JP5187924B2 - Screen printing plate surface treatment agent - Google Patents
Screen printing plate surface treatment agent Download PDFInfo
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- JP5187924B2 JP5187924B2 JP2007215240A JP2007215240A JP5187924B2 JP 5187924 B2 JP5187924 B2 JP 5187924B2 JP 2007215240 A JP2007215240 A JP 2007215240A JP 2007215240 A JP2007215240 A JP 2007215240A JP 5187924 B2 JP5187924 B2 JP 5187924B2
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- screen printing
- printing plate
- plate
- plate surface
- treating agent
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- 238000007650 screen-printing Methods 0.000 title claims description 109
- 239000012756 surface treatment agent Substances 0.000 title claims description 11
- -1 silane compound Chemical class 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000010702 perfluoropolyether Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 description 58
- 239000003921 oil Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000679 solder Inorganic materials 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- 229920001709 polysilazane Polymers 0.000 description 14
- 230000002940 repellent Effects 0.000 description 14
- 239000005871 repellent Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 125000001033 ether group Chemical group 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000012954 diazonium Substances 0.000 description 5
- 150000001989 diazonium salts Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical group C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 1
- LOUICXNAWQPGSU-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxirane Chemical group FC1(F)OC1(F)F LOUICXNAWQPGSU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BQAYEMVVKATQOU-UHFFFAOYSA-N N-[bis(difluoroamino)-(1,1,2,2,2-pentafluoroethyl)silyl]-N,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-octadecafluorooctan-1-amine Chemical compound FC(F)(F)C(F)(F)[Si](N(F)F)(N(F)F)N(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BQAYEMVVKATQOU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XTWQIWXBJRROJN-UHFFFAOYSA-N bis(1,1,2,2,3,3,3-heptafluoropropoxy)-(1,1,2,2,2-pentafluoroethyl)-(1,1,1,2,2,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-tricosafluoroundecan-3-yloxy)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)C(F)(F)F)(C(F)(F)C(F)(F)F)OC(F)(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XTWQIWXBJRROJN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical group FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical group FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Printing Plates And Materials Therefor (AREA)
Description
本発明は、長期に亙って鮮明な印刷を行うことのできるスクリーン印刷版を得るために使用する、スクリーン印刷版の版面処理剤に関するものである。 The present invention relates to a plate surface treating agent for a screen printing plate, which is used for obtaining a screen printing plate capable of performing clear printing over a long period of time.
スクリーン印刷版は、スクリーン表面に感光性樹脂組成物を塗布・乾燥して得られたスクリーン印刷版材を使用し、このスクリーン印刷版材の感光性樹脂上に画像形成用フィルムを置き、露光した後、現像して製造されるものである。画像形成用フィルムとして、たとえばポジフィルムを使用した場合には、画像部に対応している感光性樹脂は露光されずに硬化せず、非画像部に対応している感光性樹脂は露光されて硬化する。そして、そのあと現像することによって、露光されなかった感光性樹脂を洗い流す。このようにして得られたスクリーン印刷版は、画像部には感光性樹脂が存在せず、非画像部には硬化した感光性樹脂が残存しているものである。このスクリーン印刷版は、スクリーン印刷版の裏面から印刷インキ等を供給しながらスキージすると、画像部から印刷インキ等がスクリーン印刷版の表面（版面）に滲み出して、被印刷物面に画像が印刷されるのである。 The screen printing plate uses a screen printing plate material obtained by applying and drying a photosensitive resin composition on the screen surface, and an image forming film is placed on the photosensitive resin of the screen printing plate material and exposed. After that, it is developed and manufactured. For example, when a positive film is used as the image forming film, the photosensitive resin corresponding to the image portion is not exposed and cured, and the photosensitive resin corresponding to the non-image portion is exposed. Harden. Then, development is performed thereafter to wash away the unexposed photosensitive resin. In the screen printing plate thus obtained, no photosensitive resin is present in the image area, and the cured photosensitive resin remains in the non-image area. When this screen printing plate is squeeged while supplying printing ink from the back side of the screen printing plate, the printing ink oozes out from the image portion onto the surface (plate surface) of the screen printing plate, and the image is printed on the surface of the substrate. It is.
また、半田ペースト印刷用のスクリーン印刷版として、金属製薄板をエッチング等の手段によってステンシル加工した印刷版板を、スクリーンに貼合したものも、しばしば用いられている。この印刷版板は、ステンシル加工によって孔が開けられた箇所が画像部となり、孔の開けられなかった箇所が非画像部となる。このスクリーン印刷版も裏面から、半田ペースト等を供給しながらスキージすると、画像部から半田ペースト等がスクリーン印刷版の表面（版面）に滲み出して、各種基板上に半田バンプ等が形成されるのである。 Further, as a screen printing plate for solder paste printing, a plate obtained by bonding a printing plate obtained by stenciling a metal thin plate by means such as etching is often used. In this printing plate, a portion where a hole is formed by stencil processing becomes an image portion, and a portion where the hole is not formed becomes a non-image portion. If this screen printing plate is also squeezed while supplying solder paste from the back side, the solder paste etc. oozes out from the image area to the surface (plate surface) of the screen printing plate, and solder bumps etc. are formed on various substrates. is there.
このようにしてスクリーン印刷版は使用されるのであるが、従来より、長期に亙って印刷を続けていると、印刷インキ等のダレやニジミが生じ、印刷が徐々に不鮮明になるということがあった。すなわち、スクリーン印刷版の裏面を何度もスキージしていると、版面に印刷インキが回り込み、印刷が不鮮明になるのである。印刷が不鮮明になると、回路パターンの印刷の場合には、パターン相互の接続による短絡等が問題となるし、文字印刷の場合には、文字の判読が困難になるという問題を惹起する。 Screen printing plates are used in this way, but if printing has been continued for a long time, sagging and blurring of printing ink will occur, and printing will gradually become blurred. there were. That is, if the back side of the screen printing plate is squeezed many times, the printing ink wraps around the plate surface and printing becomes unclear. When printing is unclear, a short circuit due to connection between patterns becomes a problem in the case of circuit pattern printing, and a problem that it becomes difficult to interpret characters in the case of character printing.
