixture was diluted with toluene, and the organic layer was washed 3 times with water and dried over magnesium sulfate. Toluene was removed using an evaporator and a vacuum pump to obtain a crude product. This crude product was washed with a solvent of toluene / hexane = 1/5 to obtain 71.5 g of a white solid compound (2) (two-stage yield: 72.6%, GC purity: 99.0%). . ¹ H-NMR (400 MHz, DMSO, TMS, ppm) δ: 6.03 (1H), δ: 5.73 (1H), δ: 5.62 (1H), δ: 5.31 (2H), δ : 4.57 (2H), δ: 1.87 (3H)
[Synthesis of Compound (4)]

Example 2 (Synthesis of Compound (4))
In a 100 mL eggplant flask, 10.0 g (0.022 mol, GC purity: 64.0%) of compound (10) -1 synthesized as described above, 4.0 g (0.026 mol, 2-methacryloyloxyethyl isocyanate) Showa Denko Co., Ltd.) and dibutyltin dilaurate 0.014 g (manufactured by Kyodo Yakuhin Co., Ltd.) were added and stirred at room temperature for 8 hours using a magnetic stirrer. After the reaction, 20 ml of methanol and 1.0 ml of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for 4 hours using a magnetic stirrer. After the reaction, the reaction mixture was diluted with toluene, and the organic layer was washed 3 times with water and dried over magnesium sulfate. Toluene was removed using an evaporator and a vacuum pump to obtain a crude product. This crude product was washed with a solvent of THF / hexane = 1/5, and 7.23 g of a white solid compound (4) (two-stage yield: yield 90.8%, GC purity: 95.5%) was obtained. Obtained. ¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 6.08 (1H), δ: 5.57 (1H), δ: 5.39 (2H), δ: 5.21 (1H), δ: 5.01 (2H), δ: 4.81 (2H), δ: 4.21 (2H), δ: 3.49 (2H)
Example 3 (Synthesis of Compound (6))

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol (hereinafter abbreviated as “MTFBAL” manufactured by SHANG YU FINECHEM CHEMICAL Co., Ltd.) in a 200 mL three-necked flask equipped with an air introduction tube and a stirring blade 18.0 g (0.080 mol), 50 ml of toluene, 12.0 g (0.14 mol) of methacrylic acid and 0.74 g (0.0075 mol) of sulfuric acid were added, and the mixture was stirred at 120 ° C. for 7 hours while stirring in an air stream. After the reaction, the reaction solution was diluted with toluene, the organic layer was washed with deionized water, 5% aqueous sodium hydroxide solution and deionized water in this order, and the organic layer was dried over magnesium sulfate. Furthermore, toluene was removed using an evaporator and a vacuum pump to obtain 22.0 g (yield 93.7%) of Compound (6) having a GC purity of 98.1%. ¹ H-NMR (400 MHz, CDCl 3, TMS, ppm) δ: 6.10 (1H), δ: 5.59 (1H), δ: 5.28 (2H), δ: 4.57 (2H), δ : 3.39 (3H), [delta]: 1.92 (3H).

  Example 4 (Synthesis Example of Compound (8))

In a 50 mL Erlenmeyer flask, MTFBAL 8.96 g (0.040 mol, SHANG YU FINECHEM CHEMICAL), 2-methacryloyloxyethyl isocyanate 6.20 g (0.040 mol, Showa Denko KK), dibutyltin dilaurate 0.0027 g (manufactured by Kyodo Pharmaceutical Co., Ltd.) was added, and the mixture was stirred at room temperature for 8 hours. After the reaction, the solid was washed with hexane to obtain 15.0 g (yield 98.9%) of a white solid (8) having a GC purity of 96.4%. ¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 6.08 (1H), δ: 5.57 (1H), δ: 5.22 (2H), δ: 4.97 (1H), δ: 4.56 (2H), δ: 4.22 (2H), δ: 3.52 (2H), δ: 3.38 (3H), δ: 1.92 (3H).

Example 5 (polymerization of compound (2))
In a 50 mL eggplant flask, 3.0 g (0.011 mol) of the compound (2) synthesized as described above, 0.060 g of benzoyl peroxide (0.25 mmol, manufactured by Kanto Chemical Co., Inc.), 7.0 g of butyl acetate (Manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred at 90 ° C. for 3 hours using a magnetic stirrer and oil bath. After the reaction, the mixture was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 2.50 g of a white solid polymer compound (yield: 83%, Mn / Mw = 9700/60000).

