WO2021161931A1 - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- WO2021161931A1 WO2021161931A1 PCT/JP2021/004453 JP2021004453W WO2021161931A1 WO 2021161931 A1 WO2021161931 A1 WO 2021161931A1 JP 2021004453 W JP2021004453 W JP 2021004453W WO 2021161931 A1 WO2021161931 A1 WO 2021161931A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
- C08F20/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
Abstract
The present invention relates to a curable resin composition comprising 100 parts by mass of a fluoropolymer (P), 0.01-10 parts by mass of a compound (A) represented by general formula (1), which has a fluorothioether skeleton, and 0.05-5 parts by mass of an initiator (B). (In general formula (1), R1 to R4 each independently represent an alkylene group having 1-10 carbon atoms and Rf1 and Rf2 each independently represent an alkyl group having 1-20 carbon atoms which has one or more fluorine atoms and may contain an etheric oxygen atom between carbon atoms.)
Description
本発明は、硬化性樹脂組成物に関する。
The present invention relates to a curable resin composition.
一般的に、樹脂は熱や光に対する安定性が乏しく、熱や光に晒されると容易に酸化や劣化を引き起こし必要な製品寿命が得られない。これらを防止するために酸化防止剤などが用いられている。
In general, resins have poor stability to heat and light, and when exposed to heat and light, they easily oxidize and deteriorate, and the required product life cannot be obtained. Antioxidants and the like are used to prevent these.
高透明で高耐熱な樹脂として含フッ素ポリマーが広く知られているが、一般的な酸化防止剤では含フッ素ポリマーとの相溶性が悪い。そこで、酸化防止剤の相溶性を上げるためにフェノール系酸化防止剤の置換基をフッ素で置換した含フッ素化合物や、メルカプト基を有する含フッ素化合物が開示されている（特許文献１～３）。一方、汎用樹脂用防汚剤として、撥油性を有する含フッ素酸化防止剤を組み合わせることが開示されている（特許文献４）。
Fluororepolymer is widely known as a highly transparent and highly heat-resistant resin, but general antioxidants have poor compatibility with fluoropolymer. Therefore, in order to improve the compatibility of the antioxidant, a fluorine-containing compound in which the substituent of the phenolic antioxidant is replaced with fluorine and a fluorine-containing compound having a mercapto group are disclosed (Patent Documents 1 to 3). On the other hand, it is disclosed that a fluorine-containing antioxidant having oil repellency is combined as an antifouling agent for general-purpose resins (Patent Document 4).
しかし、これらの含フッ素ポリマーへの含フッ素化合物の添加は相溶性改善に係るものであり、一方汎用樹脂への含フッ素化合物の添加は、含フッ素化合物自体が有する撥油性、防汚性を発現させるために添加されたものである。
However, the addition of the fluorinated compound to these fluoropolymers is related to the improvement of compatibility, while the addition of the fluorinated compound to the general-purpose resin exhibits the oil repellency and antifouling property of the fluorinated compound itself. It was added to make it.
これまで、相溶性や撥油性を向上させるために含フッ素ポリマーに対して含フッ素化合物を添加することは知られていたが、含フッ素化合物の中でも特に含フッ素チオエーテル化合物を、含フッ素ポリマーを用いた硬化物の透過率低下を抑制させるために添加することは見出されていなかった。
本発明は、含フッ素ポリマーを硬化させた硬化物の透過率低下を抑制し、且つ含フッ素ポリマーとの相溶性に優れた、硬化性樹脂組成物を提供することを課題とする。 Until now, it has been known to add a fluorine-containing compound to a fluorine-containing polymer in order to improve compatibility and oil repellency. It has not been found to be added in order to suppress a decrease in the permeability of the cured product.
An object of the present invention is to provide a curable resin composition which suppresses a decrease in the transmittance of a cured product obtained by curing a fluoropolymer and has excellent compatibility with the fluoropolymer.
本発明は、含フッ素ポリマーを硬化させた硬化物の透過率低下を抑制し、且つ含フッ素ポリマーとの相溶性に優れた、硬化性樹脂組成物を提供することを課題とする。 Until now, it has been known to add a fluorine-containing compound to a fluorine-containing polymer in order to improve compatibility and oil repellency. It has not been found to be added in order to suppress a decrease in the permeability of the cured product.
An object of the present invention is to provide a curable resin composition which suppresses a decrease in the transmittance of a cured product obtained by curing a fluoropolymer and has excellent compatibility with the fluoropolymer.
本発明は、含フッ素ポリマー（Ｐ）１００質量部に対し、下記一般式（１）で表される含フッ素チオエーテル骨格を有する化合物（Ａ）を０．０１～１０質量部、開始剤（Ｂ）を０．０５～５質量部含有する硬化性樹脂組成物に関する。
In the present invention, 0.01 to 10 parts by mass of the compound (A) having a fluoroether skeleton represented by the following general formula (1) is added to 100 parts by mass of the fluoropolymer (P), and the initiator (B) is used. The present invention relates to a curable resin composition containing 0.05 to 5 parts by mass of.
（一般式（１）中、Ｒ１～Ｒ４は各々独立に、炭素数１～１０のアルキレン基を表す。Ｒｆ１およびＲｆ２は各々独立に、フッ素原子を有する炭素数１～２０のアルキル基を表し、炭素原子間にエーテル性酸素原子を含んでいてもよい。）
(In the general formula (1), R 1 to R 4 independently represent an alkylene group having 1 to 10 carbon atoms. Rf 1 and Rf 2 each independently represent an alkyl having 1 to 20 carbon atoms having a fluorine atom. It represents a group and may contain etheric oxygen atoms between carbon atoms.)
本発明によれば、含フッ素ポリマーの透過率低下を抑制し、且つ含フッ素ポリマーとの相溶性に優れた、硬化性樹脂組成物を提供できる。
According to the present invention, it is possible to provide a curable resin composition that suppresses a decrease in the transmittance of the fluoropolymer and has excellent compatibility with the fluoropolymer.
以下、本発明の硬化性樹脂組成物について具体的に説明する。
用語の説明として、以下の通りとする。
「（メタ）アクリル基」とはアクリル基またはメタアクリル基の総称である。
数値範囲を示す「～」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。 Hereinafter, the curable resin composition of the present invention will be specifically described.
The explanation of terms is as follows.
"(Meta) acrylic group" is a general term for acrylic group or methacrylic group.
“～” Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
用語の説明として、以下の通りとする。
「（メタ）アクリル基」とはアクリル基またはメタアクリル基の総称である。
数値範囲を示す「～」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。 Hereinafter, the curable resin composition of the present invention will be specifically described.
The explanation of terms is as follows.
"(Meta) acrylic group" is a general term for acrylic group or methacrylic group.
“～” Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
［含フッ素ポリマー（Ｐ）］
含フッ素ポリマー（Ｐ）は、分子中に１個以上のフッ素原子を有する樹脂である。含フッ素ポリマーの中でも、末端がアクリル基またはメタアクリル基を有するモノマーの重合体であることが好ましい。含フッ素ポリマーの具体例としては日本国特開２０１３－１８１１４０号公報、国際公開第２０１７／０１８４８９号、国際公開第２０１４／１３６７３１号に記載のモノマーを重合して得られる樹脂が挙げられる。 [Fluororesin-containing polymer (P)]
The fluoropolymer (P) is a resin having one or more fluorine atoms in the molecule. Among the fluoropolymers, a polymer of a monomer having an acrylic group or a methacrylic group at the end is preferable. Specific examples of the fluoropolymer include a resin obtained by polymerizing the monomers described in Japanese Patent Application Laid-Open No. 2013-181140, International Publication No. 2017/018489, and International Publication No. 2014/136731.