このため、特許文献１では、硬化した感光性樹脂（版膜）の表面（版面）や、ステンシル加工された印刷版の表面（版面）に、フッ素系又はシリコーン系撥水撥油剤の被膜を形成することが提案されている。この技術は、版面に撥水撥油剤の被膜を形成することにより、印刷インキ等と版面との親和性が低下し、版面への印刷インキ等の回り込みを防止できるというものである。したがって、印刷インキ等のダレやニジミを防止でき、鮮明な印刷が可能となるという面で、好ましいものである。 For this reason, in Patent Document 1, a film of a fluorine-based or silicone-based water / oil repellent agent is formed on the surface (plate surface) of a cured photosensitive resin (plate film) or the surface (plate surface) of a stencil-processed printing plate. It has been proposed to do. According to this technique, by forming a film of a water / oil repellent agent on the plate surface, the affinity between the printing ink or the like and the plate surface is reduced, and the printing ink or the like can be prevented from wrapping around the plate surface. Therefore, it is preferable in terms of preventing sagging and blurring of printing ink and enabling clear printing.
しかしながら、特許文献１に記載された技術においては、フッ素系又はシリコーン系撥水撥油剤と版面との接着強度が低く、何度もスキージを続けていると、フッ素系又はシリコーン系撥水撥油剤が版面から剥離してゆくということがあった。そして、剥離すると、印刷インキ等のダレやニジミが生じやすくなり、印刷が不鮮明になるという欠点が生じることがあった。 However, in the technique described in Patent Document 1, the adhesive strength between the fluorine-based or silicone-based water / oil repellent and the plate surface is low, and if the squeegee is continued many times, the fluorine-based or silicone-based water / oil repellent Sometimes peeled off from the plate. And when it peels, it will become easy to produce sagging and blurring of printing ink etc., and the fault that printing became unclear sometimes occurred.
このため、本発明者等は、フッ素系又はシリコーン系撥水撥油剤に代えて、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリプロポキシシラン、パーフルオロオクチルエチルトリアミノシラン又はパーフルオロオクチルエチルトリクロロシラン等のシラン系化合物からなる撥水撥油剤を使用することを提案した（特許文献２）。この撥水撥油剤は版面との接着強度が高く、長期に亙って印刷インキ等のダレやニジミが生じにくくなり、好ましいものである。 For this reason, the present inventors have replaced perfluorooctylethyltrimethoxysilane, perfluorooctylethyltripropoxysilane, perfluorooctylethyltriaminosilane or perfluorooctylethyltriol in place of the fluorine-based or silicone-based water / oil repellent. It has been proposed to use a water / oil repellent comprising a silane compound such as chlorosilane (Patent Document 2). This water / oil repellent is preferable because it has a high adhesive strength with the plate surface and is less likely to cause sagging and blurring of printing ink over a long period of time.
本発明者等は、特許文献２に記載された撥水撥油剤よりも、さらに撥油性に優れたものを開発すべく検討していたところ、特許文献２に記載されていない特定の構造を持つシラン系化合物が撥油性に優れていることを見出した。本発明は、このような知見に基づくものである。 The inventors of the present invention have been studying to develop an oil repellency superior to the water / oil repellent described in Patent Document 2, and have a specific structure not described in Patent Document 2. It has been found that silane compounds are excellent in oil repellency. The present invention is based on such knowledge.
すなわち、本発明は、一般式（１）で表されるシラン系化合物を含有することを特徴とするスクリーン印刷版の版面処理剤に関するものである。
ＯＡは、ＯＣＦ2ＣＦ2ＣＦ2，ＯＣＦ（ＣＦ3）ＣＦ2，ＯＣＦ2ＣＦ2及びＯＣＦ2よりなる群から選ばれる１種以上の基を示す。
Ｘは、ヨウ素原子、臭素原子又は水素原子を示す。
Ｙは、水素原子又は低級アルキル基を示す。
Ｒ１は、加水分解性基を示す。
Ｒ２は、水素原子又は非加水分解性基を示す。
ｍ及びｎは、０〜２の整数を示す。
ｐは、１〜１０の整数を示す。
ｑは、１又は２を示す。
ｒは、１〜２００の整数を示す。］
That is, this invention relates to the plate surface treating agent of the screen printing plate characterized by containing the silane type compound represented by General formula (1).
OA represents one or more groups selected from the group consisting of OCF 2 CF 2 CF 2 , OCF (CF 3 ) CF 2 , OCF 2 CF 2, and OCF 2 .
X represents an iodine atom, a bromine atom or a hydrogen atom.
Y represents a hydrogen atom or a lower alkyl group.
R1 represents a hydrolyzable group.
R2 represents a hydrogen atom or a non-hydrolyzable group.
m and n show the integer of 0-2.
p represents an integer of 1 to 10.
q represents 1 or 2.
r represents an integer of 1 to 200. ]
本発明に係る版面処理剤は、一般式（１）で表されるシラン系化合物を含有するものである。このシラン系化合物は、炭素数１〜１６の直鎖状又は分岐状のパーフルオロアルキル基を持っている。炭素数が１未満のパーフルオロアルキル基は、版面に十分な撥水性及び撥油性を与えにくくなるため、好ましくない。また、炭素数が１６を超えるパーフルオロアルキル基を持つ化合物を用いると、溶剤に溶解しにくくなり、版面処理剤を溶液状として取り扱いにくくなるため、好ましくない。パーフルオロアルキル基と珪素原子とは、パーフルオロポリアルキレンエーテル基、パーフルオロメチレン基及びポリメチレン基を介して結合されている。 The plate surface treating agent according to the present invention contains a silane compound represented by the general formula (1). This silane compound has a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. A perfluoroalkyl group having a carbon number of less than 1 is not preferable because it makes it difficult to impart sufficient water and oil repellency to the plate surface. Moreover, it is not preferable to use a compound having a perfluoroalkyl group having more than 16 carbon atoms because it is difficult to dissolve in a solvent and the plate surface treating agent is difficult to handle as a solution. The perfluoroalkyl group and the silicon atom are bonded via a perfluoropolyalkylene ether group, a perfluoromethylene group, and a polymethylene group.
