JP2007153970A - Method for producing amorphous fluorine-containing resin - Google Patents
Method for producing amorphous fluorine-containing resin Download PDFInfo
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- JP2007153970A JP2007153970A JP2005348715A JP2005348715A JP2007153970A JP 2007153970 A JP2007153970 A JP 2007153970A JP 2005348715 A JP2005348715 A JP 2005348715A JP 2005348715 A JP2005348715 A JP 2005348715A JP 2007153970 A JP2007153970 A JP 2007153970A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 81
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011737 fluorine Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000011347 resin Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000002834 transmittance Methods 0.000 claims description 20
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 14
- 230000035699 permeability Effects 0.000 abstract description 6
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052805 deuterium Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- IZLFSDDOEKWVLD-UHFFFAOYSA-N 2-chloro-1,1,3,4,4,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(C(F)(F)F)C(C(C(=C(F)F)Cl)F)(F)F IZLFSDDOEKWVLD-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
Description
本発明は、非晶性含フッ素樹脂の製造方法に関する。 The present invention relates to a method for producing an amorphous fluorine-containing resin.
非晶性含フッ素樹脂は、各種樹脂材料の中でも紫外線領域（波長２００〜３８０ｎｍ）における光線透過率が特に高く、紫外線領域における透明性が要求される光学用途に適している。非晶性含フッ素樹脂の中でも脂肪族環構造を有する非晶性含フッ素樹脂は、紫外線透過性および紫外線耐久性に優れており、紫外線用レンズ、紫外線光源の封止材として有用である。 The amorphous fluorine-containing resin has a particularly high light transmittance in the ultraviolet region (wavelength 200 to 380 nm) among various resin materials, and is suitable for optical applications that require transparency in the ultraviolet region. Among the amorphous fluorine-containing resins, the amorphous fluorine-containing resin having an aliphatic ring structure is excellent in ultraviolet transmittance and ultraviolet durability, and is useful as a sealing material for ultraviolet lenses and ultraviolet light sources.
脂肪族環構造を有する非晶性含フッ素樹脂の製造方法としては、特定の重合開始剤を用い、含フッ素脂肪族環構造を有するモノマーおよび／または２つ以上の重合性二重結合を有する含フッ素モノマーを塊状重合する方法が開示されている（特許文献１）。しかし、該方法で得られた非晶性含フッ素樹脂は、不安定な高分子鎖末端および／または微量の不純物を含んでいる場合があり、紫外線透過性は必ずしも充分ではない。 As a method for producing an amorphous fluorine-containing resin having an aliphatic ring structure, a specific polymerization initiator is used, and a monomer having a fluorine-containing aliphatic ring structure and / or two or more polymerizable double bonds are contained. A method for bulk polymerization of a fluorine monomer is disclosed (Patent Document 1). However, the amorphous fluorine-containing resin obtained by this method may contain unstable polymer chain ends and / or a small amount of impurities, and the ultraviolet ray permeability is not always sufficient.
不安定な高分子鎖末端および微量の不純物を除去する方法としては、非晶性含フッ素樹脂をフッ素ガスで処理する方法が開示されている（特許文献２）。しかし、該方法は、非常に煩雑であるため生産性が低い。よって、非晶性含フッ素樹脂に含まれる不安定な高分子鎖末端および微量の不純物をより簡便に除去する方法が要求されている。
本発明の目的は、生産性の高い簡便な方法で、紫外線透過性に優れる非晶性含フッ素樹脂を得ることができる製造方法を提供することである。 The objective of this invention is providing the manufacturing method which can obtain the amorphous fluorine-containing resin which is excellent in ultraviolet-ray permeability with a simple method with high productivity.
本発明の非晶性含フッ素樹脂の製造方法は、非晶性含フッ素樹脂に紫外線を照射する処理を含むことを特徴とする。
非晶性含フッ素樹脂は、脂肪族環構造を有する非晶性含フッ素樹脂であることが好ましい。
高圧水銀灯または低圧水銀灯を用いて紫外線を照射することが好ましい。
The method for producing an amorphous fluorine-containing resin of the present invention is characterized by including a treatment of irradiating the amorphous fluorine-containing resin with ultraviolet rays.
The amorphous fluorine-containing resin is preferably an amorphous fluorine-containing resin having an aliphatic ring structure.
It is preferable to irradiate ultraviolet rays using a high-pressure mercury lamp or a low-pressure mercury lamp.
