JP2005170936A - Method of manufacturing (meth)acrylate with fluorinated alkyl group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of easily manufacturing a (meth)acrylate with a fluorinated alkyl group under mild conditions, which can be preferably used for an optical material, a coating material or the like. <P>SOLUTION: In the method, of manufacturing the (meth)acrylate with the fluorinated alkyl group, the (meth)acrylate with fluorinated alkyl group is manufactured through Michael addition reaction, using a compound (a1) with two or more (meth)acryloyl group, and a compound (a2) with a fluorinated alkyl group and an active hydrogen. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a mild and simple method for producing a fluorinated alkyl group-containing (meth) acrylate.

  Conventionally, fluorinated alkyl group-containing (meth) acrylates are used alone as optical materials such as anti-reflective coatings in order to form a three-dimensional structure through cross-linking reactions with optical properties such as reducing the refractive index. Alternatively, it is useful to use a curable composition containing the same, and various compounds, production methods thereof, and compositions containing the same have been proposed (see, for example, Patent Document 1). However, the fluorinated alkyl group-containing (meth) acrylate described in Patent Document 1 uses a condensation reaction between a polyol, perfluoroalkylcarboxylic acid, and (meth) acrylic acid as a production method thereof, so that sulfuric acid or the like is used as a synthesis catalyst. In addition, since the condensation reaction is an equilibrium reaction, it is necessary to exclude water produced as a by-product in the system in order to make the synthesis reaction proceed smoothly. Since it is heated to a high temperature, there are problems such as not only severe reaction conditions but also limited equipment that can be used.

JP-A-9-157326 (page 3)

  In view of such a situation, an object of the present invention is to provide a milder and simpler method for producing a fluorinated alkyl group-containing (meth) acrylate.

  The present inventors diligently studied to solve the above-described problems, and as a result, a Michael addition reaction was performed using a compound having two or more (meth) acryloyl groups and a compound having a fluorinated alkyl group and active hydrogen. The inventors have found that a method for producing a fluorinated alkyl group-containing (meth) acrylate can solve these problems, and have completed the present invention.

  That is, the present invention uses a compound (a1) having two or more (meth) acryloyl groups and a compound (a2) having a fluorinated alkyl group and active hydrogen, and then fluorinated via a Michael addition reaction. The present invention provides a method for producing a fluorinated alkyl group-containing (meth) acrylate, characterized by producing an alkyl group-containing (meth) acrylate.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing simply the fluorinated alkyl group containing (meth) acrylate which can be used suitably for optical materials, a coating material, etc. on mild conditions can be provided. In this production method, a commercially available or manufacturable polyfunctional (meth) acrylate can be used as a raw material, and since the Michael addition reaction is applied, there is no by-product component and the reaction proceeds stoichiometrically. A fluorinated alkyl group-containing (meth) acrylate having a desired fluorine atom content can be obtained, and has high industrial application value.

Hereinafter, the present invention will be described in detail.
In the present invention, the (meth) acryloyl group is a generic term for an acryloyl group and a methacryloyl group. In addition, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group), and one in which some hydrogen atoms in the alkyl group are substituted with fluorine atoms ( For example, HCF ₂ CF ₂ CF ₂ CF ₂ — and the like. Incidentally, those containing an oxygen atom in the fluorinated alkyl group _{(e.g., CF 3 - (OCF 2 CF} 2) 2 - , etc.) is also included in this definition.

  The production method of the present invention utilizes a Michael addition reaction of an active hydrogen-containing group to a (meth) acryloyl group, and specifically, to a compound (a1) containing two or more (meth) acryloyl groups. This utilizes a Michael addition reaction between the compound (a2) having a fluorinated alkyl group and active hydrogen. Since this reaction is an addition reaction, there are no compounds by-produced by the reaction, and the reaction conditions described below can be allowed to proceed under mild conditions.

  The compound (a1) having two or more (meth) acryloyl groups used in the present invention is not particularly limited as long as it contains two or more (meth) acryloyl groups in the molecule. Although selected, from the viewpoint of easy industrial availability of raw materials and the ability to select mild reaction conditions, the following general formula (3)

〔式中、Ｒ’は炭素数１〜２４のアルキル基、炭素数１〜２４のアルキルカルボニルオキシ基、ＣＨ_２＝ＣＨＣＯ_２ＣＨ_２−、ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ_２ＣＨ_２−、繰り返し数が１以上で末端が水素原子或いは炭素数１〜１８のアルキル基で封鎖された（ポリ）オキシアルキレン基、炭素数１〜１２のアルキロール基、又は下記一般式（４）

[Wherein, R ′ represents an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, (Poly) oxyalkylene group having 1 or more repeats and the end blocked with a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkylol group having 1 to 12 carbon atoms, or the following general formula (4)

（式中、Ｒ^３は（メタ）アクリロイル基であり、Ｒ^４は水素原子又は炭素数１〜１８のアルキルカルボニル基であり、ｔは０〜３の整数であり、ｕは０〜３の整数であって且つｔ＋ｕ＝３である。）
で表される基であり、Ｒ^１は（メタ）アクリロイル基であり、Ｒ^２は水素原子又は炭素数１〜１８のアルキルカルボニル基であり、ｒは２又は３であり、ｓは０又は１であって且つｒ＋ｓ＝３である。〕
で表される化合物（ａ１−１）、シアヌレート環含有トリ（メタ）アクリレート（ａ１−３）、又はリン酸トリ（メタ）アクリレート（ａ１−４）であることが好ましい。

(In the formula, R ³ is a (meth) acryloyl group, R ⁴ is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, t is an integer of 0 to 3, and u is an integer of 0 to 3) And t + u = 3.)
R ¹ is a (meth) acryloyl group, R ² is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, r is 2 or 3, and s is 0 or 1 And r + s = 3. ]
It is preferable that it is a compound (a1-1) represented by these, a cyanurate ring containing tri (meth) acrylate (a1-3), or phosphoric acid tri (meth) acrylate (a1-4).