パーフルオロポリアルキレンエーテル基は、パーフルオロプロピレンエーテル基（ＯＣＦ2ＣＦ2ＣＦ2），パーフルオロイソプロピレンエーテル基（ＯＣＦ（ＣＦ3）ＣＦ2），パーフルオロエチレンエーテル基（ＯＣＦ2ＣＦ2）及びパーフルオロメチレンエーテル基（ＯＣＦ2）よりなる群から選ばれる１種以上の基が採用され、これらの基が単独で又は混合して採用される。パーフルオロポリアルキレンエーテル基は、上記した基が少なくとも１個以上で多くとも２００個以下結合されてなる。パーフルオロポリアルキレンエーテル基の結合数が１個未満であると、得られる被膜の動摩擦係数が大きくなり、印刷インキ等がスクリーン印刷版を通過しにくくなる。パーフルオロポリアルキレンエーテル基の結合数が２００個を超えても、印刷インキ等のスクリーン印刷版の通過性がもはや向上しないので合理的ではない。一般に、パーフルオロポリアルキレンエーテル基の結合数は、２０〜３０個程度である。 Perfluoropolyalkylene ether groups include perfluoropropylene ether groups (OCF 2 CF 2 CF 2 ), perfluoro isopropylene ether groups (OCF (CF 3 ) CF 2 ), perfluoroethylene ether groups (OCF 2 CF 2 ) and One or more groups selected from the group consisting of perfluoromethylene ether groups (OCF 2 ) are employed, and these groups are employed alone or in combination. The perfluoropolyalkylene ether group is formed by bonding at least one group and at most 200 groups described above. When the number of bonds of the perfluoropolyalkylene ether group is less than 1, the dynamic friction coefficient of the resulting film increases, and it becomes difficult for printing ink or the like to pass through the screen printing plate. Even if the number of perfluoropolyalkylene ether group bonds exceeds 200, the passability of a screen printing plate such as printing ink no longer improves, which is not reasonable. Generally, the number of bonds of the perfluoropolyalkylene ether group is about 20 to 30.
パーフルオロメチレン基は、パーフルオロポリアルキレンエーテル基とポリメチレン基の間に挿入されている。パーフルオロメチレン基は、パーフルオロモノメチレン基又はパーフルオロジメチレン基である。ポリメチレン基は、ジメチレン基、トリメチレン基及びテトラメチレン基よりなる群から選ばれるものである。パーフルオロメチレン基とポリメチレン基によって、シラン系化合物に十分な撥水性を与える。 The perfluoromethylene group is inserted between the perfluoropolyalkylene ether group and the polymethylene group. The perfluoromethylene group is a perfluoromonomethylene group or a perfluorodimethylene group. The polymethylene group is selected from the group consisting of a dimethylene group, a trimethylene group and a tetramethylene group. The perfluoromethylene group and the polymethylene group give the silane compound sufficient water repellency.
ポリメチレン基に結合している珪素原子には、加水分解性基が１個乃至３個結合されている。この加水分解性基によって、シラン系化合物同士及びシラン系化合物と感光性樹脂組成物中のポリビニルアルコールや金属等とが結合し、版面に対して強固に接着するのである。加水分解性基としては、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、アミノ基、ハロゲン基等が用いられる。 One to three hydrolyzable groups are bonded to the silicon atom bonded to the polymethylene group. By this hydrolyzable group, the silane compounds, and the silane compound and polyvinyl alcohol, metal, etc. in the photosensitive resin composition are bonded and firmly bonded to the plate surface. As the hydrolyzable group, an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, an amino group, a halogen group, or the like is used.
一般式（１）で表されるシラン系化合物の代表例としては、下記構造式（２）で表されるものが用いられる。
また、一般式（１）で表されるシラン系化合物は、以下の測定方法で動摩擦係数を測定すると、概ね０．０６〜０．１３の範囲内となる。
（ｉ）厚さ１ｍｍで大きさ３０ｍｍ×８０ｍｍのＳＵＳ３０４板の片面を平均粗さが１．２μｍ程度に整面した。
（ii）当該片面を脱脂し、稀酸で洗浄し、更に水洗して前処理した。
（iii ）微量の酸触媒と共にポリシラザン１．０ｇをミネラルターペン９９．０ｇに溶解した溶液を、当該片面に刷毛塗りにより塗布し、常温で１０分間乾燥した。
（iv）一般式（１）で表されるシラン系化合物を溶剤に溶解した溶液状版面処理剤を刷毛塗りより塗布した後、４０℃の恒温室で２４時間乾燥させて、動摩擦試験用テストピースを得た。
（ｖ）表面性測定機（ＨＥＩＤＯＮ １４ＦＷ）に、動摩擦試験用テストピースをセットし、測定機に備えつけられているＳＵＳ１０ｍｍφのボールに、垂直荷重１００ｇを加え、摺動距離を４０ｍｍ（１往復）、線速度を２０００ｍｍ／ｍｉｎとして、このときの動摩擦係数を３回測定して、その平均値を算出した。
なお、本発明においては、以上のようにして得られた平均値のことを、（iv）で使用したシラン系化合物の動摩擦係数であると定義している。この定義に基づくと、上記構造式（２）で表されたシラン系化合物の動摩擦係数は０．０９である。
Moreover, the silane compound represented by the general formula (1) is approximately in the range of 0.06 to 0.13 when the dynamic friction coefficient is measured by the following measuring method.
(I) One surface of a SUS304 plate having a thickness of 1 mm and a size of 30 mm × 80 mm was adjusted to an average roughness of about 1.2 μm.
(Ii) The one surface was degreased, washed with dilute acid, further washed with water, and pretreated.
(Iii) A solution prepared by dissolving 1.0 g of polysilazane together with a trace amount of acid catalyst in 99.0 g of mineral terpenes was applied to one side by brushing and dried at room temperature for 10 minutes.
(Iv) After applying a solution-like plate surface treatment agent in which the silane compound represented by the general formula (1) is dissolved in a solvent by brush coating, it is dried in a constant temperature room at 40 ° C. for 24 hours, and is a test piece for dynamic friction test Got.
(V) A test piece for a dynamic friction test is set on a surface property measuring machine (HEIDON 14FW), a vertical load of 100 g is applied to a ball of SUS 10 mmφ provided in the measuring machine, and a sliding distance is 40 mm (one reciprocation). The linear velocity was set to 2000 mm / min, the dynamic friction coefficient at this time was measured three times, and the average value was calculated.
In the present invention, the average value obtained as described above is defined as the dynamic friction coefficient of the silane compound used in (iv). Based on this definition, the dynamic friction coefficient of the silane compound represented by the structural formula (2) is 0.09.
構造式（２）で代表的に表される一般式（１）で表されるシラン系化合物は、一般的に、溶剤に溶解され、溶液状で取り扱われる。溶剤としては、イソプロピルアルコール、アセトン、ハイドロフルオロエーテル類、パーフルオロポリエーテル類、ハイドロフルオロカーボン類、パーフルオロカーボン類、ハイドロフルオロポリエーテル類又はフッ素系アルコール類等が用いられる。また、溶液状にした場合のシラン系化合物の濃度は、０．０５〜０．５重量％程度であるのが、好ましい。 The silane compound represented by the general formula (1) typically represented by the structural formula (2) is generally dissolved in a solvent and handled in the form of a solution. As the solvent, isopropyl alcohol, acetone, hydrofluoroethers, perfluoropolyethers, hydrofluorocarbons, perfluorocarbons, hydrofluoropolyethers or fluorine alcohols are used. Moreover, it is preferable that the density | concentration of the silane type compound at the time of making it into a solution form is about 0.05 to 0.5 weight%.