含フッ素ポリマー（Ｐ）は、分子中に１個以上のフッ素原子を有する樹脂である。含フッ素ポリマーの中でも、末端がアクリル基またはメタアクリル基を有するモノマーの重合体であることが好ましい。含フッ素ポリマーの具体例としては日本国特開２０１３－１８１１４０号公報、国際公開第２０１７／０１８４８９号、国際公開第２０１４／１３６７３１号に記載のモノマーを重合して得られる樹脂が挙げられる。 [Fluororesin-containing polymer (P)]
The fluoropolymer (P) is a resin having one or more fluorine atoms in the molecule. Among the fluoropolymers, a polymer of a monomer having an acrylic group or a methacrylic group at the end is preferable. Specific examples of the fluoropolymer include a resin obtained by polymerizing the monomers described in Japanese Patent Application Laid-Open No. 2013-181140, International Publication No. 2017/018489, and International Publication No. 2014/136731.
例えば、後述する化合物（Ａ）との相溶性の観点から、含フッ素ポリマー（Ｐ）におけるモノマーとしては、分子中のフッ素原子の質量割合が１０％以上のモノマーが好ましく、２０％以上のモノマーがより好ましく、２５％以上のモノマーがさらに好ましい。加えて、硬化性を有することが好ましく、末端にアクリル基またはメタクリル基を１つ以上有することが好ましい。
For example, from the viewpoint of compatibility with the compound (A) described later, as the monomer in the fluoropolymer (P), a monomer having a mass ratio of fluorine atoms in the molecule of 10% or more is preferable, and a monomer having a mass ratio of 20% or more is preferable. More preferably, 25% or more of the monomers are further preferable. In addition, it is preferably curable and preferably has one or more acrylic or methacrylic groups at the ends.
含フッ素ポリマー（Ｐ）は、以下に示すモノマーや、式（Ｍ－１）、式（Ｍ－２）に示すモノマーを重合して得られる樹脂であることが好ましい。
The fluoropolymer (P) is preferably a resin obtained by polymerizing the following monomers or the monomers represented by the formulas (M-1) and (M-2).
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３。 CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = C (CH 3 ) C (O) O-CH 2 -CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 3,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 3,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = CHC (O) O-CH 2 -CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 3,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 3,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 7 CF 3.
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）６ＣＦ３、
ＣＨ２＝Ｃ（Ｆ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）７ＣＦ３。 CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (CH 3) C (O) O-C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = C (CH 3 ) C (O) O-CH 2 -CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 3,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 3,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = CHC (O) O -C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = CHC (O) O-CH 2 -CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 3,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 3,
CH 2 = CHC (O) O -CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (Cl) C (O) O-C 2 H 4 - (CF 2) 7 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 3 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 4 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 5 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 6 CF 3,
CH 2 = C (F) C (O) O-C 2 H 4 - (CF 2) 7 CF 3.
市販品としては、新中村化学工業社製ＮＫエステルＤＡ－Ｆ４ＥＯ、Ｓｏｌｖａｙスペシャリティケミカル社製フルオロリンクＭＤ－７００等が挙げられる。
Examples of commercially available products include NK ester DA-F4EO manufactured by Shin Nakamura Chemical Industry Co., Ltd. and Fluorolink MD-700 manufactured by Solvay Specialty Chemical Co., Ltd.
［化合物（Ａ）］
含フッ素チオエーテル骨格を有する化合物（Ａ）は、以下の一般式（１）で表される化合物である。 [Compound (A)]
The compound (A) having a fluorine-containing thioether skeleton is a compound represented by the following general formula (1).
含フッ素チオエーテル骨格を有する化合物（Ａ）は、以下の一般式（１）で表される化合物である。 [Compound (A)]
The compound (A) having a fluorine-containing thioether skeleton is a compound represented by the following general formula (1).
上記一般式（１）中、Ｒ１～Ｒ４は各々独立に、炭素数１～１０のアルキレン基を表す。Ｒｆ１およびＲｆ２は各々独立に、フッ素原子を有する炭素数１～２０のアルキル基を表す。
In the above general formula (1), R 1 to R 4 independently represent an alkylene group having 1 to 10 carbon atoms. Rf 1 and Rf 2 each independently represent an alkyl group having a fluorine atom and having 1 to 20 carbon atoms.
Ｒ１～Ｒ４で表される炭素数１～１０のアルキレン基としては、直鎖および分岐のアルキレン基が挙げられ、透過率低下を抑制する観点から炭素数１～６のアルキレン基が好ましく、炭素数１～４のアルキレン基がより好ましく、メチレン基、エチレン基、プロピレン基が更に好ましく、エチレン基が特に好ましい。これらの中でも、Ｒ１～Ｒ４が全てエチレン基であることが含フッ素ポリマーへの相溶性や透過率低下の抑制の観点から最も好ましい。
Examples of the alkylene group having 1 to 10 carbon atoms represented by R 1 to R 4 include linear and branched alkylene groups, and an alkylene group having 1 to 6 carbon atoms is preferable from the viewpoint of suppressing a decrease in permeability. An alkylene group having 1 to 4 carbon atoms is more preferable, a methylene group, an ethylene group, and a propylene group are more preferable, and an ethylene group is particularly preferable. Among these, it is most preferable that R 1 to R 4 are all ethylene groups from the viewpoint of compatibility with the fluoropolymer and suppression of decrease in transmittance.
Ｒｆ１およびＲｆ２で表されるフッ素原子を有する炭素数１～２０のアルキル基としては、直鎖および分岐のアルキル基が挙げられ、炭素原子上の全ての水素原子がフッ素原子で置換されたものであってもよく、一部の水素原子がフッ素原子に置換されたものであってもよく、炭素原子の間にエーテル性酸素原子を含んでいてもよい。炭素数としては炭素数１～１０のアルキル基が好ましく、炭素数１～８のアルキル基が好ましく、炭素数２～６のアルキル基がより好ましい。特に、パーフルオロエチル基（Ｃ２Ｆ５－）、直鎖および分岐を含むパーフルオロプロピル基（ｎ－Ｃ３Ｆ７－、（ＣＦ３）２ＣＦ－）、直鎖および分岐を含むパーフルオロブチル基（ｎ－Ｃ４Ｆ９－、（ＣＦ３）２ＣＦＣＦ２－）等）、直鎖および分岐を含むパーフルオロヘキシル基（ｎ－Ｃ６Ｆ１３－等）が好ましい。これらの中でも、Ｒｆ１とＲｆ２が共にパーフルオロヘキシル基であることが含フッ素ポリマーへの相溶性の観点から最も好ましい。
Examples of the alkyl group having 1 to 20 carbon atoms having a fluorine atom represented by Rf 1 and Rf 2 include linear and branched alkyl groups, in which all hydrogen atoms on the carbon atom were replaced with fluorine atoms. It may be one in which a part of hydrogen atoms is replaced with a fluorine atom, or an ether oxygen atom may be contained between carbon atoms. As the number of carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 2 to 6 carbon atoms is more preferable. In particular, perfluoroethyl group (C 2 F 5 -), perfluoropropyl group including straight chain and branched (n-C 3 F 7 - , (CF 3) 2 CF-), linear and perfluoro including branching butyl group (n-C 4 F 9 - , (CF 3) 2 CFCF 2 -) , etc.), straight and perfluorohexyl group containing branched (n-C 6 F 13 -, etc.) is preferred. Of these, it is most preferable that both Rf 1 and Rf 2 are perfluorohexyl groups from the viewpoint of compatibility with fluoropolymers.
［開始剤（Ｂ）］
開始剤は、光硬化または熱硬化等の硬化方法に応じて選択され、光重合開始剤や熱重合開始剤等が用いられる。 [Initiator (B)]
The initiator is selected according to a curing method such as photocuring or thermosetting, and a photopolymerization initiator, a thermopolymerization initiator, or the like is used.
開始剤は、光硬化または熱硬化等の硬化方法に応じて選択され、光重合開始剤や熱重合開始剤等が用いられる。 [Initiator (B)]
The initiator is selected according to a curing method such as photocuring or thermosetting, and a photopolymerization initiator, a thermopolymerization initiator, or the like is used.