Among these, the compound (a1) having two or more (meth) acryloyl groups is represented by the general formula (3) [wherein R ′ is a linear alkyl group having 1 to 4 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, or an alkylol group having 1 to 3 carbon atoms, or a group represented by the general formula (4), and R ³ Is a hydrogen atom or an alkylcarbonyl group having 1 to 12 carbon atoms. It is especially preferable that it is a compound represented by this.

  Specific examples of the compound (a1) having two or more (meth) acryloyl groups include the following compounds.

  First, as the bifunctional (meth) acrylate, for example, 1,3-butylene glycol diacrylate (for example, SR-212 manufactured by Kayaku Sartomer Co., Ltd.), 1,4-diol diacrylate (for example, Osaka Organic Chemistry) Biscoat # 195, etc.), 1,6-hexanediol diacrylate (for example, 1,6HX-A manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide (hereinafter abbreviated as EO) modified 1,6-hexanediol diacrylate (for example, RCC13-361 manufactured by San Nopco Co., Ltd.), epichlorohydrin (hereinafter abbreviated as ECH) modified 1,6-hexanediol diacrylate (eg Kayrad R-167 manufactured by Nippon Kayaku Co., Ltd.), 1,9-nonanediol Diacrylate (for example, Biscoat # 21 manufactured by Osaka Organic Chemical Co., Ltd.) Etc.), diethylene glycol diacrylate (for example, Bremer ADE-100 manufactured by Nippon Oil & Fats Co., Ltd.), ECH-modified hexahydrophthalic acid diacrylate (for example, Denacol acrylate DA-722 manufactured by Nagase Kasei Co., Ltd.), neopentyl hydroxypivalate, etc. Glycol diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate HPP-A etc.), neopentyl glycol diacrylate (eg Nippon Kayaku Co., Ltd. Kayrad NPGDA etc.), EO modified neopentyl glycol diacrylate (eg Sannopco Co., Ltd.) Photomer 4160, etc.), propylene oxide (hereinafter abbreviated as PO) -modified neopentyl glycol diacrylate (eg, SR-9003 manufactured by Kayaku Sartomer Co., Ltd.), stearic acid-modified pentae, etc. Thritol diacrylate (for example, Aronix M-233 manufactured by Toagosei Co., Ltd.), polyethylene glycol diacrylate (for example, Bremer ADE-200 manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol diacrylate (for example, manufactured by Nippon Oil & Fats Co., Ltd.) Blemmer ADP-200, etc.), polyethylene glycol-propylene glycol-polyethylene glycol diacrylate (for example, Blemmer ADC series manufactured by NOF Corporation), polytetramethylene diglycol diacrylate (for example, light acrylate PTMGA- manufactured by Kyoeisha Chemical Co., Ltd.) 250), polyethylene glycol diacrylate (for example, Light Acrylate 3EG-A, etc., manufactured by Kyoeisha Chemical Co., Ltd.), dimethylol dicyclopentanediacrolein (For example, IRR214 manufactured by Daicel UCB Co., Ltd.), tricyclodecane dimethanol diacrylate (for example, LUMICURE DCA-200 manufactured by Dainippon Ink & Chemicals, Inc.), neopentyl glycol-modified trimethylolpropane diacrylate (for example, Japan) Kayrad R-604 manufactured by Kayaku Co., Ltd.) and triglycerol diacrylate (for example, epoxy ester 80MFA manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the trifunctional (meth) acrylate include EO-modified glycerol acrylate (for example, New Frontier GE3A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), PO-modified glycerol triacrylate (for example, Beam Set 720 manufactured by Arakawa Chemical Co., Ltd.), Pentaerythritol triacrylate (PETA) (for example, New Frontier PET-3 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), EO-modified phosphate triacrylate (for example, Biscoat 3A manufactured by Osaka Organic Chemical Co., Ltd.), trimethylolpropane triacrylate ( TMTPA) (for example, New Frontier TMTP manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), caprolactone-modified trimethylolpropane triacrylate (for example, Ebecryl 2047 manufactured by Daicel UCB Corporation), HPA-modified Limethylolpropane triacrylate (for example, Kayrad THE-330 manufactured by Nippon Kayaku Co., Ltd.), (EO) or (PO) modified trimethylolpropane triacrylate (for example, LUMICURE ETA-300 manufactured by Dainippon Ink & Chemicals, Inc., Daiichi Kogyo Seiyaku Co., Ltd. New Frontier TMP-3P, etc.), alkyl-modified dipentaerythritol triacrylate (eg, Kayrad D-330 produced by Nippon Kayaku Co., Ltd.), tris (acryloxyethyl) isocyanurate (eg, Hitachi) And the like.

  Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetraacrylate (DTMPTA) (for example, LUMICURE DTA-400 manufactured by Dainippon Ink & Chemicals, Inc.), pentaerythritol ethoxytetraacrylate (for example, Mitsubishi Rayon Co., Ltd.) Diabeam UK-4154 manufactured by the company), pentaerythritol tetraacrylate (PETTA) (for example, NK Ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  As pentafunctional or hexafunctional (meth) acrylate, dipentaerythritol hydroxypentaacrylate (for example, SR-399E manufactured by Kayaku Sartomer Co., Ltd.), alkyl-modified dipentaerythritol pentaacrylate (for example, Nippon Kayaku Co., Ltd.) Kayalad D-310), dipentaerythritol hexaacrylate (for example, DAP-600 manufactured by Dainippon Ink & Chemicals, Inc.), dipentaerythritol penta and hexaacrylate based polyfunctional monomer mixture (for example, Dainippon Ink and Chemicals Inc.) And LMICURE DPA-620 manufactured by the company).

  Needless to say, the present invention is not limited to these specific examples. These may be used alone, or may be a mixture of a plurality of compounds having different (meth) acryloyl group numbers, or a mixture of a plurality of compounds having different structures. Further, the compound (a1) that is generally commercially available is often a mixture of compounds having different numbers of (meth) acryloyl groups with respect to the target compound as the main component. In use, the compound having the desired number of (meth) acryloyl groups may be taken out and used by various purification methods such as chromatography and extraction, but may be used as a mixture.

  Moreover, as said compound (a1) used by this invention, it is also possible to use urethane (meth) acrylate (a1-2). There is no restriction | limiting as a manufacturing method of the said urethane (meth) acrylate (a1-2), For example, the polyaddition of the hydroxyl-containing (meth) acrylate (x1) which has two or more (meth) acryloyl groups, and an isocyanate compound It can be obtained by reaction or the like.

  The reaction can be performed without a catalyst, but a reaction aid such as a urethanization catalyst can be used from the viewpoint of reaction efficiency. Examples of the urethanization catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1 , 4-diazabicyclo [2.2.2] octane and the like, and 0.01 to 10% by weight is used with respect to the total weight of the hydroxyl group-containing (meth) acrylate (x1) and isocyanate compound used as a raw material. preferable.

  Examples of the hydroxyl group-containing (meth) acrylate (x1) include 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol hydroxypentaacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate ( For example, Nippon Oil & Fat Co., Ltd. Bremer GAM etc.) etc. are mentioned.

  As the isocyanate compound, any of an aromatic isocyanate compound, an aliphatic isocyanate compound, and an alicyclic isocyanate compound can be used. For example, toluene diisocyanate, tolylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Examples thereof include trimethylhexamethylene diisocyanate and adamantyl diisocyanate. From the viewpoint of the glass transition temperature of the resulting cured product and the scratch resistance of the cured product, it is preferable to have an alicyclic structure, for example, norbornane diisocyanate. Isophorone diisocyanate and adamantyl diisocyanate are preferably used. That is, as urethane (meth) acrylate (a1-2), a hydroxyl group-containing (meth) acrylate (x1) having two or more (meth) acryloyl groups and an isocyanate compound (x2) having an alicyclic structure are reacted. It is preferable that it is urethane (meth) acrylate obtained. In addition, the compound obtained by introducing a fluorinated alkyl group into the urethane (meth) acrylate (a1-2) by Michael addition uses a compound having a hydroxyl group as the compound (a1-1), and this is a Michael addition reaction. It is also possible to synthesize by introducing a fluorinated alkyl group by the reaction with an isocyanate compound, and the reaction order is not particularly limited.

Next, the compound (a2) having a fluorinated alkyl group and active hydrogen will be described.
The fluorinated alkyl group is preferably a perfluoroalkyl group from the viewpoint that the performance derived from a fluorine atom can be effectively expressed. In addition, when a fluorinated alkyl group other than a perfluoroalkyl group is used, the compatibility with other components to be blended as necessary is improved, and as a result, the translucency of the cured product is improved. It is also effective when used in applications where the toughness and adhesion of the cured product are required. The structure and type of the fluorinated alkyl group depends on the required level of performance and application. Is preferably selected.

As the compound (a2), it is easy to obtain industrially, and from the viewpoint that mild reaction conditions can be selected, the following general formula (1)
Rf (CH ₂ ) _m ZH (1)
[In the formula, m is an integer of 0 to 20, Rf is —C _n F _{2n + 1} (n is an integer of 1 to 20), and Z is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. A nitrogen atom, an oxygen atom, a sulfur atom, or —SO ₂ —NR— (wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms). ]
Or a compound represented by the following general formula (2)