本発明に係るスクリーン印刷版の製造方法においては、まずスクリーン印刷版本体を製造する。スクリーン印刷版本体は、従来のスクリーン印刷版の製造方法によって製造すればよい。たとえば、感光性樹脂組成物を用いてスクリーン印刷版本体を製造する方法は、以下のとおりである。すなわち、まず、スクリーン表面に感光性樹脂組成物を塗布・乾燥して、スクリーン印刷版材を得る。使用する感光性樹脂組成物としても、従来公知のものが使用され、具体的には、ポリビニルアルコールに重クロム酸塩或いはジアゾニウム塩を配合した水系組成物、ポリビニルアルコール−酢酸ビニル共重合体エマルジョンに重クロム酸塩或いはジアゾニウム塩を配合した水系組成物、ポリビニルアルコールと酢酸ビニル重合体エマルジョンとからなる乳液にジアゾニウム塩を配合した水系組成物、ポリビニルアルコールとアクリルモノマーと酢酸ビニル重合体エマルジョンからなる乳液にジアゾニウム塩を配合した水系組成物、又はこれらの水系組成物に更に、側鎖にスチルバゾリウム基が導入されたポリビニルアルコール誘導体を添加してなる水系組成物を使用することができる。 In the method for producing a screen printing plate according to the present invention, a screen printing plate main body is first produced. What is necessary is just to manufacture a screen printing plate main body with the manufacturing method of the conventional screen printing plate. For example, a method for producing a screen printing plate body using a photosensitive resin composition is as follows. That is, first, a photosensitive resin composition is applied to the screen surface and dried to obtain a screen printing plate material. As the photosensitive resin composition to be used, conventionally known ones are used. Specifically, an aqueous composition in which a dichromate or a diazonium salt is blended with polyvinyl alcohol, or a polyvinyl alcohol-vinyl acetate copolymer emulsion. An aqueous composition containing a dichromate or a diazonium salt, an aqueous composition containing a diazonium salt in an emulsion comprising a polyvinyl alcohol and a vinyl acetate polymer emulsion, and an emulsion comprising a polyvinyl alcohol, an acrylic monomer and a vinyl acetate polymer emulsion. An aqueous composition prepared by adding a diazonium salt to the aqueous composition, or an aqueous composition obtained by adding a polyvinyl alcohol derivative having a stilbazolium group introduced into the side chain to these aqueous compositions can be used.
得られたスクリーン印刷版材は、スクリーンの片面に感光性樹脂が積層接着した形態や、感光性樹脂層中にスクリーンが埋入した形態となっている。このスクリーン印刷版材の感光性樹脂層上に、画像形成用フィルムを置く。この画像形成用フィルムは、ポジフィルムでもネガフィルムでもよい。そして、ポジフィルム又はネガフィルムの面に、ケミカルランプや紫外線ランプで光を照射し、露光する。この露光によって、ポジフィルムの場合は、ポジフィルムの画像部からは光が透過せず、非画像部から光が透過する。したがって、非画像部に対応している感光性樹脂は硬化し、画像部に対応している感光性樹脂は硬化しない。また、ネガフィルムの場合は、ネガフィルムの非画像部からは光が透過せず、画像部から光が透過する。したがって、画像部に対応している感光性樹脂は硬化し、非画像部に対応している感光性樹脂は硬化しない。そして、露光した後、アルカリ水溶液或いは単なる水によって現像し、硬化していない感光性樹脂を洗い流して、スクリーン印刷版本体を得る。 The obtained screen printing plate material has a form in which a photosensitive resin is laminated and adhered to one side of the screen or a form in which the screen is embedded in the photosensitive resin layer. An image forming film is placed on the photosensitive resin layer of the screen printing plate material. The image forming film may be a positive film or a negative film. Then, the surface of the positive film or negative film is exposed by irradiating light with a chemical lamp or an ultraviolet lamp. With this exposure, in the case of a positive film, light is not transmitted from the image portion of the positive film, but light is transmitted from the non-image portion. Therefore, the photosensitive resin corresponding to the non-image portion is cured, and the photosensitive resin corresponding to the image portion is not cured. In the case of a negative film, light is not transmitted from the non-image part of the negative film, but light is transmitted from the image part. Therefore, the photosensitive resin corresponding to the image portion is cured, and the photosensitive resin corresponding to the non-image portion is not cured. And after exposure, it develops with alkaline aqueous solution or simple water, and wash | cleans the uncured photosensitive resin, and obtains a screen printing plate main body.
また、金属製薄板をステンシル加工した印刷版板を用いてスクリーン印刷版本体を製造する方法は、以下のとおりである。まず、ステンレス等の金属薄板に、画像部以外の箇所にレジスト膜を設ける。そして、エッチング処理によってレジスト膜を形成した以外の箇所を腐食して孔を開けた後、レジスト膜を除去して、ステンシル加工した印刷版板を得る。この印刷版板とスクリーンとを貼合して、スクリーン印刷版本体を得る。 Moreover, the method of manufacturing a screen printing plate main body using the printing plate which stencil-processed the metal thin plate is as follows. First, a resist film is provided on a portion other than the image portion on a thin metal plate such as stainless steel. And after corroding a part except having formed the resist film by an etching process and making a hole, the resist film is removed to obtain a stencil-processed printing plate. The printing plate and the screen are bonded to obtain a screen printing plate body.
以上のようにして得られたスクリーン印刷版本体に、予め準備した溶液状版面処理剤を付与する。溶液状版面処理剤は、一般式（１）で表されるシラン系化合物を溶剤に溶解したものである。スクリーン印刷版本体に、溶液状版面処理剤を付与する方法としては、スクリーン印刷版本体を溶液状版面処理剤中に浸漬する方法、スクリーン印刷版本体の版面にコーティング法、スプレー法、刷毛塗り法等で、溶液状版面処理剤を塗布する方法等を採用することができる。この際、溶液状版面処理剤の液温は、一般的に常温で使用されるが、常温より高い温度であっても差し支えない。 A previously prepared solution-like plate surface treating agent is applied to the screen printing plate body obtained as described above. The solution type plate surface treating agent is obtained by dissolving the silane compound represented by the general formula (1) in a solvent. As a method of applying a solution-like plate surface treatment agent to the screen printing plate body, a method of immersing the screen printing plate body in a solution-like plate surface treatment agent, a coating method, a spray method, a brush coating method on the plate surface of the screen printing plate body For example, a method of applying a solution type plate surface treating agent can be employed. At this time, the liquid temperature of the solution-type plate surface treating agent is generally used at room temperature, but may be higher than room temperature.