光重合開始剤としては、アルキルフェノン系光重合開始剤、アシルホスフィンオキシド系光重合開始剤、チタノセン系光重合開始剤、オキシムエステル系光重合開始剤、オキシフェニル酢酸エステル系光重合開始剤、ベンゾイン系光重合開始剤、ベンゾフェノン系光重合開始剤、チオキサントン系光重合開始剤、ベンジル－（ｏ－エトキシカルボニル）－α－モノオキシム、グリオキシエステル、３－ケトクマリン、２－エチルアンスラキノン、カンファーキノン、テトラメチルチウラムスルフィド、アゾビスイソブチロニトリル、ベンゾイルペルオキシド、ジアルキルペルオキシド、ｔｅｒｔ－ブチルペルオキシピバレート等が挙げられる。光ラジカル重合開始剤としては、感度が高く、硬化性樹脂組成物への溶解性が高い点から、アルキルフェノン系光重合開始剤、アシルホスフィンオキシド系光重合開始剤、ベンゾイン系光重合開始剤またはベンゾフェノン系光重合開始剤が好ましい。
光重合開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an oxyphenylacetate-based photopolymerization initiator, and a benzoin. Photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, benzyl- (o-ethoxycarbonyl) -α-monooxime, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, Examples thereof include tetramethylthium sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and tert-butyl peroxypivalate. The photoradical polymerization initiator includes an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a benzoin-based photopolymerization initiator, or a benzoin-based photopolymerization initiator because of its high sensitivity and high solubility in a curable resin composition. Benzoinone-based photopolymerization initiators are preferred.
As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
光重合開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an oxyphenylacetate-based photopolymerization initiator, and a benzoin. Photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, benzyl- (o-ethoxycarbonyl) -α-monooxime, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, Examples thereof include tetramethylthium sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and tert-butyl peroxypivalate. The photoradical polymerization initiator includes an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a benzoin-based photopolymerization initiator, or a benzoin-based photopolymerization initiator because of its high sensitivity and high solubility in a curable resin composition. Benzoinone-based photopolymerization initiators are preferred.
As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
熱重合開始剤としては、２，２’－アゾビスイソブチロニトリル、ベンゾイルペルオキシド、ｔｅｒｔ－ブチルヒドロペルオキシド、クメンヒドロペルオキシド、ジ－ｔｅｒｔ－ブチルペルオキシド、ジクミルペルオキシド等が挙げられる。熱重合開始剤としては、熱分解温度が低い点から、２，２’－アゾビスイソブチロニトリル、ベンゾイルペルオキシドが好ましい。熱重合開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide and the like. As the thermal polymerization initiator, 2,2'-azobisisobutyronitrile and benzoyl peroxide are preferable because the thermal decomposition temperature is low. As the thermal polymerization initiator, one type may be used alone, or two or more types may be used in combination.
開始剤としては、硬化物の製造のしやすさから、光重合開始剤が好ましい。
As the initiator, a photopolymerization initiator is preferable because of the ease of producing a cured product.
［含フッ素フェノール系酸化防止剤（Ｃ）］
本発明の硬化性樹脂組成物は、さらに以下の一般式（２）で表される含フッ素フェノール系酸化防止剤（Ｃ）を含有してもよい。 [Fluorine-containing phenolic antioxidant (C)]
The curable resin composition of the present invention may further contain a fluorine-containing phenolic antioxidant (C) represented by the following general formula (2).
本発明の硬化性樹脂組成物は、さらに以下の一般式（２）で表される含フッ素フェノール系酸化防止剤（Ｃ）を含有してもよい。 [Fluorine-containing phenolic antioxidant (C)]
The curable resin composition of the present invention may further contain a fluorine-containing phenolic antioxidant (C) represented by the following general formula (2).
一般式（２）中、Ｒ５およびＲ６は各々独立に、水素原子、ハロゲン原子、ヒドロキシ基、シアノ基、ニトロ基、カルボキシル基、リン酸基、炭素数１～１０のアルキル基または炭素数１～１０のアルコキシ基を表す。Ｒ７およびＲ８は各々独立に、炭素数１～１０のアルキレン基を表す。Ｒｆ３はフッ素原子を有する炭素数１～２０のアルキル基を表す。
In the general formula (2), R 5 and R 6 are independently hydrogen atom, halogen atom, hydroxy group, cyano group, nitro group, carboxyl group, phosphoric acid group, alkyl group having 1 to 10 carbon atoms or carbon number of carbon atoms. Represents 1 to 10 alkoxy groups. R 7 and R 8 each independently represent an alkylene group having 1 to 10 carbon atoms. Rf 3 represents an alkyl group having a fluorine atom and having 1 to 20 carbon atoms.
Ｒ５およびＲ６で表される炭素数１～１０のアルキル基としては、直鎖または分岐のアルキル基が挙げられ、ラジカルの自動酸化連鎖を効果的に抑制できる観点から炭素数１～８のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。特に、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｔ－ブチル基、ｎ－ヘキシル基が好ましい。これらの中でも、Ｒ５とＲ６が共にｔ－ブチル基であることがラジカルの自動酸化連鎖を効果的に抑制できる観点から最も好ましい。
Examples of the alkyl group having 1 to 10 carbon atoms represented by R 5 and R 6 include a linear or branched alkyl group, which has 1 to 8 carbon atoms from the viewpoint of effectively suppressing the automatic oxidation chain of radicals. Alkyl groups are preferable, and alkyl groups having 1 to 6 carbon atoms are more preferable. In particular, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group and an n-hexyl group are preferable. Of these, it is most preferable that both R 5 and R 6 are t-butyl groups from the viewpoint of effectively suppressing the autoxidation chain of radicals.
Ｒ７およびＲ８で表される炭素数１～１０のアルキレン基としては、直鎖または分岐のアルキレン基が挙げられ含フッ素ポリマーへの相溶性の観点から炭素数１～６のアルキレン基が好ましく、炭素数１～４のアルキレン基がより好ましく、メチレン基、エチレン基、プロピレン基が更に好ましく、エチレン基が特に好ましい。これらの中でも、Ｒ７およびＲ８が共にエチレン基であることが含フッ素ポリマーへの相溶性の観点から最も好ましい。
Examples of the alkylene group having 1 to 10 carbon atoms represented by R 7 and R 8 include a linear or branched alkylene group, and an alkylene group having 1 to 6 carbon atoms is preferable from the viewpoint of compatibility with a fluorine-containing polymer. , An alkylene group having 1 to 4 carbon atoms is more preferable, a methylene group, an ethylene group and a propylene group are further preferable, and an ethylene group is particularly preferable. Of these, it is most preferable that both R 7 and R 8 are ethylene groups from the viewpoint of compatibility with the fluoropolymer.
Ｒｆ３で表されるフッ素原子を有する炭素数１～２０のアルキル基としては、直鎖または分岐のアルキル基が挙げられ、含フッ素ポリマーへの相溶性の観点から炭素原子上の全ての水素原子がフッ素原子で置換されたものであってもよく、一部の水素原子がフッ素原子に置換されたものであってもよく、炭素原子の間にエーテル性酸素原子を含んでいてもよい。炭素数としては炭素数１～１０のアルキル基が好ましく、炭素数１～８のアルキル基が好ましく、炭素数２～６のアルキル基がより好ましい。特に、パーフルオロエチル基（Ｃ２Ｆ５－）、直鎖および分岐を含むパーフルオロプロピル基（ｎ－Ｃ３Ｆ７－、（ＣＦ３）２ＣＦ－）、直鎖および分岐を含むパーフルオロブチル基（ｎ－Ｃ４Ｆ９－、（ＣＦ３）２ＣＦＣＦ２－）等）、直鎖および分岐を含むパーフルオロヘキシル基（ｎ－Ｃ６Ｆ１３－等）が好ましい。これらの中でも、パーフルオロヘキシル基であることが含フッ素ポリマーへの相溶性の観点から最も好ましい。
Examples of the alkyl group having 1 to 20 carbon atoms having a fluorine atom represented by Rf 3 include a linear or branched alkyl group, and all hydrogen atoms on the carbon atom from the viewpoint of compatibility with a fluorine-containing polymer. May be substituted with a fluorine atom, some hydrogen atoms may be substituted with a fluorine atom, and an ether oxygen atom may be contained between carbon atoms. As the number of carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 2 to 6 carbon atoms is more preferable. In particular, perfluoroethyl group (C 2 F 5 -), perfluoropropyl group including straight chain and branched (n-C 3 F 7 - , (CF 3) 2 CF-), linear and perfluoro including branching butyl group (n-C 4 F 9 - , (CF 3) 2 CFCF 2 -) , etc.), straight and perfluorohexyl group containing branched (n-C 6 F 13 -, etc.) is preferred. Among these, a perfluorohexyl group is most preferable from the viewpoint of compatibility with a fluoropolymer.