〔式中、Ｙは酸素原子、又は硫黄原子であり、ｐとｑは同一でも異なっていても良い１〜４の整数であり、ＲｆとＲｆ^１は同一でも異なっていても良い−Ｃ_ｎＦ_２ｎ＋１（ｎは１〜２０の整数である。）である。〕
で表される化合物であることが好ましく、より温和な反応条件を選択できる点から、Ｚが水素原子若しくは炭素数１〜６のアルキル基を有する窒素原子、硫黄原子、又は−ＮＲ−ＳＯ_２−（Ｒは炭素数１〜６のアルキル基である。）である、或いは前記一般式（２）中のＹが硫黄原子であり、Ｒｆ^１の炭素数ｎが４、６、又は８であり、且つ前記一般式（１）中のＲｆの炭素数ｎが４、６、又は８であることが特に好ましい。

[Wherein, Y is an oxygen atom or a sulfur atom, p and q are the same or different integers of 1 to 4, and Rf and Rf ¹ may be the same or different -C _n F _{2n + 1} (n is an integer of 1 to 20). ]
In view of the fact that milder reaction conditions can be selected, Z is a nitrogen atom having a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a sulfur atom, or —NR—SO ₂ —. (R is an alkyl group having 1 to 6 carbon atoms), or Y in the general formula (2) is a sulfur atom, and the carbon number n of Rf ¹ is 4, 6, or 8. And it is particularly preferred that the carbon number n of Rf in the general formula (1) is 4, 6, or 8.

  The fluorinated alkyl group-containing (meth) acrylate produced using the compound represented by the general formula (1) or the general formula (2) has an application viewpoint, that is, when applied to a photocurable composition. It is advantageous for compatibility with other components used in combination as needed, transparency of the resulting cured product, surface characteristics derived from fluorine atoms, and optical characteristics.

Examples of the compound represented by the general formula (1) include the following compounds, which may be used alone or as a mixture of two or more.
_{C 4 F 9 SO 2 N (} CH 3) H (a2-1)
_{C 4 F 9 SO 2 N (} C 3 H 7) H (a2-2)
_{C 4 F 9 CH 2 CH 2} N (C 8 H 17) H (a2-3)
_{C 4 F 9 CH 2 CH 2} SH (a2-4)
_{C 6 F 13 CH 2 CH 2} SO 2 N (C 8 H 17) H (a2-5)
_{C 6 F 13 CH 2 CH 2} SH (a2-6)
_{C 6 F 13 CH 2 CH 2} N (C 4 H 9) H (a2-7)
_{C 8 F 17 CH 2 CH 2} SH (a2-8)
_{C 8 F 17 CH 2 N (} C 3 H 7) H (a2-9)
_{C 9 F 19 CH 2 CH 2} SH (a2-10)
_{C 10 F 21 CH 2 CH 2} CH 2 N (C 3 H 7) H (a2-11)
_{C 12 F 25 CH 2 CH 2} SH (a2-12)

  Examples of the method for producing the compound represented by the general formula (2) include 2-hydroxysuccinic acid (hereinafter referred to as malic acid) and 2-mercaptosuccinic acid (hereinafter referred to as thiomalic acid). And a method in which a fluorinated alkyl group-containing alcohol or a fluorinated alkyl group-containing mercaptan is reacted to form a diester, specifically, the following compounds may be mentioned.

  The charging ratio of the compound (a1) and the compound (a2) is appropriately adjusted depending on the intended use of the resulting photocurable composition and the intended physical properties. After the Michael addition reaction, (meth) acryloyl There is no limitation as long as the charge ratio is such that one or more groups remain. Specifically, in order to efficiently express effects derived from fluorine atoms such as surface characteristics and optical characteristics of the obtained cured product, the compound (a2) is usually used in an amount of [0.01 per 1 mol of the compound (a1). ~ (K-1) [k is the average number of (meth) acryloyl groups in one molecule of the compound (a1)]] mole, preferably [0.05- (k-1)] mole, It is more preferable to use in the range of [0.1 to (k-1)].

  The reaction between the compound (a1) and the compound (a2) may be carried out in accordance with the usual Michael addition reaction method, and special consideration by having a fluorine atom is not particularly required. Can be manufactured. When a solvent is used, it is appropriately selected in consideration of the solubility, boiling point, equipment used, etc. of the compound (a1) and the compound (a2), specifically, ethyl acetate, Esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl isobutyl ketone (Hereinafter abbreviated as MIBK), alcohols such as methanol, ethanol and isopropanol, aprotic polar compounds such as dimethylformamide, dimethylformacetamide and dimethylsulfoxide, ethers such as diethyl ether and tetrahydrofuran, Aliphatic hydrocarbons such as hexane and heptane It is, may be used alone or in combination of two or more solvents. Among these, it is preferable to use esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformacetamide, dimethyl sulfoxide, and the like, and esters, ketones, alcohols, ethers are preferably used. Particularly preferred.

  This reaction can be performed without a catalyst, but from the viewpoint of reaction efficiency, a reaction aid such as a catalyst can be appropriately selected and used. Examples of the reaction aid include metal alcoholates such as sodium methoxide and sodium ethoxide, amines such as trimethylamine, triethylamine and 1,4-diazabicyclo- [2.2.2] -octane, sodium hydride, hydrogen Metal hydrides such as lithium iodide, ammonium salts such as benzyltrimethylammonium hydroxide, tetraammonium fluoride, peroxides such as peracetic acid, etc., preferably metal alcoholates, amines, ammonium salts Particularly preferred are amines. The amount of the reaction aid used is not particularly limited, but is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on 1 mol of the compound (a1) used as a raw material. is there.