スクリーン印刷版本体に、溶液状版面処理剤を付与した後、乾燥する。乾燥温度は室温か又は室温よりも若干高めがよく、２５〜４５℃程度が好ましい。乾燥時間は、１日程度でよい。この乾燥時に、空気中の水分又は感光性樹脂中に存在する水分の作用で、版面処理剤の加水分解性基が分解し、シラン系化合物同士、感光性樹脂中のポリビニルアルコールのＯＨ基又は印刷版板の金属原子と結合し、感光性樹脂又は金属薄板よりなる版面と強固に接着するのである。 After applying a solution-like plate surface treating agent to the screen printing plate main body, it is dried. The drying temperature is room temperature or slightly higher than room temperature, and is preferably about 25 to 45 ° C. The drying time may be about one day. At the time of drying, hydrolyzable groups of the plate surface treating agent are decomposed by the action of moisture in the air or moisture present in the photosensitive resin, and silane compounds, OH groups of polyvinyl alcohol in the photosensitive resin, or printing. It bonds with the metal atoms of the plate and firmly adheres to the plate surface made of a photosensitive resin or a metal thin plate.
版面と版面処理剤とを更に強固に接着させるために、溶液状版面処理剤を付与する前、予め版面に、シリカ系コーティング剤等の版面処理剤と結合しやすい物質を含浸塗布されておくことも、好ましいことである。シリカ系コーティング剤としては、ポリシラザンやコロイダルシリカ等を用いることができる。 In order to bond the plate surface and the plate surface treatment agent more firmly, before applying the solution type plate surface treatment agent, the plate surface should be impregnated and coated with a substance that easily binds to the plate surface treatment agent such as a silica-based coating agent in advance. Is also preferable. As the silica-based coating agent, polysilazane, colloidal silica, or the like can be used.
本発明に係るスクリーン印刷版は、スクリーン印刷版本体に、溶液状版面処理剤を付与した後、乾燥して、得ることができる。このスクリーン印刷版は、非画像部に残存している硬化した感光性樹脂表面（版面）又は非画像部を形成する金属薄板表面（版面）に、一般式（１）で表されるシラン系化合物を含有する版面処理剤が接着して被膜が形成され、この結果、版面の耐水性、撥水性及び撥油性が向上し、ひいては印刷時における印刷インキや半田ペーストの版面への回り込みが防止されるのである。そして、本発明に係るスクリーン印刷版は、スクリーン印刷版の裏面から印刷インキ等を供給しながら、その裏面をスキージするという従来公知の方法で、スクリーン印刷に使用されるのである。 The screen printing plate according to the present invention can be obtained by applying a solution type plate surface treating agent to the screen printing plate body and then drying it. The screen printing plate has a silane compound represented by the general formula (1) on the surface of the cured photosensitive resin (plate surface) remaining in the non-image area or the surface of the metal thin plate (plate surface) forming the non-image area. The plate surface treatment agent containing the material is bonded to form a film, and as a result, the water resistance, water repellency and oil repellency of the plate surface are improved, and consequently, the printing ink and solder paste are prevented from wrapping around the plate surface during printing. It is. The screen printing plate according to the present invention is used for screen printing by a conventionally known method in which printing ink or the like is supplied from the back surface of the screen printing plate and the back surface is squeegeeed.
本発明に係る版面処理剤を用い、上記した方法でスクリーン印版版を得ると、これは、版面に一般式（１）で表されるシラン系化合物が強固に接着し、被膜が形成されてなるものである。そして、この被膜は耐水性、撥水性及び撥油性に優れている。したがって、本発明に係るスクリーン印刷版を使用してスクリーン印刷を繰り返し行っても、シラン系化合物よりなる被膜が剥離しにくく、版面への印刷インキや半田ペーストの回り込みを長期に亙って防止しうるという効果を奏する。よって、本発明に係るスクリーン印刷版を用いれば、長期に亙って多数枚の印刷を行っても、当初の印刷状態を維持した鮮明な印刷物が得られるという効果を奏する。 When the plate surface treatment agent according to the present invention is used to obtain a screen printing plate by the above-described method, the silane compound represented by the general formula (1) is firmly adhered to the plate surface, and a film is formed. It will be. And this film is excellent in water resistance, water repellency, and oil repellency. Therefore, even if screen printing is repeatedly performed using the screen printing plate according to the present invention, the coating made of the silane compound is difficult to peel off, and the wrapping of the printing ink or solder paste on the plate surface is prevented over a long period of time. Has the effect of urging. Therefore, when the screen printing plate according to the present invention is used, there is an effect that a clear printed matter can be obtained in which the original printing state is maintained even if a large number of sheets are printed over a long period of time.
また、本発明に係る版面処理剤を用いて得られた被膜は、動摩擦係数が０．０６〜０．１３程度で小さいという特徴を持っている。したがって、本発明に係る版面処理剤を用いて得られたスクリーン印刷版で印刷すると、印刷インキや半田ペーストがスクリーン印刷版を通過しやすくなり、印刷によって付与する印刷インキや半田ペーストの量を一定量に維持することができるという効果を奏する。すなわち、印刷インキや半田ペーストが、スクリーン印刷版の画像部（開孔部）の壁面に付着滞留して、付与量が少なくなることを防止しうるという効果を奏する。 Moreover, the film obtained by using the plate surface treating agent according to the present invention has a characteristic that the coefficient of dynamic friction is as small as about 0.06 to 0.13. Therefore, when printing is performed with a screen printing plate obtained using the plate surface treating agent according to the present invention, the printing ink and solder paste can easily pass through the screen printing plate, and the amount of printing ink and solder paste applied by printing is constant. There is an effect that the amount can be maintained. That is, it is possible to prevent the printing ink and the solder paste from adhering and staying on the wall surface of the image portion (opening portion) of the screen printing plate and reducing the applied amount.
以下、実施例に基づいて、本発明は実施例に限定されるものではない。本発明は、一般式（１）で表されるシラン系化合物が、スクリーン印刷版の版面処理剤として優れているとの知見も基づくものとして、解釈されるべきである。 Hereinafter, based on an Example, this invention is not limited to an Example. The present invention should be construed based on the knowledge that the silane compound represented by the general formula (1) is excellent as a plate surface treating agent for screen printing plates.