［チオール化合物（Ｄ）］
本発明の硬化性樹脂組成物は、さらにチオール化合物を含有してもよい。チオール化合物としては、炭素数１～２０のアルキルチオールが挙げられ、樹脂組成物への溶解性の観点から炭素数２～１８のアルキルチオールが好ましく、炭素数６～１８のアルキルチオールが、臭気が弱まるためにより好ましく、炭素数１２のアルキルチオールが樹脂組成物への溶解性と臭気低減の観点から特に好ましい。 [Thiol compound (D)]
The curable resin composition of the present invention may further contain a thiol compound. Examples of the thiol compound include alkylthiols having 1 to 20 carbon atoms. From the viewpoint of solubility in the resin composition, alkylthiols having 2 to 18 carbon atoms are preferable, and alkylthiols having 6 to 18 carbon atoms have an odor. It is more preferable because it weakens, and an alkyl thiol having 12 carbon atoms is particularly preferable from the viewpoint of solubility in the resin composition and reduction of odor.
本発明の硬化性樹脂組成物は、さらにチオール化合物を含有してもよい。チオール化合物としては、炭素数１～２０のアルキルチオールが挙げられ、樹脂組成物への溶解性の観点から炭素数２～１８のアルキルチオールが好ましく、炭素数６～１８のアルキルチオールが、臭気が弱まるためにより好ましく、炭素数１２のアルキルチオールが樹脂組成物への溶解性と臭気低減の観点から特に好ましい。 [Thiol compound (D)]
The curable resin composition of the present invention may further contain a thiol compound. Examples of the thiol compound include alkylthiols having 1 to 20 carbon atoms. From the viewpoint of solubility in the resin composition, alkylthiols having 2 to 18 carbon atoms are preferable, and alkylthiols having 6 to 18 carbon atoms have an odor. It is more preferable because it weakens, and an alkyl thiol having 12 carbon atoms is particularly preferable from the viewpoint of solubility in the resin composition and reduction of odor.
［硬化性樹脂組成物］
本発明の硬化性樹脂組成物は、上記含フッ素ポリマー（Ｐ）と、前記化合物（Ａ）と、前記開始剤（Ｂ）を含有する。 [Curable resin composition]
The curable resin composition of the present invention contains the fluoropolymer (P), the compound (A), and the initiator (B).
本発明の硬化性樹脂組成物は、上記含フッ素ポリマー（Ｐ）と、前記化合物（Ａ）と、前記開始剤（Ｂ）を含有する。 [Curable resin composition]
The curable resin composition of the present invention contains the fluoropolymer (P), the compound (A), and the initiator (B).
本発明の硬化性樹脂組成物は、含フッ素ポリマー（Ｐ）１００質量部に対し、前記化合物（Ａ）を０．０１～１０質量部、前記開始剤（Ｂ）を０．０５～５質量部含有する。
The curable resin composition of the present invention contains 0.01 to 10 parts by mass of the compound (A) and 0.05 to 5 parts by mass of the initiator (B) with respect to 100 parts by mass of the fluoropolymer (P). contains.
前記化合物（Ａ）の含有量は、透過率低下を抑制するために、含フッ素ポリマー（Ｐ）１００質量部に対し、０．０５～８質量部が好ましく、０．０８～５質量部がより好ましく、０．１～３質量部がさらに好ましい。化合物（Ａ）の含有量が０．０１質量部以上であれば透過率低下を抑制する効果が発現しやすく、１０質量部以下であれば含フッ素ポリマーへの相溶性が良好である。
The content of the compound (A) is preferably 0.05 to 8 parts by mass, more preferably 0.08 to 5 parts by mass with respect to 100 parts by mass of the fluoropolymer (P) in order to suppress a decrease in transmittance. It is preferable, and 0.1 to 3 parts by mass is more preferable. When the content of the compound (A) is 0.01 parts by mass or more, the effect of suppressing the decrease in transmittance is likely to be exhibited, and when the content is 10 parts by mass or less, the compatibility with the fluoropolymer is good.
前記開始剤（Ｂ）の含有量は、硬化性樹脂組成物を効率的に硬化させるために、含フッ素ポリマー（Ｐ）１００質量部に対し、０．０８～５質量部が好ましく、０．１～４質量部がより好ましく、０．５～３質量部がさらに好ましい。化合物（Ｂ）の含有量が０．０５質量部以上であれば硬化性樹脂組成物の硬化性が良好であり、５質量部以下であれば含フッ素ポリマーへの相溶性が良好であり、また含フッ素ポリマーの着色を誘発するおそれが少ない。
The content of the initiator (B) is preferably 0.08 to 5 parts by mass with respect to 100 parts by mass of the fluoropolymer (P) in order to efficiently cure the curable resin composition, and is 0.1. Up to 4 parts by mass is more preferable, and 0.5 to 3 parts by mass is further preferable. When the content of the compound (B) is 0.05 parts by mass or more, the curability of the curable resin composition is good, and when the content of the compound (B) is 5 parts by mass or less, the compatibility with the fluoropolymer is good. There is little risk of inducing coloration of the fluoropolymer.
本発明の硬化性樹脂組成物は、さらに、含フッ素フェノール系酸化防止剤（Ｃ）を含フッ素ポリマー（Ｐ）１００質量部に対し、０．０１～１０質量部含有することが透過率低下の抑制の観点から好ましい。
The curable resin composition of the present invention further contains 0.01 to 10 parts by mass of the fluorophenol-based antioxidant (C) with respect to 100 parts by mass of the fluoropolymer (P) to reduce the transmittance. It is preferable from the viewpoint of suppression.
前記含フッ素フェノール系酸化防止剤（Ｃ）は、透過率低下を抑制できるため、前記化合物（Ａ）と併用することが好ましく、含有量は、含フッ素ポリマー（Ｐ）１００質量部に対し、０．０５～８質量部がさらに好ましく、０．１～５質量部がより好ましく、０．５～３質量部が特に好ましい。化合物（Ｃ）の含有量が０．０１質量部以上であれば透過率低下を抑制する併用効果が発現しやすく、１０質量部以下であれば含フッ素ポリマーへの相溶性が良好であり、また含フッ素ポリマーの着色を誘発するおそれが少ない。
Since the fluorophenol-based antioxidant (C) can suppress a decrease in transmittance, it is preferable to use it in combination with the compound (A), and the content is 0 with respect to 100 parts by mass of the fluoropolymer (P). .05 to 8 parts by mass is more preferable, 0.1 to 5 parts by mass is more preferable, and 0.5 to 3 parts by mass is particularly preferable. When the content of the compound (C) is 0.01 parts by mass or more, the combined effect of suppressing the decrease in transmittance is likely to be exhibited, and when the content is 10 parts by mass or less, the compatibility with the fluoropolymer is good, and the compatibility with the fluoropolymer is good. There is little risk of inducing coloring of the fluoropolymer.