照射する紫外線の２５４ｎｍにおける積算光量は、２０Ｊ／ｃｍ2 以上であることが好ましい。
非晶性含フッ素樹脂は、成形体であってもよい。
波長３００ｎｍにおける光線透過率が８５％未満である非晶性含フッ素樹脂に紫外線を照射し、紫外線照射後の非晶性含フッ素樹脂の、波長３００ｎｍにおける光線透過率を８６％以上とすることが好ましい。
The integrated light quantity at 254 nm of the ultraviolet rays to be irradiated is preferably 20 J / cm 2 or more.
The amorphous fluorine-containing resin may be a molded body.
Irradiating the amorphous fluorine-containing resin having a light transmittance of less than 85% at a wavelength of 300 nm with ultraviolet rays, and setting the light transmittance at a wavelength of 300 nm of the amorphous fluorine-containing resin after the ultraviolet irradiation to 86% or more. preferable.
本発明の非晶性含フッ素樹脂の製造方法でよれば、生産性の高い簡便な方法で、紫外線透過性に優れる非晶性含フッ素樹脂を得ることができる。 According to the method for producing an amorphous fluorine-containing resin of the present invention, an amorphous fluorine-containing resin excellent in ultraviolet transmittance can be obtained by a simple method with high productivity.
本明細書においては、式（１）で表される化合物を化合物（１）と記す。他の式で表される化合物も同様に記す。 In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
本発明の非晶性含フッ素樹脂の製造方法は、非晶性含フッ素樹脂に紫外線を照射する処理を含む製造方法である。「非晶性含フッ素樹脂」とは、熱分析によって明確な融点を示さない含フッ素樹脂を意味する。 The method for producing an amorphous fluorine-containing resin of the present invention is a production method including a treatment of irradiating the amorphous fluorine-containing resin with ultraviolet rays. “Amorphous fluorine-containing resin” means a fluorine-containing resin that does not show a clear melting point by thermal analysis.
非晶性フッ素樹脂としては、分子鎖中に炭素−水素結合を有していない非晶性フッ素樹脂が好ましい。また、主鎖に脂肪族環構造を有する非晶性フッ素樹脂（以下、非晶性フッ素樹脂（ａ）と記す。）が好ましい。「主鎖に含フッ素脂肪族環構造を有する」とは、脂肪族環を構成する炭素原子の１以上が主鎖を構成する炭素連鎖中の炭素原子であり、かつ脂肪族環を構成する炭素原子の少なくとも一部にフッ素原子またはフッ素含有基が結合している構造を有していることを意味する。また、脂肪族環は、エーテル結合を有していてもよい。 As the amorphous fluororesin, an amorphous fluororesin having no carbon-hydrogen bond in the molecular chain is preferable. Further, an amorphous fluororesin having an aliphatic ring structure in the main chain (hereinafter referred to as amorphous fluororesin (a)) is preferable. “Having a fluorinated aliphatic ring structure in the main chain” means that one or more of the carbon atoms constituting the aliphatic ring is a carbon atom in the carbon chain constituting the main chain, and the carbon constituting the aliphatic ring It means having a structure in which a fluorine atom or a fluorine-containing group is bonded to at least a part of the atoms. In addition, the aliphatic ring may have an ether bond.
非晶性フッ素樹脂（ａ）としては、含フッ素脂肪族環構造を有するモノマーを重合して得られる重合体（ａ−１）、２つ以上の重合性二重結合を有する含フッ素モノマーを環化重合して得られる重合体（ａ−２）、含フッ素脂肪族環構造を有するモノマーと、２つ以上の重合性二重結合を有する含フッ素モノマーとを共重合して得られる重合体（ａ−３）等が挙げられ、含フッ素脂肪族環構造を有するモノマーを重合して得られる重合体（ａ−１）または重合体（ａ−３）が好ましい。重合体（ａ−１）〜（ａ−３）は、含フッ素脂肪族環構造を有するモノマーおよび／または２つ以上の重合性二重結合を有する含フッ素モノマーと、他のラジカル重合性モノマーとの共重合体であってもよい。 The amorphous fluororesin (a) includes a polymer (a-1) obtained by polymerizing a monomer having a fluorine-containing aliphatic ring structure, and a fluorine-containing monomer having two or more polymerizable double bonds. A polymer (a-2) obtained by chemical polymerization, a polymer obtained by copolymerizing a monomer having a fluorine-containing aliphatic ring structure and a fluorine-containing monomer having two or more polymerizable double bonds ( a-3) and the like, and a polymer (a-1) or a polymer (a-3) obtained by polymerizing a monomer having a fluorine-containing aliphatic ring structure is preferable. Polymers (a-1) to (a-3) are a monomer having a fluorine-containing aliphatic ring structure and / or a fluorine-containing monomer having two or more polymerizable double bonds, and another radical polymerizable monomer. The copolymer may be used.