実施例１
スクリーンとして２５０メッシュのテトロン織布を使用し、このスクリーンを枠に張設した。そして、このスクリーンの全面に、１６重量％濃度のポリビニルアルコール水溶液６２重量部と、酢酸ビニルエマルジョン３８重量部とを混合した乳液に、ジアゾニウム塩水溶液を添加してなる水系感光性樹脂組成物（感光乳剤）を塗布し、乾燥してスクリーン印刷版材を得た。このスクリーン印刷版材は、スクリーンの片面に感光性樹脂層が形成されてなるものであった。そして、スクリーン印刷版材の感光性樹脂層上に、画像形成用ネガフィルムを置いて、真空焼枠にセットし、ケミカルランプにて露光した。その後、真空焼枠から取り外して、水現像し、次いで乾燥してスクリーン印刷版本体（Ａ版，Ｂ版，Ｃ版，Ｄ版，Ｅ版及びＦ版の六枚）を得た。なお、このスクリーン印刷版本体に残存している硬化した感光性樹脂の膜厚は１０μｍであった。次に、Ａ版の版面（感光性樹脂層の表面、すなわち、被印刷物に接する面）に、以下の溶液状版面処理剤を刷毛塗りにより、塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は７１°であった。
［溶液状版面処理剤］
構造式（２）のシラン系化合物０．１ｇを、沸点７６℃のハイドロフルオロエーテル１００ｇに溶解させたもの。
Example 1
A 250-mesh tetron woven fabric was used as a screen, and this screen was stretched around a frame. A water-based photosensitive resin composition (photosensitive material) is obtained by adding a diazonium salt aqueous solution to an emulsion obtained by mixing 62 parts by weight of a 16% by weight polyvinyl alcohol aqueous solution and 38 parts by weight of a vinyl acetate emulsion on the entire surface of the screen. Emulsion) was applied and dried to obtain a screen printing plate material. This screen printing plate material has a photosensitive resin layer formed on one side of the screen. And the negative film for image formation was set | placed on the photosensitive resin layer of a screen printing plate material, and it set to the vacuum baking frame, and exposed with the chemical lamp. Then, it was removed from the vacuum baking frame, developed with water, and then dried to obtain a screen printing plate main body (6 plates of A plate, B plate, C plate, D plate, E plate and F plate). The film thickness of the cured photosensitive resin remaining on the screen printing plate main body was 10 μm. Next, the following solution type plate surface treating agent was applied to the plate surface of the A plate (the surface of the photosensitive resin layer, that is, the surface in contact with the printing material) by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 71 °.
[Solution plate surface treatment agent]
A solution obtained by dissolving 0.1 g of the silane compound of the structural formula (2) in 100 g of hydrofluoroether having a boiling point of 76 ° C.
比較例１
実施例１で得られたスクリーン印刷版本体Ｂ版を使用し、版面処理剤による処理を行わないで、そのまま、スクリーン印刷版とした。このスクリーン印刷版の版面の初期撥油性を、実施例１と同様の方法で測定したところ、０°であった。
Comparative Example 1
The screen printing plate main body B plate obtained in Example 1 was used, and a screen printing plate was used as it was without being treated with a plate surface treating agent. The initial oil repellency of the plate surface of this screen printing plate was measured by the same method as in Example 1 and found to be 0 °.
実施例２
実施例１で得られたスクリーン印刷版本体Ｃ版を使用し、このＣ版の版面に、微量の酸触媒と共にポリシラザン１．０ｇをミネラルターペン９９．０ｇに溶解したものを、刷毛塗りにより塗布した。その後、常温で１０分間乾燥させ、ポリシラザン層を形成した。次いで、実施例１で用いた溶液状版面処理剤をＣ版の版面（ポリシラザン層の表面）に、刷毛塗りにより塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は７４°であった。
Example 2
The screen printing plate main body C plate obtained in Example 1 was used, and a solution obtained by dissolving 1.0 g of polysilazane together with a small amount of an acid catalyst in 99.0 g of mineral terpenes was applied to the plate surface of this C plate by brush coating. . Thereafter, it was dried at room temperature for 10 minutes to form a polysilazane layer. Subsequently, the solution type plate surface treating agent used in Example 1 was applied to the plate surface of the C plate (the surface of the polysilazane layer) by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 74 °.
比較例２
実施例１で得られたスクリーン印刷版本体Ｄ版を使用し、このＤ版の版面に、以下の溶液状撥水撥油剤を刷毛塗りにより、塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は７７°であった。
［溶液状撥水撥油剤］
パーフルオロアルキルアクリレート重合体２．０ｇを、沸点７６℃のハイドロフルオロエーテル１００ｇに溶解させたもの。
Comparative Example 2
The screen printing plate body D plate obtained in Example 1 was used, and the following solution-like water and oil repellent agent was applied to the plate surface of the D plate by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 77 °.
[Solution-like water and oil repellent]
A solution obtained by dissolving 2.0 g of a perfluoroalkyl acrylate polymer in 100 g of hydrofluoroether having a boiling point of 76 ° C.
比較例３
実施例１で得られたスクリーン印刷版本体Ｅ版を使用し、このＥ版の版面に、以下の溶液状撥水撥油剤を刷毛塗りにより、塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は６３°であった。
［溶液状撥水撥油剤］
パーフルオロオクチルエチルトリメトキシシラン０．１ｇを、沸点７６℃のハイドロフルオロエーテル１００ｇに溶解させたもの。なお、パーフルオロオクチルエチルトリメトキシシランの動摩擦係数は０．３４であった。
Comparative Example 3
The screen printing plate main body E plate obtained in Example 1 was used, and the following solution-like water and oil repellent agent was applied to the plate surface of this E plate by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 63 °.
[Solution-like water and oil repellent]
A solution obtained by dissolving 0.1 g of perfluorooctylethyltrimethoxysilane in 100 g of hydrofluoroether having a boiling point of 76 ° C. The dynamic friction coefficient of perfluorooctylethyltrimethoxysilane was 0.34.
比較例４
実施例１で得られたスクリーン印刷版本体Ｆ版を使用し、このＦ版の版面に、微量の酸触媒と共にポリシラザン１．０ｇをミネラルターペン９９．０ｇに溶解したものを、刷毛塗りにより塗布した。その後、常温で１０分間乾燥させ、ポリシラザン層を形成した。次いで、比較例３で用いた溶液状撥水撥油剤をＦ版の版面（ポリシラザン層の表面）に、刷毛塗りにより塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は７０°であった。
Comparative Example 4
The screen printing plate main body F plate obtained in Example 1 was used, and a solution obtained by dissolving 1.0 g of polysilazane in 99.0 g of a mineral terpene together with a small amount of an acid catalyst was applied to the plate surface of this F plate by brush coating. . Thereafter, it was dried at room temperature for 10 minutes to form a polysilazane layer. Next, the solution-like water and oil repellent used in Comparative Example 3 was applied to the plate surface of the F plate (the surface of the polysilazane layer) by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 70 °.