本発明の硬化性樹脂組成物は、さらに、チオール化合物（Ｄ）を０．１～５質量部含有することが透過率低下の抑制効果を高める観点から好ましい。
It is preferable that the curable resin composition of the present invention further contains 0.1 to 5 parts by mass of the thiol compound (D) from the viewpoint of enhancing the effect of suppressing the decrease in transmittance.
前記チオール化合物（Ｄ）は、透過率低下を抑制できるため、前記化合物（Ａ）と併用することが好ましく、含有量は、含フッ素ポリマー（Ｐ）１００質量部に対し、０．１～３質量部が好ましく、０．３～３質量部がより好ましく、０．５～２質量部がさらに好ましい。化合物（Ｄ）の含有量が０．１質量部以上であれば透過率低下を抑制する併用効果が発現しやすく、５質量部以下であれば含フッ素ポリマーへの相溶性が良好である。
Since the thiol compound (D) can suppress a decrease in transmittance, it is preferably used in combination with the compound (A), and the content is 0.1 to 3% by mass with respect to 100 parts by mass of the fluoropolymer (P). Parts are preferable, 0.3 to 3 parts by mass is more preferable, and 0.5 to 2 parts by mass is further preferable. When the content of the compound (D) is 0.1 part by mass or more, the combined effect of suppressing the decrease in transmittance is likely to be exhibited, and when the content is 5 parts by mass or less, the compatibility with the fluoropolymer is good.
本発明の硬化性樹脂組成物には、上記以外にも、各種添加剤として界面活性剤、リン系酸化防止剤、チクソトロピック剤、消泡剤、ゲル化防止剤、光増感剤、樹脂、金属酸化物微粒子、炭素化合物、金属微粒子、シランカップリング剤、他の有機化合物等を必要に応じて０．００１～５質量部添加してもよい。
In addition to the above, the curable resin composition of the present invention includes various additives such as surfactants, phosphorus-based antioxidants, thixotropic agents, antifoaming agents, antigelling agents, photosensitizers, resins, and the like. If necessary, 0.001 to 5 parts by mass of metal oxide fine particles, carbon compounds, metal fine particles, a silane coupling agent, other organic compounds and the like may be added.
［硬化物］
本発明の硬化物は、本発明の硬化性樹脂組成物を硬化した硬化物である。 [Cured product]
The cured product of the present invention is a cured product obtained by curing the curable resin composition of the present invention.
本発明の硬化物は、本発明の硬化性樹脂組成物を硬化した硬化物である。 [Cured product]
The cured product of the present invention is a cured product obtained by curing the curable resin composition of the present invention.
硬化物の厚みは、特に限定されず、例えば、０．０５～１０．０ｍｍが好ましい。硬化物の形成方法としては、微細パターンの反転パターンを表面に有するモールドと硬化性樹脂組成物とを接触させた状態で前記硬化性樹脂組成物を硬化させ、微細パターンを表面に有する硬化物を形成する方法（インプリント法）を例示できる。また、モールドのキャビティ内に硬化性樹脂組成物を注入し、前記硬化性樹脂組成物を硬化させて硬化物を形成する方法（注型成形法）でもよい。
The thickness of the cured product is not particularly limited, and is preferably 0.05 to 10.0 mm, for example. As a method for forming the cured product, the curable resin composition is cured in a state where the mold having the inverted pattern of the fine pattern on the surface and the curable resin composition are in contact with each other, and the cured product having the fine pattern on the surface is obtained. The method of forming (imprint method) can be exemplified. Alternatively, a method of injecting a curable resin composition into the cavity of the mold and curing the curable resin composition to form a cured product (casting molding method) may also be used.
以下では実施例により本発明をより具体的に説明するが、本発明は後述する実施例に限定されず、本発明の要旨を変更しない限り、種々の変更が可能である。
なお、例１～９は実施例であり、例１０～１５は比較例である。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples described later, and various modifications can be made as long as the gist of the present invention is not changed.
Examples 1 to 9 are examples, and examples 10 to 15 are comparative examples.
なお、例１～９は実施例であり、例１０～１５は比較例である。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples described later, and various modifications can be made as long as the gist of the present invention is not changed.
Examples 1 to 9 are examples, and examples 10 to 15 are comparative examples.
［含フッ素ポリマー（Ｐ）］
Ｍ－１：１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（２０ｇ）、カレンズＢＥＩ（昭和電工社製）（１２．７ｇ）、ジブチルヒドロキシトルエン（０．０５ｇ）、ジブチルスズジラウレート（０．１ｇ）を３００ｍＬの３つ口フラスコに入れ、５０℃で２時間攪拌した。ＦＴ－ＩＲスペクトルの２５００ｃｍ－１ピークが消失したことを確認した後、酢酸エチルと１ｍｏｌ／Ｌの塩酸を１００ｍＬずつ加えて攪拌した。有機層を飽和重曹水、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。溶媒を減圧留去し、含フッ素ジアクリレート（Ｍ－１）を得た。 [Fluororesin-containing polymer (P)]
M-1: 1H, 1H, 2H, 2H-Tridecafluoro-1-octanol (20 g), Karenz BEI (manufactured by Showa Denko) (12.7 g), dibutylhydroxytoluene (0.05 g), dibutyltin dilaurate (0) .1 g) was placed in a 300 mL three-necked flask and stirred at 50 ° C. for 2 hours. After confirming that the 2500 cm -1 peak of the FT-IR spectrum had disappeared, 100 mL each of ethyl acetate and 1 mol / L hydrochloric acid were added and stirred. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a fluorine-containing diacrylate (M-1).
Ｍ－１：１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（２０ｇ）、カレンズＢＥＩ（昭和電工社製）（１２．７ｇ）、ジブチルヒドロキシトルエン（０．０５ｇ）、ジブチルスズジラウレート（０．１ｇ）を３００ｍＬの３つ口フラスコに入れ、５０℃で２時間攪拌した。ＦＴ－ＩＲスペクトルの２５００ｃｍ－１ピークが消失したことを確認した後、酢酸エチルと１ｍｏｌ／Ｌの塩酸を１００ｍＬずつ加えて攪拌した。有機層を飽和重曹水、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。溶媒を減圧留去し、含フッ素ジアクリレート（Ｍ－１）を得た。 [Fluororesin-containing polymer (P)]
M-1: 1H, 1H, 2H, 2H-Tridecafluoro-1-octanol (20 g), Karenz BEI (manufactured by Showa Denko) (12.7 g), dibutylhydroxytoluene (0.05 g), dibutyltin dilaurate (0) .1 g) was placed in a 300 mL three-necked flask and stirred at 50 ° C. for 2 hours. After confirming that the 2500 cm -1 peak of the FT-IR spectrum had disappeared, 100 mL each of ethyl acetate and 1 mol / L hydrochloric acid were added and stirred. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a fluorine-containing diacrylate (M-1).
Ｍ－２：Ｆｏｍｂｌｉｎ－Ｄ２（Ｓｏｌｖａｙ社製）（３ｇ）、アサヒクリンＡＥ－３０００（アサヒクリンはＡＧＣの登録商標）（２０ｍＬ）、トリエチルアミン（１．５ｇ）を１００ｍＬの３つ口フラスコに入れ、氷浴下で攪拌した。アクリル酸クロリド（１ｇ）を５分かけて滴下したあと、５０℃で１２時間攪拌した。室温に戻したあと、１ｍｏｌ／Ｌの塩酸を１００ｍＬ加えて攪拌した。有機層を飽和重曹水、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。シリカゲルクロマトグラフィで精製をおこない含フッ素ジアクリレート（Ｍ－２）を得た。
M-2: Fomblin-D2 (manufactured by Solvay) (3 g), Asahiclin AE-3000 (Asahiclin is a registered trademark of AGC) (20 mL), and triethylamine (1.5 g) are placed in a 100 mL three-necked flask. Stirred under an ice bath. Acrylic acid chloride (1 g) was added dropwise over 5 minutes, and then the mixture was stirred at 50 ° C. for 12 hours. After returning to room temperature, 100 mL of 1 mol / L hydrochloric acid was added and stirred. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. Purification was performed by silica gel chromatography to obtain a fluorine-containing diacrylate (M-2).