Example 6 (Copolymerization of Compound (2))
In a 50 mL two-necked eggplant flask, the compound (2) synthesized as described above 2.22 g (0.0080 mol), tetrahydrofurfuryl acrylate 1.25 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0080 mol), Light ester HO-MS 0.47 g (trade name, manufactured by Kyoeisha Chemical Co., Ltd., 2-methacryloyloxyethyl succinic acid 0.0020 mol), benzoyl peroxide 0.037 g (manufactured by Kanto Chemical Co., Ltd.), butyl acetate 13.0 g And stirred at 90 ° C. for 3 hours using a magnetic stirrer and oil bath. After the reaction, reprecipitation with hexane, and the resulting solid was filtered and dried, and 3.90 g of a white solid polymer compound (yield: 99.0%, Mn / Mw = 18600/114000, acid value: 36.5 mg KOH) / G).

Example 7 (Copolymerization of Compound (2))
In a 50 mL two-necked eggplant flask, 2.78 g (0.01 mol) of compound (2) synthesized as described above, 1.56 g of tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.01 mol), 0.58 g of light ester HO-MS (manufactured by Kyoeisha Chemical Co., Ltd., 0.0025 mol), 0.20 g of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 0.0013 mol), dimethyl azobis (isobutyrate) 055 g (Wako Pure Chemical Industries, Ltd.) and 20.0 g of ethanol were added, and the mixture was refluxed for 5 hours using a magnetic stirrer and oil bath. After the reaction, it was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 4.73 g of a white solid polymer compound (yield: 97.0%, Mn / Mw = 10000/44000).

Example 8 (polymerization of compound (6))
In a 50 mL two-necked eggplant flask, 4.00 g (0.014 mol) of the compound (6) synthesized as described above, 0.040 g of benzoyl peroxide (manufactured by Kanto Chemical Co., Inc.), and 16.0 g of butyl acetate were added. In addition, the mixture was stirred at 90 ° C. for 3 hours using a magnetic stirrer and an oil bath. After the reaction, it was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 3.40 g of a white solid polymer compound (yield: 85.0%, Mn / Mw = 6500/22500).

Example 9 (copolymerization of compound (6))
In a 50 mL two-necked eggplant flask, compound (6) synthesized as described above 2.34 g (0.080 mol), tetrahydrofurfuryl acrylate 1.25 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0080 mol), Add 0.46 g of light ester HO-MS (manufactured by Kyoeisha Chemical Co., Ltd., 0.0020 mol), 0.033 g of benzoyl peroxide (manufactured by Kanto Chemical Co., Ltd.), 15.0 g of butyl acetate, and use a magnetic stirrer and oil bath. Stir at 90 ° C. for 3 hours. After the reaction, the mixture was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 3.80 g (yield: 93.8%, Mn / Mw = 13200/67100) of a white solid polymer compound.

Example 10 (Copolymerization of Compound (8))
In a 50 mL two-necked eggplant flask, 3.03 g (0.080 mol) of the compound (8) synthesized as described above, 1.25 g of tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0080 mol), Add 0.46 g of light ester HO-MS (manufactured by Kyoeisha Chemical Co., Ltd., 0.0020 mol), 0.040 g of benzoyl peroxide (manufactured by Kanto Chemical Co., Ltd.), 16.0 g of butyl acetate, and use a magnetic stirrer and oil bath. Stir at 90 ° C. for 3 hours. After the reaction, it was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 4.45 g of a white solid polymer compound (yield: 93.7%, Mn / Mw = 11400/71200).

Example 11 (Copolymerization of Compound (2))
In a 100 mL two-necked eggplant flask, 7.00 g (0.0256 mol) of the compound (2) synthesized as described above, 3.00 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (Tokyo Chemical Industry Co., Ltd.) , 0.030 mol), benzoyl peroxide 0.10 g (manufactured by Kanto Chemical Co., Inc.) and butyl acetate 40.0 g were added, and the mixture was stirred at 90 ° C. for 3 hours using a magnetic stirrer and oil bath. After the reaction, the mixture was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 9.50 g (yield: 95.0%, Mn / Mw = 19600/88500) of a white solid polymer compound.