重合体（ａ−１）〜（ａ−３）としては、具体的には下式（Ｉ）〜(VII）から選ばれる構成単位を有する重合体が挙げられる。該重合体のフッ素原子は、一部が塩素原子で置換されていてもよい。 Specific examples of the polymers (a-1) to (a-3) include polymers having structural units selected from the following formulas (I) to (VII). A part of the fluorine atom of the polymer may be substituted with a chlorine atom.
ただし、ｈは０〜５の整数であり、ｉは０〜４の整数であり、ｊは０または１であり、ｈ＋ｉ＋ｊは１〜６であり、ｓは０〜５の整数であり、ｔは０〜４の整数であり、ｕは０または１であり、ｓ＋ｔ＋ｕは１〜６であり、ｐ、ｑ、ｒはそれぞれ独立に０〜５の整数であり、ｐ＋ｑ＋ｒは１〜６であり、Ｒ1 〜Ｒ4 、Ｘ1 、Ｘ2 はそれぞれ独立にＨ、Ｄ（重水素）Ｆ、ＣｌまたはＣn Ｆ2n+1Ｏk であり、Ｒ5 〜Ｒ8 はそれぞれ独立にＨ、Ｄ（重水素）、Ｆ、Ｃｌ、Ｃn Ｆ2n+1、Ｃn Ｆ2n+1-mＣｌm Ｏk またはＣn Ｆ2n+1-mＨm Ｏk であり、Ｒ7 とＲ8 とが連結して環を形成する場合は、Ｒ7 とＲ8 とからなる連結部分はＣx Ｆ2xＯy またはＣx Ｆ2x-zＣｌz Ｏy であり、Ｙ1 は単結合、Ｏ、Ｃx Ｆ2xＯy またはＣx Ｆ2x-zＣｌz Ｏy であり、ｎは１〜５の整数であり、ｍは０〜５の整数であり、ｋは０〜２の整数であり、ｘは１〜１０の整数であり、ｙは０〜２の整数であり、ｚは０〜５の整数である。また、２ｎ＋１≧ｍであり、２ｘ≧ｚである。 However, h is an integer of 0-5, i is an integer of 0-4, j is 0 or 1, h + i + j is 1-6, s is an integer of 0-5, t is An integer of 0-4, u is 0 or 1, s + t + u is 1-6, p, q, r are each independently an integer of 0-5, p + q + r is 1-6, R 1 to R 4 , X 1 , and X 2 are each independently H, D (deuterium) F, Cl, or C n F 2n + 1 O k , and R 5 to R 8 are independently H, D (deuterium). hydrogen), F, Cl, a C n F 2n + 1, C n F 2n + 1-m Cl m O k or C n F 2n + 1-m H m O k, coupling and the R 7 and R 8 When a ring is formed, the connecting portion consisting of R 7 and R 8 is C x F 2x O y or C x F 2x-z Cl z O y , Y 1 is a single bond, O, C x F 2x O y or C x F 2x-z Cl z O y , n is 1 to 5 M is an integer of 0 to 5, k is an integer of 0 to 2, x is an integer of 1 to 10, y is an integer of 0 to 2, and z is 0 to 5 Is an integer. Further, 2n + 1 ≧ m and 2x ≧ z.
含フッ素脂肪族環構造を有するモノマーとしては、化合物（１）〜（４）が好ましい。 As the monomer having a fluorine-containing aliphatic ring structure, compounds (1) to (4) are preferable.