Ｍ－３：フルオロリンクＭＤ７００（ＳＯＬＶＡＹ社製）
Ｍ－４：３，３，４，４，５，５，６，６，７，７，８，８，８－トリデカフルオロオクチルメタクリレート M-3: Fluorolink MD700 (manufactured by SOLVAY)
M-4: 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl methacrylate
Ｍ－４：３，３，４，４，５，５，６，６，７，７，８，８，８－トリデカフルオロオクチルメタクリレート M-3: Fluorolink MD700 (manufactured by SOLVAY)
M-4: 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl methacrylate
［化合物（Ａ）］
［化合物（Ａ－１）の合成］
以下に記載する方法で合成し、化合物（Ａ－１）とした。
３，３’－チオジプロピオン酸の２５ｇと１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（１０３ｇ）、トルエン（２０ｍＬ）、パラトルエンスルホン酸（０．１ｇ）を２００ｍＬの３つ口フラスコで攪拌し、１２５℃で加熱しながらディーンスターク装置を用いて、生じる水を除きながら１０時間反応させた。室温に戻した後アサヒクリンＡＥ－３０００（１００ｍＬ）を加え、有機層を飽和重曹水と飽和食塩水で洗浄した。溶媒を留去したのち、メタノールに室温で溶解させ、５℃に冷却することで白色結晶（Ａ－１）を１００ｇ得た。 [Compound (A)]
[Synthesis of compound (A-1)]
It was synthesized by the method described below to obtain compound (A-1).
25 g of 3,3'-thiodipropionic acid and 200 mL of 1H, 1H, 2H, 2H-tridecafluoro-1-octanol (103 g), toluene (20 mL) and paratoluenesulfonic acid (0.1 g) The mixture was stirred in a mouth flask and reacted for 10 hours while heating at 125 ° C. using a Dean-Stark apparatus to remove the resulting water. After returning to room temperature, Asahiclean AE-3000 (100 mL) was added, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine. After distilling off the solvent, it was dissolved in methanol at room temperature and cooled to 5 ° C. to obtain 100 g of white crystals (A-1).
［化合物（Ａ－１）の合成］
以下に記載する方法で合成し、化合物（Ａ－１）とした。
３，３’－チオジプロピオン酸の２５ｇと１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（１０３ｇ）、トルエン（２０ｍＬ）、パラトルエンスルホン酸（０．１ｇ）を２００ｍＬの３つ口フラスコで攪拌し、１２５℃で加熱しながらディーンスターク装置を用いて、生じる水を除きながら１０時間反応させた。室温に戻した後アサヒクリンＡＥ－３０００（１００ｍＬ）を加え、有機層を飽和重曹水と飽和食塩水で洗浄した。溶媒を留去したのち、メタノールに室温で溶解させ、５℃に冷却することで白色結晶（Ａ－１）を１００ｇ得た。 [Compound (A)]
[Synthesis of compound (A-1)]
It was synthesized by the method described below to obtain compound (A-1).
25 g of 3,3'-thiodipropionic acid and 200 mL of 1H, 1H, 2H, 2H-tridecafluoro-1-octanol (103 g), toluene (20 mL) and paratoluenesulfonic acid (0.1 g) The mixture was stirred in a mouth flask and reacted for 10 hours while heating at 125 ° C. using a Dean-Stark apparatus to remove the resulting water. After returning to room temperature, Asahiclean AE-3000 (100 mL) was added, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine. After distilling off the solvent, it was dissolved in methanol at room temperature and cooled to 5 ° C. to obtain 100 g of white crystals (A-1).
［開始剤（Ｂ）］
開始剤（Ｂ－１）：Ｏｍｎｉｒａｄ１１７３（ＩＧＭ Ｒｅｓｉｎｓ社製） [Initiator (B)]
Initiator (B-1): Omnirad 1173 (manufactured by IGM Resins)
開始剤（Ｂ－１）：Ｏｍｎｉｒａｄ１１７３（ＩＧＭ Ｒｅｓｉｎｓ社製） [Initiator (B)]
Initiator (B-1): Omnirad 1173 (manufactured by IGM Resins)
［含フッ素フェノール系酸化防止剤（Ｃ）］
酸化防止剤（Ｃ－１）：日本国特開２０１４－１１８３５５号公報の例２の方法に従って、以下に記載する方法で合成し、下記化合物（Ｃ－１）を得た。
３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸（２５ｇ）と１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（２９．５ｇ）とジクロロメタン（１４０ｍＬ）、テトラヒドロフラン（７０ｍＬ）を３００ｍＬの３つ口フラスコで攪拌した。ジメチルアミノピリジン（０．３４ｇ）と１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩（１７ｇ）を加え室温で１８時間攪拌した後、１ｍｏｌ／Ｌの塩酸と飽和食塩水で有機層を洗浄し、硫酸マグネシウムで乾燥した。シリカゲルカラムクロマトグラフィで生成をおこなった後、メタノールで再結晶をおこない白色結晶（Ｃ－１）を２１ｇ得た。 [Fluorine-containing phenolic antioxidant (C)]
Antioxidant (C-1): The following compound (C-1) was obtained by synthesizing by the method described below according to the method of Example 2 of Japanese Patent Application Laid-Open No. 2014-118355.
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (25 g) and 1H, 1H, 2H, 2H-tridecafluoro-1-octanol (29.5 g) and dichloromethane (140 mL), Tetrahydrofuran (70 mL) was stirred in a 300 mL three-necked flask. After adding dimethylaminopyridine (0.34 g) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (17 g) and stirring at room temperature for 18 hours, an organic layer is added with 1 mol / L hydrochloric acid and saturated brine. Was washed and dried over magnesium sulfate. After the production by silica gel column chromatography, it was recrystallized from methanol to obtain 21 g of white crystals (C-1).
酸化防止剤（Ｃ－１）：日本国特開２０１４－１１８３５５号公報の例２の方法に従って、以下に記載する方法で合成し、下記化合物（Ｃ－１）を得た。
３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸（２５ｇ）と１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（２９．５ｇ）とジクロロメタン（１４０ｍＬ）、テトラヒドロフラン（７０ｍＬ）を３００ｍＬの３つ口フラスコで攪拌した。ジメチルアミノピリジン（０．３４ｇ）と１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩（１７ｇ）を加え室温で１８時間攪拌した後、１ｍｏｌ／Ｌの塩酸と飽和食塩水で有機層を洗浄し、硫酸マグネシウムで乾燥した。シリカゲルカラムクロマトグラフィで生成をおこなった後、メタノールで再結晶をおこない白色結晶（Ｃ－１）を２１ｇ得た。 [Fluorine-containing phenolic antioxidant (C)]
Antioxidant (C-1): The following compound (C-1) was obtained by synthesizing by the method described below according to the method of Example 2 of Japanese Patent Application Laid-Open No. 2014-118355.
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (25 g) and 1H, 1H, 2H, 2H-tridecafluoro-1-octanol (29.5 g) and dichloromethane (140 mL), Tetrahydrofuran (70 mL) was stirred in a 300 mL three-necked flask. After adding dimethylaminopyridine (0.34 g) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (17 g) and stirring at room temperature for 18 hours, an organic layer is added with 1 mol / L hydrochloric acid and saturated brine. Was washed and dried over magnesium sulfate. After the production by silica gel column chromatography, it was recrystallized from methanol to obtain 21 g of white crystals (C-1).