  Furthermore, depending on the compound (a1) and the compound (a2) to be used, heat can be used alone or in combination as a reaction activation energy source. The reaction temperature is usually 0 ° C. to reflux temperature, preferably 20 to 100 ° C., particularly preferably 20 to 70 ° C. When a solvent or the like is used during the reaction, the solute concentration is usually 2 to 90% by weight, preferably 20 to 80% by weight. There is no particular limitation on the order of the reaction materials. The product thus obtained can be used after being purified by extraction, column chromatography, or the like, but can also be used as it is. In particular, when the compound (a1) having a large number of (meth) acryloyl groups is used, it is usually difficult to control the place where the compound (a2) is added. A fluorinated alkyl group-containing (meth) acrylate can be obtained, but even in this case, it is not necessary to take out a single substance by isolation and purification, and it is used as a mixture of various compounds having different positions of the Michael addition reaction. It is possible.

  As described above, it is possible to pass fluorine through a Michael addition reaction between the compound (a1) and the compound (a2) under a simpler and milder condition without undergoing a condensation reaction that requires a strong acid catalyst or the like. An alkyl group-containing (meth) acrylate can be produced. In addition, since various polyfunctional (meth) acrylates that are currently available as commercial products or can be easily synthesized can be used as starting materials, it contains fluorinated alkyl group-containing (meth) acrylates. It is easy to change the structure or the fluorine atom content in one molecule or the number of (meth) acryloyl groups as appropriate for the intended purpose, application and required characteristics of the photocurable composition to be used, and a more effective production method It can be said.

  Specific examples of the fluorinated alkyl group-containing (meth) acrylate obtained by the above method include the following compounds. The following specific examples show the case of acrylate, and any acryloyl group in the formula can be changed to a methacryloyl group. Further, the following specific examples are compounds purified when acrylate is used as the (meth) acrylate used as a raw material, and any one of the hydrogen atoms in the methylene group bonded to the carbonyl carbon can be changed to a methyl group. .

  There is no restriction | limiting in particular as a usage method and a use of the fluorinated alkyl group containing (meth) acrylate obtained in this way. For example, the acrylate can be used alone or in combination with other compounds to be used as a curable composition. When the acrylate is polymerized and cured alone, a cured product having optical properties such as a low refractive index can be obtained. In addition, depending on the use, purpose, required performance, etc., when polymerizing and curing a curable composition containing other compounds, it can be applied to an optical material such as an antireflection film derived from a decrease in the refractive index of the resulting cured product. Application can be expected. Further, it can be applied to an antifouling coating agent using a high water and oil repellency of a perfluoroalkyl group. In designing such a curable composition, from the viewpoint of mechanical properties such as glass transition point, strength, and coating film hardness of the resulting cured product, and economic efficiency, other compounds to be blended include, for example, non-fluorine Examples include (meth) acrylates, non-fluorine polyfunctional monomers, other fluorine-containing (meth) acrylates, and fluorine-based polymers.

  The fluorinated alkyl group-containing (meth) acrylate obtained in the present invention or a curable composition containing the fluorinated alkyl group is applied or impregnated in a form that matches the intended use of the cured product, and then light, electron beam, radiation, etc. By irradiating the active energy ray, it can be polymerized and cured to form a desired cured product. In some cases, heat can be used alone or in combination as an energy source.

  In the case of polymerization by light, it is preferable to add a photopolymerization initiator to the fluorinated alkyl group-containing (meth) acrylate or a curable composition containing the same, more preferably 0.01 to 10% by weight, more preferably Add 0.1-7 wt%. When polymerizing and curing by electron beam or radiation, addition of a polymerization initiator is not particularly required.

  Further, when using heat as an energy source, in the presence of a polymerization initiator such as no catalyst or azobisisobutyronitrile, benzoin peroxide, methyl ethyl ketone peroxide, cobalt naphthenate, etc., for example, at 80 to 200 ° C. It can be polymerized and cured.

  On the other hand, when polymerizing and curing with active energy rays, germicidal lamps, UV fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light An ultraviolet ray as a light source, an electric wire by a scanning type, or a curtain type electron accelerator can be used. Moreover, it is also possible to irradiate in inert gas atmosphere, such as nitrogen gas, at the point of avoiding the oxygen disorder | damage | failure etc. at the time of ultraviolet curing.

  From the viewpoints of workability, productivity and economic efficiency in polymerization and curing, and further from the viewpoint of the performance of the cured product, it is preferable to cure the curable composition by any one of ultraviolet rays, electron beams and radiation. Among these, the method of polymerizing and curing with ultraviolet rays is the simplest and economical.

  The cured product thus obtained has optical characteristics such as a low refractive index or surface characteristics such as high water and oil repellency. And when compared with the hardened | cured material obtained using the (meth) acrylate proposed by the said patent document 1, it will be excellent also in the surface of the long-term performance maintenance of hardened | cured material. This is because the (meth) acrylate proposed in Patent Document 1 has a structure in which the perfluoroalkyl group is directly bonded to the carbonyl carbon in the ester bond, resulting in a decrease in the electric density of the carbon atom. It is thought that it is easy to hydrolyze. Since the fluorinated alkyl group-containing (meth) acrylate that can be produced in the present invention has an alkylene chain between the perfluoroalkyl group and the carbonyl carbon, the storage stability of the (meth) acrylate and the resulting curing It is excellent in hydrolysis resistance of products and is industrially useful.