ただし、Ｘ3 〜Ｘ8 はそれぞれ独立にＨ、Ｄ（重水素）、Ｆ、ＣｌまたはＣn Ｆ2n+1Ｏk であり、Ｒ9 およびＲ10はそれぞれ独立にＨ、Ｄ（重水素）、Ｆ、Ｃｌ、Ｃn Ｆ2n+1、Ｃn Ｆ2n+1-mＣｌm Ｏk またはＣn Ｆ2n+1-mＨm Ｏk であり、Ｒ9 とＲ10とが連結して環を形成する場合は、Ｒ9 とＲ10とからなる連結部分はＣx Ｆ2xＯy またはＣx Ｆ2x-zＣｌz Ｏy であり、Ｙ2 は単結合、Ｏ、Ｃx Ｆ2xＯy またはＣx Ｆ2x-zＣｌz Ｏy であり、ｎは１〜５の整数であり、ｍは０〜５の整数であり、ｋは０〜２の整数であり、ｘは１〜１０の整数であり、ｙは０〜２の整数であり、ｚは０〜５の整数である。また、２ｎ＋１≧ｍであり、２ｘ≧ｚである。 However, X 3 to X 8 are each independently H, D (deuterium), F, Cl or C n F 2n + 1 O k , R 9 and R 10 are each independently H, D (deuterium) , F, Cl, a C n F 2n + 1, C n F 2n + 1-m Cl m O k or C n F 2n + 1-m H m O k, linked R 9 and R 10 In the case of forming a ring, the connecting portion composed of R 9 and R 10 is C x F 2x O y or C x F 2x-z Cl z O y , Y 2 is a single bond, O, C x F 2x O is y or C x F 2x-z Cl z O y, n is an integer from 1 to 5, m is an integer of 0 to 5, k is an integer of 0 to 2, x is 1 It is an integer of 10, y is an integer of 0-2, and z is an integer of 0-5. Further, 2n + 1 ≧ m and 2x ≧ z.
化合物（１）〜（４）の具体例としては、化合物（１−１）〜（１−３）、化合物（２−１）〜（２−３）、化合物（３−１）〜（３−２）、化合物（４−１）〜（４−６）等が挙げられる。 Specific examples of the compounds (1) to (4) include the compounds (1-1) to (1-3), the compounds (2-1) to (2-3), and the compounds (3-1) to (3- 2) and compounds (4-1) to (4-6).
２つ以上の重合性二重結合を有する含フッ素モノマーとしては、化合物（５）〜（８）が好ましい。 As the fluorine-containing monomer having two or more polymerizable double bonds, compounds (5) to (8) are preferable.
ＣＸ9 Ｘ10＝ＣＸ11ＯＣＸ12Ｘ13ＣＸ14Ｘ15ＣＸ16＝ＣＸ17Ｘ18 （５）
ＣＸ19Ｘ20＝ＣＸ21ＯＣＸ22Ｘ23ＣＸ24＝ＣＸ25Ｘ26 （６）
ＣＸ27Ｘ28＝ＣＸ29ＯＣＸ30Ｘ31ＯＣＸ32＝ＣＸ33Ｘ34 （７）
ＣＸ35Ｘ36＝ＣＸ37ＣＸ38Ｘ39ＣＸ40Ｘ41ＣＸ42Ｘ43ＣＸ44＝ＣＸ45Ｘ46 （８）
CX 9 X 10 = CX 11 OCX 12 X 13 CX 14 X 15 CX 16 = CX 17 X 18 (5)
CX 19 X 20 = CX 21 OCX 22 X 23 CX 24 = CX 25 X 26 (6)
CX 27 X 28 = CX 29 OCX 30 X 31 OCX 32 = CX 33 X 34 (7)
CX 35 X 36 = CX 37 CX 38 X 39 CX 40 X 41 CX 42 X 43 CX 44 = CX 45 X 46 (8)
ただし、Ｘ9 〜Ｘ46は、それぞれ独立にＨ、Ｄ（重水素）、Ｆ、ＣｌまたはＣＦ3 である。
化合物（５）〜（８）の具体例としては、以下の化合物等が挙げられる。
However, X 9 to X 46 are each independently H, D (deuterium), F, Cl or CF 3.
Specific examples of the compounds (5) to (8) include the following compounds.