Comparative Example 1
In a 50 mL two-necked eggplant flask, 0.80 g of methyl methacrylate (manufactured by Kanto Chemical Co., 0.080 mol), 1.25 g of tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0080 mol), light ester HO -MS 0.46 g (manufactured by Kyoeisha Chemical Co., Ltd., 0.0020 mol), 0.023 g of benzoyl peroxide (manufactured by Kanto Chemical Co., Ltd.), 12.0 g of butyl acetate were added, and at 90 ° C. using a magnetic stirrer and oil bath. Stir for 3 hours. After the reaction, it was reprecipitated with hexane, and the resulting solid was filtered and dried to obtain 2.40 g of polymer compound (yield: 94.9%, Mn / Mw = 24400/70100).

[Preparation of specimen]
Example 6-1
After the polymer compound of Example 6 was dissolved in 1,3-dioxolane, it was applied to Shimbox BXS10-005 (SUS, manufactured by Iwata Manufacturing Co., Ltd.) (hereinafter, SUS) and dried at 120 ° C. for 1 hour. As a result, a test piece with a microorganism adhesion preventing film was obtained. This was designated Example 6-1.

Example 6-2
3.1 g of the polymer compound obtained in Example 6 and bisphenol A type epoxy resin Epototo YD-128 (manufactured by Nippon Steel Chemical Co., Ltd.) 0.38 g, triphenylphosphine as a catalyst (manufactured by Hokuko Chemical Co., Ltd.) After dissolving 17 mg in 1,3-dioxolane, it was applied to SUS and cured at 120 ° C. for 3 hours to obtain a test piece with a microorganism adhesion preventing film. This was designated Example 6-2.

Example 7-1
Example 7 After dissolving 1.00 g of the obtained polymer compound and 10 mg of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) as a catalyst in propylene glycol monomethyl ether acetate, it is applied to SUS and cured at 120 ° C. for 2 hours. Thus, a test piece with a microorganism adhesion preventing film was obtained.

Example 8-1
Using the polymer compound of Example 8, a test piece with a microorganism adhesion preventing film was obtained in the same manner as in Example 6-1.

Example 9-1
Using the polymer compound of Example 9, a test piece with a microorganism adhesion preventing film was obtained in the same manner as in Example 6-1.

Example 10-1
Using the polymer compound of Example 10, a test piece with a microorganism adhesion preventing film was obtained in the same manner as in Example 6-1.

Comparative Example 1-1
Comparative Example 1-1 was obtained by preparing a coating film of the polymer compound of Comparative Example 1 in the same manner as in Example 6-1.

Comparative Example 2
Untreated SUS was used as a comparative test piece. This was designated as Comparative Example 2.

[Evaluation of antimicrobial adhesion performance]
About the obtained test piece, the microorganisms adhesion prevention function was evaluated by the following E. coli exposure test.

(1) Escherichia coli suspension preparation The E. coli JM109 strain was incubated at 37 ° C on LBplate (1% peptone, 0.5% yeast extract, 0.5% sodium chloride, 2% agar sterilized after 121 ° C / 20 minutes sterilization). Incubated overnight. The grown colonies were inoculated with 5 ml of LBbroth (1% peptone, 0.5% yeast extract, 0.5% sodium chloride, sterilized at 121 ° C / 20 minutes), and cultured with shaking at 37 ° C overnight. . Turbidity was about 3 (late logarithmic phase). This suspension was diluted 10-fold with physiological saline (0.2 μm filter sterilized by filtration) and immediately used.

(2) Escherichia coli exposure and measurement The test pieces of Examples and Comparative Examples were cut into about 10 mm squares and placed in 12-well microplates. 3 mL of the aforementioned E. coli suspension was added thereto. After shaking for 3 hours at 80 rpm, the test piece was taken out and transferred to a 12-well microplate containing 3 ml of pure water for washing (washing 3 times). Next, the test piece was placed in a 24-well microplate, and 0.5 mL of an aqueous solution of 5% Alamar Blue (registered trademark, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto.

Here, an unexposed test piece as a blank was placed in another 24-well microplate, and a solution in which 0.5 ml of 5% Alamar Blue aqueous solution was similarly added was also prepared.
After standing for 2 hours, 100 μL of a part of the solution was transferred to a 96-well microplate and excited at a wavelength of 560 nm, and the fluorescence intensity at 590 nm was measured. It has been confirmed in advance that there is a correlation between the measured fluorescence intensity and the amount of microorganisms, and that the fluorescence intensity is an indicator of the amount of microorganisms. And the difference of the fluorescence intensity of a sample and a blank is taken and the relative value of the fluorescence intensity of the Example and the comparative example 3 when the fluorescence intensity measured by the below-mentioned comparative example 2 is set to 100 is shown in the graph of FIG. It was.