  Next, in order to explain the present invention in more detail, examples will be given, but it goes without saying that the present invention is not limited to these examples.

Example 1 Synthesis of fluorinated alkyl group-containing methacrylate Average number of added functional groups 1
Into a 200 ml reaction flask, 67.0 g (0.20 mol) of trimethylolpropane trimethacrylate (NK ester TMTP manufactured by Shin-Nakamura Chemical Co., Ltd.) and 56.0 g (0.20 mol) of perfluorobutylethyl mercaptan were added and stirred. Then, 2 g of triethylamine was gradually added. The reaction temperature rose to 35 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of stirring, triethylamine was distilled off under reduced pressure while blowing water at a water bath temperature of 50 ° C. or lower, and further dried with a vacuum pump, whereby the acryloyl group in the structural formula (iv) was a methacryloyl group, 120.0 g of a fluorinated alkyl group-containing methacrylate having a structure having a methyl group on a carbon atom adjacent to carbon was obtained. The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
0.87 (t, J = 7.0Hz, 3H)
1.25 (d, J = 7.2 Hz, 3H
1.31-1.60 (m, 2H)
2.22-2.52 (m, 1H)
2.43-3.00 (m, 6H)
4.20-4.40 (m, 6H)
5.85 (d, J = 10.2 Hz, 2H)
6.1 (dd, J = 10.2, 17.3 Hz, 2H)
6.45 (d, J = 17.3 Hz, 2H)

Example 2 Synthesis of fluorinated alkyl group-containing acrylate Average addition functional group number 1
Into a 200 ml reaction flask, 59.7 g (0.20 mol) of pentaerythritol triacrylate (Da Nippon Ink Chemical Co., Ltd. LUMICURE PEA-300) and 101 g (0.20 mol) of N-propyl-perfluorooctylethylamine were added. Stir on a hot water bath to make it uniform. To this, 2.0 g of triethylamine was gradually added. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine was distilled off under reduced pressure using an evaporator at 50 ° C. or lower, and further dried with a vacuum pump, whereby 160.0 g of the fluorinated alkyl group-containing acrylate represented by the structural formula (v) was obtained. Obtained. The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
2.20-2.50 (m, 2H),
2.50-2.90 (m, 6H),
3.30-3.60 (m, 2H),
4.10-4.30 (m, 6H),
5.86 (d, J = 10.3 Hz, 2H),
6.10 (dd, J = 10.3, 17.3 Hz, 2H),
6.40 (d, J = 17.3 Hz, 2H)

Example 3 Synthesis of fluorinated alkyl group-containing acrylate Average number of functional groups added 2
In a 200 ml reaction flask, 26.2 g (0.05 mol) of dipentaerythritol hydroxypentaacrylate (SR-399E manufactured by Kayaku Sartomer Co., Ltd.), 19.1 g (0.05 mol) of perfluorohexylethyl mercaptan and perfluorooctylethyl Mercaptan (24.1 g, 0.05 mol) was added, and 1.0 g of triethylamine was gradually added with stirring. After the addition, the mixture was further stirred at 50 ° C. for 3 hours. Next, 69.4 g of a fluorinated alkyl group-containing acrylate represented by the structural formula (xiv) was obtained by distilling off triethylamine under reduced pressure using an evaporator (bath temperature of 50 ° C. or lower). The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
2.20-2.50 (m, 4H),
2.50-2.90 (m, 12H),
3.30-3.60 (m, 2H),
3.60-3.80 (m, 4H),
4.10-4.30 (m, 10H),
5.86 (d, J = 10.3 Hz, 6H),
6.10 (dd, J = 10.3, 17.3 Hz, 6H),
6.40 (d, J = 17.3 Hz, 6H)

Example 4 Synthesis of fluorinated alkyl group-containing acrylate Average number of added functional groups: 1
Synthesis of mercaptosuccinic acid diester A 500 ml flask equipped with a stirrer and a Dean-stark trap was charged with 150.0 g of perfluorohexyl ethyl mercaptan, 30.0 g of thiomalic acid, 1.5 g of concentrated sulfuric acid, and 200 ml of toluene, and the theoretical amount of water Heating under reflux was carried out until (7.2 g) could be removed. After cooling to 60 ° C., 20 g of slaked lime was added and stirred at the same temperature for 30 minutes. After separation by filtration, toluene was distilled off under reduced pressure to obtain 168.0 g of thiomalic acid di- (perfluorohexylethyl ester) as a yellow transparent viscous liquid.