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＣｌ2 ＣＦ2 ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＣｌ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦＣｌＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＦ＝ＣＦＣｌ、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）ＣＣｌ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ（ＣＦ3 ）ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＦ2 ＯＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＣｌＯＣＦ2 ＯＣＣｌ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣＣｌ2 ＯＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯＣ（ＣＦ3 ）2 ＯＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＣＣｌ2 ＣＦ2 ＣＦ2 ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＣＦ2 ＣＦ2 ＣＦ2 ＣＦ＝ＣＦ2 。
CF 2 = CFOCF 2 CF 2 CF = CF 2 ,
CF 2 = CFOCCl 2 CF 2 CF = CF 2 ,
CF 2 = CFOCF 2 CF 2 CCl = CF 2 ,
CF 2 = CFOCF 2 CF 2 CF = CF 2 ,
CF 2 = CFOCF 2 CFClCF = CF 2 ,
CF 2 = CFOCF 2 CF 2 CF = CFCl,
CF 2 = CFOCF 2 CF (CF 3 ) CF = CF 2 ,
CF 2 = CFOCF 2 CF (CF 3 ) CCl = CF 2 ,
CF 2 = CFOCF 2 CF = CF 2 ,
CF 2 = CFOCF (CF 3 ) CF = CF 2 ,
CF 2 = CFOCF 2 OCF = CF 2 ,
CF 2 = CClOCF 2 OCCl = CF 2 ,
CF 2 = CFOCCl 2 OCF = CF 2 ,
CF 2 = CFOC (CF 3 ) 2 OCF = CF 2 ,
CF 2 = CFCCl 2 CF 2 CF 2 CF = CF 2 ,
CF 2 = CFCF 2 CF 2 CF 2 CF = CF 2.
他のラジカル重合性モノマーとしては、テトラフルオロエチレン、クロロトリフルオロエチレン、トリフルオロエチレン、フッ化ビニリデン、ヘキサフルオロプロピレン、（パーフルオロブチル）エチレン、パーフルオロ（メチルビニルエーテル）、パーフルオロ（プロピルビニルエーテル）、メチルパーフルオロ（５−ヘキサ−６−ヘプテノエート）、エチレン、プロピレン等が挙げられ、テトラフルオロエチレン、クロロトリフルオロエチレン、パーフルオロ（メチルビニルエーテル）等の含フッ素モノマーが好ましい。 Other radical polymerizable monomers include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, (perfluorobutyl) ethylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether) Methyl perfluoro (5-hexa-6-heptenoate), ethylene, propylene, and the like, and fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, and perfluoro (methyl vinyl ether) are preferable.
非晶性含フッ素樹脂は、たとえば、ラジカル開始剤を用いてモノマーを重合し、非晶性含フッ素樹脂を得る工程（重合工程）、非晶性含フッ素樹脂に紫外線を照射する工程（紫外線照射工程）を経て製造される。 The amorphous fluorine-containing resin is, for example, a step of polymerizing a monomer using a radical initiator to obtain an amorphous fluorine-containing resin (polymerization step), a step of irradiating the amorphous fluorine-containing resin with ultraviolet rays (ultraviolet irradiation). Manufactured through a process.
重合法としては、懸濁重合、溶液重合、塊状重合等が挙げられ、不純物の混入が少ない塊状重合が好ましい。
ラジカル開始剤としては、パーフルオロ（ジ−ｔｅｒｔ−ブチルパーオキシド）、パーフルオロ（ジ−ｔｅｒｔ−ペンチルパーオキシド）等の含フッ素開始剤が好ましい。重合温度は、０〜２００℃が好ましく、３０〜１５０℃がより好ましい。
Examples of the polymerization method include suspension polymerization, solution polymerization, bulk polymerization and the like, and bulk polymerization with less contamination of impurities is preferable.
As the radical initiator, fluorine-containing initiators such as perfluoro (di-tert-butyl peroxide) and perfluoro (di-tert-pentyl peroxide) are preferable. The polymerization temperature is preferably 0 to 200 ° C, more preferably 30 to 150 ° C.
紫外線を照射する非晶性含フッ素樹脂の形態は、重合工程で得られた直後の懸濁液、溶液、塊状物であってもよく、これらから得られる粉末、ペレットであってもよく、これらを成形した成形体であってもよい。取扱性の点から、成形体が好ましい。 The form of the amorphous fluorine-containing resin that is irradiated with ultraviolet rays may be a suspension, solution, or lump immediately after being obtained in the polymerization step, or may be a powder or a pellet obtained from these. It may be a molded body obtained by molding. From the viewpoint of handleability, a molded body is preferable.