［チオール化合物（Ｄ）］
化合物（Ｄ－１）：ドデカンチオール（東京化成工業社製） [Thiol compound (D)]
Compound (D-1): Dodecane thiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
化合物（Ｄ－１）：ドデカンチオール（東京化成工業社製） [Thiol compound (D)]
Compound (D-1): Dodecane thiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
［化合物（Ｘ－１）］
化合物（Ｘ－１）：３，３’－チオジプロピオン酸ジドデシル（東京化成工業社製） [Compound (X-1)]
Compound (X-1): Didodecyl thiodipropionate (manufactured by Tokyo Chemical Industry Co., Ltd.)
化合物（Ｘ－１）：３，３’－チオジプロピオン酸ジドデシル（東京化成工業社製） [Compound (X-1)]
Compound (X-1): Didodecyl thiodipropionate (manufactured by Tokyo Chemical Industry Co., Ltd.)
［硬化性樹脂組成物の調製］
［例１～１５］
表１に記載の各成分を褐色のサンプル瓶を用いて、配合組成（質量部）にしたがって配合し、５０℃に保ちながらミックスローターで１時間攪拌、混合することで硬化性樹脂組成物を得た。 [Preparation of curable resin composition]
[Examples 1 to 15]
Each component shown in Table 1 is blended according to the blending composition (part by mass) using a brown sample bottle, and the curable resin composition is obtained by stirring and mixing with a mix rotor for 1 hour while keeping the temperature at 50 ° C. rice field.
［例１～１５］
表１に記載の各成分を褐色のサンプル瓶を用いて、配合組成（質量部）にしたがって配合し、５０℃に保ちながらミックスローターで１時間攪拌、混合することで硬化性樹脂組成物を得た。 [Preparation of curable resin composition]
[Examples 1 to 15]
Each component shown in Table 1 is blended according to the blending composition (part by mass) using a brown sample bottle, and the curable resin composition is obtained by stirring and mixing with a mix rotor for 1 hour while keeping the temperature at 50 ° C. rice field.
＜相溶性評価＞
上記の硬化性樹脂組成物を調製する際と、調製後２５℃で３０分放置した後に、目視で固体の析出の有無を確認した。
硬化性樹脂組成物を調製する際と調整後２５℃で３０分放置した後のいずれかもしくは両方で固体の析出がある場合を「あり」、どちらも固体の析出が無い場合を「なし」と評価した。表２に評価結果を示す。
例１３～１５では、硬化性樹脂組成物調製時の５０℃で１時間攪拌の際に、化合物（Ｘ－１）とみられる固体が溶解せず、均一な組成物の調製が困難であった。 <Compatibility evaluation>
When preparing the above curable resin composition and after leaving it at 25 ° C. for 30 minutes after preparation, the presence or absence of solid precipitation was visually confirmed.
"Yes" means that there is solid precipitation at the time of preparing the curable resin composition and / or after leaving it at 25 ° C. for 30 minutes after adjustment, and "None" means that there is no solid precipitation in either case. evaluated. Table 2 shows the evaluation results.
In Examples 13 to 15, when the curable resin composition was stirred at 50 ° C. for 1 hour, the solid considered to be compound (X-1) did not dissolve, and it was difficult to prepare a uniform composition.
上記の硬化性樹脂組成物を調製する際と、調製後２５℃で３０分放置した後に、目視で固体の析出の有無を確認した。
硬化性樹脂組成物を調製する際と調整後２５℃で３０分放置した後のいずれかもしくは両方で固体の析出がある場合を「あり」、どちらも固体の析出が無い場合を「なし」と評価した。表２に評価結果を示す。
例１３～１５では、硬化性樹脂組成物調製時の５０℃で１時間攪拌の際に、化合物（Ｘ－１）とみられる固体が溶解せず、均一な組成物の調製が困難であった。 <Compatibility evaluation>
When preparing the above curable resin composition and after leaving it at 25 ° C. for 30 minutes after preparation, the presence or absence of solid precipitation was visually confirmed.
"Yes" means that there is solid precipitation at the time of preparing the curable resin composition and / or after leaving it at 25 ° C. for 30 minutes after adjustment, and "None" means that there is no solid precipitation in either case. evaluated. Table 2 shows the evaluation results.
In Examples 13 to 15, when the curable resin composition was stirred at 50 ° C. for 1 hour, the solid considered to be compound (X-1) did not dissolve, and it was difficult to prepare a uniform composition.
＜透過率評価＞
例１～１５で得られた樹脂組成物を、１ｍｍのスペーサーを介して２枚の石英ガラスで挟み込み、紫外ＬＥＤ照射装置をもちいて、波長３６５ｎｍの光を３０００ｍＪ／ｃｍ２照射した。得られた膜状の硬化物を石英ガラス基板から離型させた。得られた膜状の硬化物を１２５℃で１５分間ベークし、厚さ１ｍｍの硬化物を得た。
上記の厚さ１ｍｍの硬化物を透過率測定サンプルとした。得られた硬化物のうち、例１３～１５の硬化性樹脂組成物を硬化させたものは、硬化物が白濁しており、透過率の評価が困難であった。
得られた硬化物のうち、例１～１２の硬化性樹脂組成物を硬化させたものの波長４００ｎｍでの透過率を、紫外・可視・近赤外分光光度計（島津製作所社製、Ｓｏｌｉｄ Ｓｐｅｃ－３７００）で測定した。初期透過率として表２に評価結果を示す。
得られた硬化物を８５℃相対湿度８５％の恒温恒湿槽に２５０時間保持したのち、波長４００ｎｍでの透過率を上記測定装置を用いて測定した。耐湿熱試験後の透過率として表２に評価結果を示す。
初期透過率から湿熱試験後の透過率を引いた値を、Δ透過率として表２に評価結果を示す。 <Transmittance evaluation>
The resin compositions obtained in Examples 1 to 15 were sandwiched between two quartz glasses via a 1 mm spacer, and irradiated with light having a wavelength of 365 nm at 3000 mJ / cm 2 using an ultraviolet LED irradiator. The obtained film-like cured product was released from the quartz glass substrate. The obtained film-like cured product was baked at 125 ° C. for 15 minutes to obtain a cured product having a thickness of 1 mm.
The cured product having a thickness of 1 mm was used as a transmittance measurement sample. Among the obtained cured products, those obtained by curing the curable resin compositions of Examples 13 to 15 had a cloudy cured product, and it was difficult to evaluate the transmittance.
Among the obtained cured products, the transmittance of the cured resin compositions of Examples 1 to 12 at a wavelength of 400 nm was measured by an ultraviolet / visible / near-infrared spectrophotometer (manufactured by Shimadzu Corporation, Solid Spec-). It was measured in 3700). Table 2 shows the evaluation results as the initial transmittance.
The obtained cured product was held in a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85% for 250 hours, and then the transmittance at a wavelength of 400 nm was measured using the above measuring device. Table 2 shows the evaluation results as the transmittance after the moisture resistance heat test.
The value obtained by subtracting the transmittance after the wet heat test from the initial transmittance is shown in Table 2 as the Δ transmittance.
例１～１５で得られた樹脂組成物を、１ｍｍのスペーサーを介して２枚の石英ガラスで挟み込み、紫外ＬＥＤ照射装置をもちいて、波長３６５ｎｍの光を３０００ｍＪ／ｃｍ２照射した。得られた膜状の硬化物を石英ガラス基板から離型させた。得られた膜状の硬化物を１２５℃で１５分間ベークし、厚さ１ｍｍの硬化物を得た。
上記の厚さ１ｍｍの硬化物を透過率測定サンプルとした。得られた硬化物のうち、例１３～１５の硬化性樹脂組成物を硬化させたものは、硬化物が白濁しており、透過率の評価が困難であった。
得られた硬化物のうち、例１～１２の硬化性樹脂組成物を硬化させたものの波長４００ｎｍでの透過率を、紫外・可視・近赤外分光光度計（島津製作所社製、Ｓｏｌｉｄ Ｓｐｅｃ－３７００）で測定した。初期透過率として表２に評価結果を示す。
得られた硬化物を８５℃相対湿度８５％の恒温恒湿槽に２５０時間保持したのち、波長４００ｎｍでの透過率を上記測定装置を用いて測定した。耐湿熱試験後の透過率として表２に評価結果を示す。
初期透過率から湿熱試験後の透過率を引いた値を、Δ透過率として表２に評価結果を示す。 <Transmittance evaluation>
The resin compositions obtained in Examples 1 to 15 were sandwiched between two quartz glasses via a 1 mm spacer, and irradiated with light having a wavelength of 365 nm at 3000 mJ / cm 2 using an ultraviolet LED irradiator. The obtained film-like cured product was released from the quartz glass substrate. The obtained film-like cured product was baked at 125 ° C. for 15 minutes to obtain a cured product having a thickness of 1 mm.