Synthesis of fluorinated alkyl group-containing acrylate In a 200 ml reaction flask, 17.6 g (0.05 mol) of pentaerythritol tetraacrylate (Aronix M-450 manufactured by Toagosei Co., Ltd.), thiomalic acid di- (perfluorohexyl ethyl ester) 43 0.7 g (0.05 mol) and 10 g of ethyl acetate were added, and 1.0 g of triethylamine was gradually added with stirring at 50 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, ethyl acetate and triethylamine were distilled off under reduced pressure at 50 ° C. or lower, and further dried with a vacuum pump to obtain 25.0 g of a fluorinated alkyl group-containing acrylate represented by the structural formula (xviii). It was. The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
2.05-2.20 (m, 2H)
2.30-2.90 (m, 12H),
3.90-4.30 (m, 9H),
5.80 (d, J = 10.2 Hz, 3H),
6.0 (dd, J = 10.2, 17.3 Hz, 3H),
6.45 (d, J = 17.3 Hz, 3H)

Example 5 Synthesis of fluorine-containing urethane acrylate Average number of additional functional groups: 2
In a 500 ml reaction flask, a solution of 16.8 g (0.1 mol) of hexamethylene diisocyanate in 100 ml of MIBK was mixed with a solution of 59.6 g (0.20 mol) of pentaerythritol triacrylate in 50 ml MIBK at 25 ° C. with air bubbling. It was dripped. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 70 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or less to obtain 74.8 g of a colorless transparent viscous liquid urethane acrylate.

A 200 ml reaction flask was charged with 37.3 g (0.05 mol) of urethane acrylate, 34.0 g (0.1 mol) of N-propyl-perfluorobutanesulfonylamide, and 60 g of MIBK to make uniform. To this mixed solution, 1.0 g of triethylamine was gradually added at 25 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine was distilled off under reduced pressure using an evaporator at 50 ° C. or lower, and further dried with a vacuum pump to obtain a fluorine-containing urethane acrylate represented by the structural formula (xix). The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
0.95 (t, J = 7.3 Hz, 6H),
1.30-1.80 (m, 12H),
3.25 (t, J = 7.0 Hz, 4H)
3.40-3.90 (m, 8H),
4.00-4.50 (m, 20H),
4.90 (brs, 2H),
5.85 (d, J = 10.2 Hz, 2H),
6.0 (dd, J = 10.2, 17.3 Hz, 2H),
6.40 (d, J = 17.3 Hz, 2H)

Example 6 Synthesis of fluorinated alkyl group-containing urethane acrylate Average number of additional functional groups: 3
In a 500 ml reaction flask, a solution of 22.2 g (0.1 mol) of isophorone diisocyanate in 100 ml of MIBK was dropped with a solution of 59.6 g (0.20 mol) of pentaerythritol triacrylate in 50 ml of MIBK at 25 ° C. while performing air bubbling. did. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 70 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or less to obtain 80.5 g of a colorless transparent viscous liquid urethane acrylate.

Into a 200 ml reaction flask, 40.8 g (0.05 mol) of the prepared urethane acrylate, 71.9 g (0.15 mol) of perfluorooctylethyl mercaptan, and 60 g of MIBK were added to make uniform. To this mixed solution, 1.0 g of triethylamine was gradually added at 25 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine was distilled off under reduced pressure using an evaporator at 50 ° C. or lower, and further dried with a vacuum pump to obtain a fluorinated alkyl group-containing urethane acrylate represented by the structural formula (xxii). . The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
0.80-1.20 (m, 9H)
1.30-1.50 (m, 6H)
2.0-3.0 (m, 24H)
3.15-3.55 (m, 16H)
5.5 (brs, 2H)
5.85 (d, J = 10.2 Hz, 3H),
6.1 (dd, J = 10.2, 17.3 Hz, 3H),
6.35 (d, J = 17.3 Hz, 3H)

Example 7 Synthesis of fluorinated alkyl group-containing urethane acrylate Average number of additional functional groups: 4
Into a 200 ml reaction flask, 15.7 g (0.03 mol) of dipentaerythritol hydroxypentaacrylate (SR-399E manufactured by Kayaku Sartomer Co., Ltd.) and 28.8 g (0.06 mol) of perfluorooctylethyl mercaptan are added and stirred. Under the above, 1.0 g of triethylamine was gradually added. After the addition, the mixture was further stirred at 50 ° C. for 3 hours. Next, 69.4 g of a fluorinated alkyl group-containing acrylate represented by the structural formula (xiii) was obtained by distilling off triethylamine under reduced pressure using an evaporator (bath temperature of 50 ° C. or lower).

In a 500 ml reaction flask, hydrogenated 4,4-diphenylmethane diisocyanate 7.86 g (0.03 mol) and MIBK 100 g mixed solution were mixed with fluorinated alkyl group-containing acrylate (xiii) 88.0 g (0.06 mol). ) Was added dropwise at 25 ° C. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 55 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or lower to obtain 91.4 g of a wax-like fluorinated alkyl group-containing urethane acrylate represented by the structural formula (xxiii). The product was obtained from the integration ratio of vinyl proton (—OCOCH═CH ₂ ) and ether-bonded carbon (C—CH ₂ —O—CH ₂ —C) in ¹ H-NMR of the product and the FT-IR spectrum. confirmed.
¹ H-NMR:
δ
Vinyl group hydrogen 5.85 (d, J = 10.2 Hz, 6H),
6.1 (dd, J = 10.2, 17.3 Hz, 6H),
6.35 (d, J = 17.3 Hz, 6H)
Ether-bonded hydrogen on carbon 3.20-3.45 (m, 8H)
FT-IR (cm ⁻¹ ): 3370, 1730, 1520, 1200