紫外線の光源としては、紫外線透過性の向上効果が高い点から、低圧水銀灯または高圧水銀灯が好ましい。
照射する紫外線の２５４ｎｍにおける積算光量は、２０Ｊ／ｃｍ2 以上が好ましく、５０Ｊ／ｃｍ2 以上がより好ましく、１００Ｊ／ｃｍ2 以上が特に好ましい。照射する紫外線の積算光量を２０Ｊ／ｃｍ2 以上とすることにより、紫外線透過性の向上効果が充分に発揮される。紫外線の積算光量は、波長２５４ｎｍにおける積算光量であり、波長２５４ｎｍにおける照度（ｍＷ／ｃｍ2 ）を積算光量計で測定し、これに照射時間（秒）を積算して求める。
As the ultraviolet light source, a low-pressure mercury lamp or a high-pressure mercury lamp is preferable because the effect of improving ultraviolet transmittance is high.
The accumulated light amount at 254 nm of ultraviolet rays to be irradiated is preferably 20 J / cm 2 or more, more preferably 50 J / cm 2 or more, and particularly preferably 100 J / cm 2 or more. By making the integrated light quantity of the irradiated ultraviolet rays 20 J / cm 2 or more, the effect of improving the ultraviolet transmittance is sufficiently exhibited. The integrated light quantity of ultraviolet rays is the integrated light quantity at a wavelength of 254 nm, and the illuminance (mW / cm 2 ) at a wavelength of 254 nm is measured with an integrated light quantity meter, and the irradiation time (seconds) is added to this.
紫外線の照射時間は、５分〜５０時間が好ましく、１０分〜２０時間がより好ましく、２０分〜１０時間が特に好ましい。紫外線の照射時間が短すぎると紫外線透過性が不充分となるおそれがあり、長すぎると生産性が低下する。
紫外線照射を行う際の温度は、２０〜２００℃が好ましく、３０〜１８０℃がより好ましい。温度が低すぎると紫外線照射の効果が充分に得られないおそれがあり、温度が高すぎると、非晶性含フッ素樹脂が劣化したり、成形体に紫外線照射する場合には成形体が変形したりするおそれがある。
The ultraviolet irradiation time is preferably 5 minutes to 50 hours, more preferably 10 minutes to 20 hours, and particularly preferably 20 minutes to 10 hours. If the irradiation time of ultraviolet rays is too short, there is a possibility that the ultraviolet ray permeability is insufficient, and if it is too long, productivity is lowered.
20-200 degreeC is preferable and the temperature at the time of performing ultraviolet irradiation has more preferable 30-180 degreeC. If the temperature is too low, the effect of ultraviolet irradiation may not be sufficiently obtained. If the temperature is too high, the amorphous fluorine-containing resin may deteriorate, or the molded product may be deformed when the molded product is irradiated with ultraviolet light. There is a risk of
非晶性含フッ素樹脂を紫外線透過性が要求される光学用途に用いる場合、紫外線の照射は、波長３００ｎｍにおける光線透過率が照射前に比べ１％以上向上するように行うことが好ましく、５％以上向上するように行うことがより好ましい。
また、波長３００ｎｍにおける光線透過率が８５％未満である非晶性含フッ素樹脂に紫外線を照射し、紫外線照射後の非晶性含フッ素樹脂の、波長３００ｎｍにおける光線透過率を８６％以上とすることが好ましい。波長３００ｎｍにおける光線透過率は、分光光度計を用いて測定する。
When the amorphous fluorine-containing resin is used for optical applications requiring ultraviolet transparency, the ultraviolet irradiation is preferably performed so that the light transmittance at a wavelength of 300 nm is improved by 1% or more as compared to before irradiation. It is more preferable to carry out so as to improve the above.
In addition, the amorphous fluorine-containing resin having a light transmittance of less than 85% at a wavelength of 300 nm is irradiated with ultraviolet rays, and the light transmittance at a wavelength of 300 nm of the amorphous fluorine-containing resin after ultraviolet irradiation is set to 86% or more. It is preferable. The light transmittance at a wavelength of 300 nm is measured using a spectrophotometer.
本発明の製造方法で得られた非晶性含フッ素樹脂の用途としては、紫外線透過性が要求される、紫外線用レンズ、紫外線光源の封止材、紫外線光源の保護カバー、光ファイバ、医療レーザー伝送等が挙げられる。 The use of the amorphous fluorine-containing resin obtained by the production method of the present invention includes ultraviolet lenses, ultraviolet light source sealing materials, ultraviolet light source protective covers, optical fibers, and medical lasers that are required to transmit ultraviolet light. Transmission and the like.