実施例１及び２、比較例１〜４で得られたスクリーン印刷版を用い、被印刷物としてテトロン布を用いて、捺染インキでスクリーン印刷を行った。このスクリーン印刷は、スクリーン印刷版の裏面から捺染インキを供給しながら、その裏面をスキージすることによって行った。その結果、実施例１及び２で得られたスクリーン印刷版は、初期印刷が鮮明で、さらに６０００往復のスキージ操作をしても、テトロン布への印刷は良好に行え、印刷が不鮮明になるということはなかった。一方、比較例１で得られたスクリーン印刷版は、スキージ操作を繰り返すと、数回で印刷が不鮮明になった。また、比較例２で得られたスクリーン印刷版は、比較例１のものに比べると、印刷が不鮮明になる程度は低かったが、４０００往復のスキージ操作を繰り返すと、印刷が不鮮明となった。さらに、比較例３及び４で得られたスクリーン印刷版は、比較例１及び２のものに比べると、長期に亙って印刷が鮮明に行えたが、スキージ操作が４５００往復を超える時点で、徐々に印刷が不鮮明になった。 Using the screen printing plates obtained in Examples 1 and 2 and Comparative Examples 1 to 4, screen printing was performed with a printing ink using a Tetron cloth as an object to be printed. This screen printing was performed by squeezing the back surface while supplying printing ink from the back surface of the screen printing plate. As a result, the screen printing plates obtained in Examples 1 and 2 have clear initial printing, and even when 6000 squeegee squeegee operations are performed, printing on Tetoron cloth can be performed satisfactorily and printing becomes unclear. It never happened. On the other hand, when the squeegee operation was repeated, the screen printing plate obtained in Comparative Example 1 was unclear in several times. Further, the screen printing plate obtained in Comparative Example 2 had a low degree of printing blur compared with that of Comparative Example 1, but the printing became unclear when 4000 reciprocating squeegee operations were repeated. Furthermore, the screen printing plates obtained in Comparative Examples 3 and 4 were able to print clearly over a long period of time compared to those of Comparative Examples 1 and 2, but when the squeegee operation exceeded 4500 reciprocations, Gradually printing became unclear.
実施例３
厚さ５０μｍで、大きさ４５０ｍｍ×４５０ｍｍのＳＵＳ３０４板の片面を平均粗さが１．２μｍ程度に整面した。続いて、当該片面を脱脂し、稀酸で洗浄した後水洗して前処理を施した。このＳＵＳ３０４板の片面には画像形成レジスト膜を、他面には保護膜としてのドライフィルムレジストを積層した。次に、印刷されない領域として紫外線を透過する部分と、印刷される領域として紫外線を透過しない領域を持つ画像パターンを備えたガラスマスクを、画像形成レジスト膜上に置き、紫外線露光装置でＵＶ露光した。一方、ドライフィルムレジスト面には全面露光をした。１５分エージングした後、縦型現像機でアルカリ現像した後、水洗して画像形成レジスト膜にパターン形成をした。
Example 3
One surface of a SUS304 plate having a thickness of 50 μm and a size of 450 mm × 450 mm was adjusted to an average roughness of about 1.2 μm. Subsequently, the one surface was degreased, washed with dilute acid, and then washed with water to perform pretreatment. An image forming resist film was laminated on one side of the SUS304 plate, and a dry film resist as a protective film was laminated on the other side. Next, a glass mask provided with an image pattern having a portion that transmits ultraviolet rays as a non-printing region and a region that does not transmit ultraviolet rays as a printing region is placed on the image forming resist film, and UV exposure is performed by an ultraviolet exposure device. . On the other hand, the entire surface of the dry film resist surface was exposed. After aging for 15 minutes, alkali development was performed with a vertical developing machine, and then washed with water to form a pattern on the image forming resist film.
画像形成レジスト膜にパターン形成したＳＵＳ３０４板を、３９％濃度の塩化第二鉄水溶液を含むエッチング液に浸漬し、ステンシル開孔部を形成した。その後、画像形成レジスト膜及びドライフィルムレジストを剥離液に浸漬して剥離除去した。最後に、４８０Ａの電流を流しながら、６０秒間電解研磨を行い、ステンシル加工した印刷版板を得た。この印刷版板を、♯１００メッシュのポリエステル製紗と貼合して、５５０×６５０ｍｍの大きさのアルミ枠の中央部に張設し、スクリーン印刷版本体（Ｇ版、Ｈ版及びＩ版の三枚）を得た。 A SUS304 plate patterned on the image-forming resist film was immersed in an etching solution containing a 39% ferric chloride aqueous solution to form a stencil opening. Thereafter, the image forming resist film and the dry film resist were immersed and removed in a stripping solution. Finally, electropolishing was performed for 60 seconds while a current of 480 A was applied to obtain a stencil-processed printing plate. This printing plate is bonded to a # 100 mesh polyester plate and stretched at the center of an aluminum frame having a size of 550 × 650 mm, and the screen printing plate main body (G plate, H plate and I plate) Three).
次に、Ｇ版の版面（ステンシル加工した印刷版板の被印刷物に接する面）に、微量の酸触媒と共にポリシラザン１．０ｇをミネラルターペン９９．０ｇに溶解したものを、刷毛塗りにより塗布した。その後、常温で１０分間乾燥させ、ポリシラザン層を形成した。次いで、実施例１で用いた溶液状版面処理剤をＧ版の版面（ポリシラザン層の表面）に、刷毛塗りにより塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は７１°であった。 Next, a solution obtained by dissolving 1.0 g of polysilazane in 99.0 g of a mineral terpene together with a trace amount of an acid catalyst was applied to the plate surface of the G plate (the surface of the printing plate subjected to stencil processing in contact with the substrate) by brush coating. Thereafter, it was dried at room temperature for 10 minutes to form a polysilazane layer. Next, the solution type plate surface treating agent used in Example 1 was applied to the plate surface of the G plate (the surface of the polysilazane layer) by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the plate surface of this screen printing plate was measured with normal hexadecane, the contact angle was 71 °.
比較例５
実施例３で得られたスクリーン印刷版本体Ｈ版を使用し、版面処理剤による処理を行わないで、そのまま、スクリーン印刷版とした。このスクリーン印刷版の版面の初期撥油性を、実施例３と同様の方法で測定したところ、０°であった。
Comparative Example 5
The screen printing plate main body H plate obtained in Example 3 was used, and a screen printing plate was used as it was without being treated with a plate surface treating agent. When the initial oil repellency of the plate surface of this screen printing plate was measured in the same manner as in Example 3, it was 0 °.