  As is clear from FIG. 5, the test piece of the example has an extremely small amount of microorganisms (fluorescence intensity) compared to the test piece of the comparative example, and it was shown that the test piece can be suitably used as a microorganism adhesion preventing material.

Claims (22)

A (meth) acrylate compound represented by the following formula (1).
Formula (1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain which may have oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group in which 1 to 4 fluorine atoms are bonded, or fluorine (It represents a divalent hydrocarbon group optionally having oxygen having a fluorophenylene group having 1 to 4 atoms bonded thereto, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The (meth) acrylate compound according to claim 1, wherein R ⁴ is a 2,3,5,6-tetrafluoro-p-xylylene group. The (meth) acrylate compound according to claim 1, wherein R ² is a single bond or —R ³ NHCOO—, and R ³ is — (CH ₂ ) ₂ —. The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (2).
Formula (2)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (3).
Formula (3)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (4).
Formula (4)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (5).
Formula (5)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (6).
Formula (6)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (7).
Formula (7)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (8).
Formula (8)
The (meth) acrylate compound according to claim 1, which is a compound represented by the following formula (9).
Formula (9)
The tetrahydropyranyl group is deprotected from the compound obtained by the reaction after reacting the hydroxy compound represented by the following formula (10) and the (meth) acryloyl group-containing compound represented by the formula (11): The manufacturing method of the (meth) acrylate compound as described in any one of claim | item 1 -7.
Formula (10)
(In the formula (10), R ⁴ is a divalent hydrocarbon which may have oxygen having a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto or a fluorophenylene group having 1 to 4 fluorine atoms bonded thereto. Represents a group.)
Formula (11)
(In Formula (11), R ¹ represents a hydrogen atom or a methyl group, X represents a halogen atom, —OCOC (R ¹ ) ═CH ₂ , —OR ⁵ or —OR ³ NCO, and R ³ represents oxygen. Represents a divalent linear hydrocarbon group which may have (provided that oxygen atoms are not continuous and oxygen atoms are not present at both ends of R ³ ), and R ⁵ is a hydrogen atom Or represents a C1-C4 alkyl group.)   The high molecular compound obtained by superposing | polymerizing independently the (meth) acrylate compound as described in any one of Claims 1-11.   The high molecular compound obtained by superposing | polymerizing the monomer containing the (meth) acrylate compound as described in any one of Claims 1-11. The polymer compound according to claim 14, obtained by copolymerizing the following (A), (B) and (C).
(A) (Meth) acrylate compound represented by the following formula (1) (1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents —R ³ NHCOO— or a single bond, and R ³ represents a divalent linear chain which may have oxygen. Represents a hydrocarbon group (however, oxygen atoms are not continuous and oxygen atoms are not attached to both ends of R ³ ), and R ⁴ is a fluorophenylene group or fluorine atom having 1 to 4 fluorine atoms bonded thereto Represents a divalent hydrocarbon group which may have oxygen having 1 to 4 bonded fluorophenylene groups, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
(B) Radical polymerizable monomer having an organic group having a cyclic ether structure of 4 or more members (C) Radical polymerizable monomer having a carboxyl group   When the total mass of (A), (B), and (C) is 100, the mass ratio of (A) :( B) :( C) is 30-80: 10-40: 5-20. The polymer compound according to claim 15. The polymer compound according to claim 15 or 16, wherein the radically polymerizable monomer (B) is represented by the following formula (12).
Formula (12)
(In formula (12), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a monovalent organic group having a cyclic ether structure of four or more members.) The polymer compound according to any one of claims 15 to 17, wherein the radically polymerizable monomer (C) is represented by the following formula (13).
Formula (13)
(In formula (13), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a divalent organic group having 2 to 6 carbon atoms, and R ¹¹ represents a divalent organic group having 2 to 8 carbon atoms)   A coating composition in which the polymer compound according to any one of claims 13 to 18 is dissolved or dispersed in a solvent.   The coating composition according to claim 19, further comprising a curing agent.   A microorganism adhesion preventing material obtained by applying the coating composition of claim 19 to a substrate and drying the solvent.   A microorganism adhesion preventing material obtained by applying the coating composition according to claim 20 to a substrate, drying the solvent, and further curing.