以上説明した本発明の非晶性含フッ素樹脂の製造方法にあっては、非晶性含フッ素樹脂に紫外線を照射することによって、非晶性含フッ素樹脂に含まれる不安定な高分子鎖末端および微量の不純物が除去されると考えられる。従来のフッ素ガスで処理する方法に比べ、生産性の高い簡便な方法で、紫外線透過性に優れる非晶性含フッ素樹脂を得ることができる。 In the method for producing the amorphous fluorine-containing resin of the present invention described above, the unstable polymer chain terminal contained in the amorphous fluorine-containing resin is irradiated by irradiating the amorphous fluorine-containing resin with ultraviolet rays. It is thought that trace amounts of impurities are removed. Compared with the conventional method of treating with fluorine gas, it is possible to obtain an amorphous fluorine-containing resin which is excellent in ultraviolet ray permeability by a simple method with high productivity.
以下、実施例を示して本発明を説明するが、本発明はこれらに限定されない。
紫外線透過性の評価は、以下に示す方法によって行った。
（紫外線透過性）
非晶性含フッ素樹脂の成形体について、島津製作所社製ＵＶ３１００を用い、波長３００ｎｍにおける光線透過率を測定した。
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated, this invention is not limited to these.
The evaluation of ultraviolet transmittance was performed by the following method.
(Ultraviolet transmission)
About the molded body of the amorphous fluorine-containing resin, light transmittance at a wavelength of 300 nm was measured using UV3100 manufactured by Shimadzu Corporation.
〔合成例１〕
外径１５ｍｍ、内径１１ｍｍのガラス管に、２０ｇのパーフルオロ（ブテニルビニルエーテル）、０．０１ｇのパーフルオロ（ジ−ｔｅｒｔ−ブチルパーオキシド）（１０時間半減温度９９℃）、および、０．２ｇのクロロホルムを仕込み、液体窒素を用いて凍結脱気を３回繰り返した後に封管した。これを９０℃のオーブン中に２日間保持したところ完全に固化した。さらに１１０℃で１日保持した後、ガラス管を壊して重合体を取り出したところ、無色透明で強靭なロッド状固体が得られた。得られたロッド状固体を長さ１５ｍｍに切断し、切断面を研磨してロッド１（非晶性含フッ素樹脂の成形体）を得た。
ロッド１の長さ方向（１５ｍｍ）について、波長３００ｎｍにおける光線透過率を測定したところ、８４．５％であった。
[Synthesis Example 1]
In a glass tube having an outer diameter of 15 mm and an inner diameter of 11 mm, 20 g of perfluoro (butenyl vinyl ether), 0.01 g of perfluoro (di-tert-butyl peroxide) (10-hour half-temperature 99 ° C.), and 0.2 g Of chloroform, and freeze-deaeration was repeated three times using liquid nitrogen, followed by sealing. When this was kept in an oven at 90 ° C. for 2 days, it completely solidified. Furthermore, after maintaining at 110 ° C. for 1 day, the glass tube was broken and the polymer was taken out. As a result, a colorless, transparent and tough rod-like solid was obtained. The obtained rod-like solid was cut into a length of 15 mm, and the cut surface was polished to obtain a rod 1 (a molded body of an amorphous fluorine-containing resin).
The light transmittance at a wavelength of 300 nm in the length direction (15 mm) of the rod 1 was measured and found to be 84.5%.
〔実施例１〕
センエンジニアリング（株）製ＰｈｏｔｏＤｒｙＣｌｅａｎｅｒＰＬ７−２００（波長２５４ｎｍにおける照度１８ｍＷ／ｃｍ2 ）を用いて、ロッド１に紫外線を２時間照射し、ロッド２を得た。このときの紫外線の２５４ｎｍにおける積算光量は、１３０Ｊ／ｃｍ2 であった。
ロッド２の長さ方向（１５ｍｍ）について、波長３００ｎｍにおける光線透過率を測定したところ、９０．０％であった。紫外線照射前後の光線透過率の差は５．５％であった。
[Example 1]
The rod 1 was irradiated with ultraviolet rays for 2 hours using a PhotoDryCleaner PL7-200 manufactured by Sen Engineering Co., Ltd. (illuminance 18 mW / cm 2 at a wavelength of 254 nm) to obtain the rod 2. At this time, the integrated light quantity of ultraviolet rays at 254 nm was 130 J / cm 2 .