The cured product having a thickness of 1 mm was used as a transmittance measurement sample. Among the obtained cured products, those obtained by curing the curable resin compositions of Examples 13 to 15 had a cloudy cured product, and it was difficult to evaluate the transmittance.
Among the obtained cured products, the transmittance of the cured resin compositions of Examples 1 to 12 at a wavelength of 400 nm was measured by an ultraviolet / visible / near-infrared spectrophotometer (manufactured by Shimadzu Corporation, Solid Spec-). It was measured in 3700). Table 2 shows the evaluation results as the initial transmittance.
The obtained cured product was held in a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85% for 250 hours, and then the transmittance at a wavelength of 400 nm was measured using the above measuring device. Table 2 shows the evaluation results as the transmittance after the moisture resistance heat test.
The value obtained by subtracting the transmittance after the wet heat test from the initial transmittance is shown in Table 2 as the Δ transmittance.
＜外観＞
上記の透過率測定サンプルの外観を目視で確認した。表２に評価結果を示す。 <Appearance>
The appearance of the above transmittance measurement sample was visually confirmed. Table 2 shows the evaluation results.
上記の透過率測定サンプルの外観を目視で確認した。表２に評価結果を示す。 <Appearance>
The appearance of the above transmittance measurement sample was visually confirmed. Table 2 shows the evaluation results.
含フッ素チオエーテル骨格を有する化合物（Ａ－１）を含む例１～９では、例１０～１２と比較してΔ透過率から明らかな様に、耐湿熱試験後の透過率低下の抑制効果に優れていた。さらに含フッ素チオエーテル骨格を有する化合物（Ａ－１）と含フッ素フェノール系酸化防止剤（Ｃ－１）を共に含む例４、７、９では湿熱試験後の透過率低下の抑制効果がより優れており、併用効果があることが明らかであった。
In Examples 1 to 9 containing the compound (A-1) having a fluorine-containing thioether skeleton, as is clear from the Δ transmittance, the effect of suppressing the decrease in transmittance after the moisture resistance test is excellent as compared with Examples 10 to 12. Was there. Further, in Examples 4, 7 and 9 containing both the compound having a fluorine-containing thioether skeleton (A-1) and the fluorine-containing phenolic antioxidant (C-1), the effect of suppressing the decrease in transmittance after the moist heat test is more excellent. It was clear that there was a combined effect.
一方、分子中にフッ素原子を含まないチオエーテル骨格を有する化合物（Ｘ－１）を含む例１３～１５では、フッ素ポリマーとの相溶性が低く、化合物（Ｘ－１）とみられる固体の析出が生じた。作製した硬化物の外観も白く濁っていた。
On the other hand, in Examples 13 to 15 containing the compound (X-1) having a thioether skeleton containing no fluorine atom in the molecule, the compatibility with the fluoropolymer is low, and the precipitation of a solid considered to be the compound (X-1) occurs. rice field. The appearance of the produced cured product was also white and cloudy.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０２０年２月１３日出願の日本特許出願（特願２０２０－２２５２０）に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on February 13, 2020 (Japanese Patent Application No. 2020-22520), the contents of which are incorporated herein by reference.
Claims (4)
- 含フッ素ポリマー（Ｐ）１００質量部に対し、下記一般式（１）で表される含フッ素チオエーテル骨格を有する化合物（Ａ）を０．０１～１０質量部、開始剤（Ｂ）を０．０５～５質量部含有する硬化性樹脂組成物。
（一般式（１）中、Ｒ１～Ｒ４は各々独立に、炭素数１～１０のアルキレン基を表す。Ｒｆ１およびＲｆ２は各々独立に、フッ素原子を有する炭素数１～２０のアルキル基を表し、炭素原子間にエーテル性酸素原子を含んでいてもよい。） With respect to 100 parts by mass of the fluoropolymer (P), 0.01 to 10 parts by mass of the compound (A) having a fluoroether skeleton represented by the following general formula (1) and 0.05 of the initiator (B). A curable resin composition containing up to 5 parts by mass.
(In the general formula (1), R 1 to R 4 independently represent an alkylene group having 1 to 10 carbon atoms. Rf 1 and Rf 2 each independently represent an alkyl having 1 to 20 carbon atoms having a fluorine atom. It represents a group and may contain etheric oxygen atoms between carbon atoms.) - 前記含フッ素ポリマー（Ｐ）１００質量部に対し、さらに含フッ素フェノール系酸化防止剤（Ｃ）を０．０１～１０質量部含有する、請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, further containing 0.01 to 10 parts by mass of the fluorophenol-based antioxidant (C) with respect to 100 parts by mass of the fluoropolymer (P).
- 前記含フッ素フェノール系酸化防止剤（Ｃ）が下記一般式（２）で表される請求項２に記載の硬化性樹脂組成物。
（一般式（２）中、Ｒ５およびＲ６は各々独立に、水素原子、ハロゲン原子、ヒドロキシ基、シアノ基、ニトロ基、カルボキシル基、リン酸基、炭素数１～１０のアルキル基または炭素数１～１０のアルコキシ基を表す。Ｒ７およびＲ８は各々独立に、炭素数１～１０のアルキレン基を表す。Ｒｆ３はフッ素原子を有する炭素数１～２０のアルキル基を表し、炭素原子間にエーテル性酸素原子を含んでいてもよい。） The curable resin composition according to claim 2, wherein the fluorine-containing phenolic antioxidant (C) is represented by the following general formula (2).
(In the general formula (2), R 5 and R 6 are independently hydrogen atom, halogen atom, hydroxy group, cyano group, nitro group, carboxyl group, phosphoric acid group, alkyl group having 1 to 10 carbon atoms or carbon. Represents an alkoxy group of numbers 1 to 10. R 7 and R 8 each independently represent an alkylene group having 1 to 10 carbon atoms. Rf 3 represents an alkyl group having 1 to 20 carbon atoms having a fluorine atom and carbon. It may contain an etheric oxygen atom between the atoms.) - 請求項１～３のいずれか一項に記載の硬化性樹脂組成物を硬化させてなる硬化物。 A cured product obtained by curing the curable resin composition according to any one of claims 1 to 3.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08325465A (en) * | 1995-06-02 | 1996-12-10 | Asahi Glass Co Ltd | Curable composition |
| JPH11349819A (en) * | 1998-06-03 | 1999-12-21 | Matsushita Electric Ind Co Ltd | Stainproofing agent for resin and stainproof resin containing the same |
| JP2014118356A (en) * | 2012-12-13 | 2014-06-30 | Fujifilm Corp | Fluorine atom-containing mercapto compound |
| WO2014141759A1 (en) * | 2013-03-14 | 2014-09-18 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic resin composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08325465A (en) * | 1995-06-02 | 1996-12-10 | Asahi Glass Co Ltd | Curable composition |
| JPH11349819A (en) * | 1998-06-03 | 1999-12-21 | Matsushita Electric Ind Co Ltd | Stainproofing agent for resin and stainproof resin containing the same |
| JP2014118356A (en) * | 2012-12-13 | 2014-06-30 | Fujifilm Corp | Fluorine atom-containing mercapto compound |
| WO2014141759A1 (en) * | 2013-03-14 | 2014-09-18 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic resin composition |
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