Example 8 Synthesis of fluorinated alkyl group-containing acrylate Average number of added functional groups: 1
In a 200 ml reaction flask was added 21.2 g (0.05 mol) of tris (acryloxyethyl) isocyanurate (Aronix M-315 manufactured by Toa Gosei Co., Ltd.), 1.0 g of triethylamine, and 15 g of ethyl acetate at room temperature with perfluorohexylethyl. 19.0 g (0.05 mol) of mercaptan was added dropwise with stirring (reaction temperature rose to 35 ° C.). After the addition, the mixture was further stirred at 50 ° C. for 3 hours, and ethyl acetate and triethylamine were distilled off under reduced pressure at 50 ° C. or lower to obtain 39.4 g of a fluorinated alkyl group-containing acrylate represented by the structural formula (xxiv). . The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
2.22-2.52 (m, 2H)
2.43-3.00 (m, 6H)
4.25-4.40 (m, 6H)
5.80 (d, J = 10.0Hz, 2H)
6.05 (dd, J = 10.0, 17.2 Hz, 2H)
6.32 (d, J = 17.2 Hz, 2H)

Example 9 Synthesis of fluorinated alkyl group-containing acrylate Average number of added functional groups: 1
Instead of 21.2 g (0.05 mol) of tris (acryloxyethyl) isocyanurate (Aronix M-315 manufactured by Toa Gosei Co., Ltd.) in Example 8, 15.1 g (0.05 mol) of EO-modified phosphoric acid triacrylate In the same manner as in Example 8 except that 24.0 g (0.05 mol) of perfluorooctylethyl mercaptan was used instead of 19.0 g (0.05 mol) of perfluorohexylethyl mercaptan. 40.0 g of a fluorinated alkyl group-containing acrylate represented by xxv) was obtained. The ¹ H-NMR spectrum peaks and integral values of the product supported the synthesis.
¹ H-NMR:
δ
2.30-2.52 (m, 2H)
2.43-3.00 (m, 6H)
4.10-4.30 (m, 6H)
4.30-4.45 (m, 6H)
5.82 (d, J = 10.0Hz, 2H)
6.05 (dd, J = 10.0, 17.2 Hz, 2H)
6.30 (d, J = 17.2 Hz, 2H)

Claims (5)

Fluorinated alkyl group-containing (meth) via Michael addition reaction using compound (a1) having two or more (meth) acryloyl groups and compound (a2) having a fluorinated alkyl group and active hydrogen A method for producing a fluorinated alkyl group-containing (meth) acrylate, which comprises producing an acrylate. The compound (a2) having a fluorinated alkyl group and active hydrogen is represented by the following general formula (1)
Rf (CH ₂ ) _m ZH (1)
[In the formula, m is an integer of 0 to 20, Rf is —C _n F _{2n + 1} (n is an integer of 1 to 20), and Z is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. A nitrogen atom, an oxygen atom, a sulfur atom, or —SO ₂ —NR— (wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms). ]
Or a compound represented by the following general formula (2)

[Wherein, Y is an oxygen atom or a sulfur atom, p and q are the same or different integers of 1 to 4, and Rf and Rf ¹ may be the same or different -C _n F _{2n + 1} (n is an integer of 1 to 20). ]
The method for producing a fluorinated alkyl group-containing (meth) acrylate according to claim 1, wherein the compound is represented by the formula: Z in the general formula (1) is a hydrogen atom, a nitrogen atom having a C 1-6 alkyl group, a sulfur atom, or —SO ₂ —NR— (R is a C 1-6 alkyl group. Or Y in the general formula (2) is a sulfur atom, the carbon number n of Rf ¹ is 4, 6 or 8, and the carbon number n of Rf in the general formula (1) The method for producing a fluorinated alkyl group-containing (meth) acrylate according to claim 2, wherein is 4, 6, or 8. The compound (a1) having two or more (meth) acryloyl groups is represented by the following general formula (3)

[Wherein, R ′ represents an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, (Poly) oxyalkylene group having 1 or more repeats and the end blocked with a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkylol group having 1 to 12 carbon atoms, or the following general formula (4)

(In the formula, R ³ is a (meth) acryloyl group, R ⁴ is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, t is an integer of 0 to 3, and u is an integer of 0 to 3) And t + u = 3.)
R ¹ is a (meth) acryloyl group, R ² is a hydrogen atom or an alkylcarbonyl group having 1 to 18 carbon atoms, r is 2 or 3, and s is 0 or 1 And r + s = 3. ]
In the compound (a1-1), urethane (meth) acrylate (a1-2), cyanurate ring-containing tri (meth) acrylate (a1-3), or phosphoric acid tri (meth) acrylate (a1-4) represented by The method for producing a fluorinated alkyl group-containing (meth) acrylate according to claim 1. The compound (a1) having two or more (meth) acryloyl groups has the above general formula (3) [wherein R ′ is a linear alkyl group having 1 to 4 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ — CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, or an alkylol group having 1 to 3 carbon atoms, or a group represented by the general formula (4), and R ³ is a hydrogen atom or It is a C1-C12 alkylcarbonyl group. A compound represented by
5. A urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate (x1) having two or more (meth) acryloyl groups with an isocyanate compound (x2) having an alicyclic structure. Of producing a fluorinated alkyl group-containing (meth) acrylate.