The light transmittance at a wavelength of 300 nm in the length direction (15 mm) of the rod 2 was measured and found to be 90.0%. The difference in light transmittance before and after UV irradiation was 5.5%.
〔合成例２〕
４ｇの化合物（３−３）、１ｇの化合物（４−６）、および１ｍｇの（Ｃ6 Ｆ5 Ｃ（Ｏ）Ｏ）2 を混合し、組成物を調製した。該組成物を６０℃で２０分加熱して、粘度が１００〜２００ｃｐｓのシロップを得た。
スライドガラスにＯリング（内径２０ｍｍ、厚さ２ｍｍ、フッ素ゴム製）をエポキシ接着剤で固定した型を作製した。該型に１ｇのシロップを流し込み、型の上にさらにスライドガラスを重ねた。型を５０℃で３時間、７０℃で５時間、１００℃で２時間、１２０℃で２時間、順次、加熱した。型を冷却してからＯリングおよびスライドガラスを外して直径２０ｍｍ、厚さ０．５ｍｍの円盤状の透明な硬化物１（非晶性含フッ素樹脂の成形体）を得た。硬化物１の厚さ方向（０．５ｍｍ）について、波長３００ｎｍにおける光線透過率を測定したところ、１３％であった。
[Synthesis Example 2]
4 g of compound (3-3), 1 g of compound (4-6), and 1 mg of (C 6 F 5 C (O) O) 2 were mixed to prepare a composition. The composition was heated at 60 ° C. for 20 minutes to obtain a syrup having a viscosity of 100 to 200 cps.
A mold in which an O-ring (inner diameter 20 mm, thickness 2 mm, made of fluoro rubber) was fixed to a slide glass with an epoxy adhesive was produced. 1 g of syrup was poured into the mold, and a glass slide was further stacked on the mold. The mold was heated sequentially at 50 ° C. for 3 hours, 70 ° C. for 5 hours, 100 ° C. for 2 hours, and 120 ° C. for 2 hours. After cooling the mold, the O-ring and the slide glass were removed to obtain a disk-shaped transparent cured product 1 (amorphous fluororesin molded product) having a diameter of 20 mm and a thickness of 0.5 mm. The light transmittance at a wavelength of 300 nm in the thickness direction (0.5 mm) of the cured product 1 was measured and found to be 13%.
〔実施例２〕
１ｋＷ高圧水銀灯（波長２５４ｎｍにおける照度４０ｍＷ／ｃｍ2 ）を用い、硬化物１に紫外線を１時間照射し、硬化物２を得た。このときの紫外線の２５４ｎｍにおける積算光量は、１４４Ｊ／ｃｍ2 であった。硬化物２の厚さ方向（０．５ｍｍ）について、波長３００ｎｍにおける光線透過率を測定したところ、９１％であった。また、硬化物２の外観に変化は見られなかった。
[Example 2]
Using a 1 kW high-pressure mercury lamp (illuminance 40 mW / cm 2 at a wavelength of 254 nm), the cured product 1 was irradiated with ultraviolet rays for 1 hour to obtain a cured product 2. The accumulated light quantity at 254 nm of ultraviolet rays at this time was 144 J / cm 2 . The light transmittance at a wavelength of 300 nm in the thickness direction (0.5 mm) of the cured product 2 was measured and found to be 91%. Further, no change was observed in the appearance of the cured product 2.
本発明の製造方法で得られる非晶性含フッ素樹脂は、紫外線透過性に優れ、紫外線用レンズ、紫外線光源の封止材、紫外線光源の保護カバー等として利用できる。
The amorphous fluorine-containing resin obtained by the production method of the present invention is excellent in ultraviolet transparency, and can be used as an ultraviolet lens, a sealing material for an ultraviolet light source, a protective cover for an ultraviolet light source, and the like.
Claims (6)
Amorphous fluorine-containing resin having a light transmittance of less than 85% at a wavelength of 300 nm is irradiated with ultraviolet rays, and the light transmittance at a wavelength of 300 nm of the amorphous fluorine-containing resin after irradiation with ultraviolet rays is 86% or more. Item 6. A method for producing an amorphous fluorine-containing resin according to any one of Items 1 to 5.
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| JP2021132138A (en) * | 2020-02-20 | 2021-09-09 | 日機装株式会社 | Semiconductor light-emitting device |
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| JPWO2022075049A1 (en) * | 2020-10-05 | 2022-04-14 |
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