比較例６
実施例３で得られたスクリーン印刷版本体Ｉ版を使用し、このＩ版の版面（ステンシル加工した印刷版板の被印刷物に接する面）に、微量の酸触媒と共にポリシラザン１．０ｇをミネラルターペン９９．０ｇに溶解したものを、刷毛塗りにより塗布した。その後、常温で１０分間乾燥させ、ポリシラザン層を形成した。次いで、比較例３で用いた撥水撥油剤をＩ版の版面（ポリシラザン層の表面）に、刷毛塗りにより塗布した。塗布後、４０℃の恒温室で２４時間乾燥させて、スクリーン印刷版を得た。このスクリーン印刷版の版面の初期撥油性をノルマルヘキサデカンで測定したところ、接触角は６４°であった。
Comparative Example 6
The screen printing plate body I plate obtained in Example 3 was used, and 1.0 g of polysilazane together with a trace amount of acid catalyst was added to a mineral turpent on the plate surface of this I plate (the surface of the stencil-processed printing plate contacting the printed material). What was dissolved in 99.0 g was applied by brushing. Thereafter, it was dried at room temperature for 10 minutes to form a polysilazane layer. Next, the water / oil repellent used in Comparative Example 3 was applied to the plate surface of the I plate (the surface of the polysilazane layer) by brush coating. After the application, it was dried in a constant temperature room at 40 ° C. for 24 hours to obtain a screen printing plate. When the initial oil repellency of the screen printing plate was measured with normal hexadecane, the contact angle was 64 °.
実施例３及び比較例５、６で得られたスクリーン印刷版を用い、被印刷物として実装前のプリント配線版を用いて、半田ペーストをスクリーン印刷した。このスクリーン印刷は、スクリーン印刷版の裏面から半田ペーストを供給しながら、その裏面をスキージすることによって行った。この結果、実施例３で得られたスクリーン印刷版を用いたものは、初期印刷が鮮明で、半田ペーストの滲みが少なく、印刷塗布量を多く良好であった。しかも、スキージ操作を３０００往復繰り返しても、この効果は持続した。一方、比較例５で得られたスクリーン印刷版を用いたものは、初期印刷時においても半田ペーストの滲みが発生した。比較例６で得られたスクリーン印刷版を用いたものは、初期印刷は鮮明であったが、半田ペーストの印刷塗布量は実施例３のものより少なかった。また、スキージ操作を１０００回繰り返すと、半田ペーストの滲みが発生した。 Using the screen printing plate obtained in Example 3 and Comparative Examples 5 and 6, a solder paste was screen printed using a printed wiring plate before mounting as a substrate to be printed. This screen printing was performed by squeezing the back surface while supplying solder paste from the back surface of the screen printing plate. As a result, using the screen printing plate obtained in Example 3, the initial printing was clear, the solder paste was less blurred, and the amount of printing applied was good. Moreover, this effect was sustained even when the squeegee operation was repeated 3000 times. On the other hand, in the case of using the screen printing plate obtained in Comparative Example 5, bleeding of the solder paste occurred even during initial printing. In the case of using the screen printing plate obtained in Comparative Example 6, the initial printing was clear, but the printing amount of the solder paste was less than that in Example 3. Further, when the squeegee operation was repeated 1000 times, solder paste bleeding occurred.
Claims (11)
ＯＡは、ＯＣＦ2ＣＦ2ＣＦ2，ＯＣＦ（ＣＦ3）ＣＦ2，ＯＣＦ2ＣＦ2及びＯＣＦ2よりなる群から選ばれる１種以上の基を示す。
Ｘは、ヨウ素原子、臭素原子又は水素原子を示す。
Ｙは、水素原子又は低級アルキル基を示す。
Ｒ１は、加水分解性基を示す。
Ｒ２は、水素原子又は非加水分解性基を示す。
ｍ及びｎは、０〜２の整数を示す。
ｐは、１〜１０の整数を示す。
ｑは、１又は２を示す。
ｒは、１〜２００の整数を示す。］ A plate surface treating agent for a screen printing plate comprising a silane compound represented by the general formula (1).
OA represents one or more groups selected from the group consisting of OCF 2 CF 2 CF 2 , OCF (CF 3 ) CF 2 , OCF 2 CF 2, and OCF 2 .
X represents an iodine atom, a bromine atom or a hydrogen atom.
Y represents a hydrogen atom or a lower alkyl group.
R1 represents a hydrolyzable group.
R2 represents a hydrogen atom or a non-hydrolyzable group.
m and n show the integer of 0-2.
p represents an integer of 1 to 10.
q represents 1 or 2.
r represents an integer of 1 to 200. ]
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| US9186879B2 (en) | 2010-05-28 | 2015-11-17 | Taiyo Yuden Chemical Technology Co., Ltd. | Screen-printing stencil having amorphous carbon films and manufacturing method therefor |
| JP5802752B2 (en) * | 2011-07-01 | 2015-11-04 | 太陽誘電ケミカルテクノロジー株式会社 | Primer composition, structure comprising primer layer comprising the composition, and method for producing the structure |
| TWI532537B (en) | 2011-08-10 | 2016-05-11 | 太陽誘電化學技術股份有限公司 | Structure for printing including thin primer film, stencil printing plate, and process for producing said structure for printing |
| CN102615932B (en) * | 2012-04-06 | 2013-12-11 | 深圳光韵达光电科技股份有限公司 | Metal printing template, manufacturing method of metal printing template and coating solution used in metal printing template |
| JP6053580B2 (en) * | 2013-03-13 | 2016-12-27 | キヤノン株式会社 | Water repellent treatment method for fine pattern surface |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05116475A (en) * | 1991-10-29 | 1993-05-14 | Kimoto & Co Ltd | Surface-improved stencil and method for improving the surface |
| JPH05220922A (en) * | 1992-02-18 | 1993-08-31 | Matsushita Electric Ind Co Ltd | Metal mask and production thereof |
| JP2874715B2 (en) * | 1995-08-11 | 1999-03-24 | ダイキン工業株式会社 | Silicon-containing organic fluoropolymer and method for producing the same |
| JP2000029631A (en) * | 1998-07-09 | 2000-01-28 | Sumitomo Chem Co Ltd | Upper transparent electrode plate for touch panel and device provided with the same |
| JP2001188102A (en) * | 1999-12-27 | 2001-07-10 | Toppan Printing Co Ltd | Antireflection film |
| JP2005305725A (en) * | 2004-04-19 | 2005-11-04 | Process Lab Micron:Kk | Metal mask and manufacturing method thereof |
| JP2006347062A (en) * | 2005-06-17 | 2006-12-28 | Fluoro Technology:Kk | Plate film surface treating agent for screen printing plate |
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