JP2017194637A5

JP2017194637A5 -

Info

Publication number: JP2017194637A5
Application number: JP2016086234A
Authority: JP
Filing date: 2016-04-22
Publication date: 2019-03-14
Anticipated expiration: 2036-04-22

Description

（樹脂Ｒ−７の合成：末端に２つ水酸基を有する重合体と芳香族テトラカルボン酸無水物との反応生成物）
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、メチルメタクリレート７５部、ｔ−ブチルアクリレート２０部、メタクリル酸５．０部、３−メルカプト−１，２−プロパンジオール２．０部、２’−アゾビスイソブチロニトリル０．１部、ＰＧＭＡｃ１０２部を添加して、１０時間反応した。固形分測定により９５％が反応したことを確認した。続いてピロメリット酸無水物３．２部、ＰＧＭＡｃ６．０部、触媒として１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン０．２０部を追加し、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化していることを確認し反応を終了した。先に合成した分散剤に不揮発分が５０重量％になるようにプロピレングリコールモノメチルエーテルアセテートを添加して、酸価４６．７、重量平均分子量１９５００の樹脂Ｒ−７を得た。

(Synthesis of Resin R-7: Reaction Product of Polymer Having Two Hydroxyl Groups at Terminal and Aromatic Tetracarboxylic Acid Anhydride)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 75 parts of methyl methacrylate, 20 parts of t-butyl acrylate, 5.0 parts of methacrylic acid , 2.0 parts of 3-mercapto-1,2-propanediol 0.1 part of 2′-azobisisobutyronitrile and 102 parts of PGMAc were added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. Subsequently, 3.2 parts of pyromellitic anhydride, 6.0 parts of PGMAc, and 0.20 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. I let you. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by weight to obtain Resin R-7 having an acid value of 46.7 and a weight average molecular weight of 19,500.

（原料フタロシアニン化合物（Ｑ−４）の製造）
上記フタロシアニン化合物（Ｑ−３）の製造において、トリクロロイソシアヌル酸１０８部をＮ−ブロモスクシンイミド１８６部に変更した以外は、（Ｑ−３）の製造と同様にして１４３部のフタロシアニン化合物（Ｑ−４）を製造した。臭素置換数を算出したところ、平均６．０個であり、マススペクトラムからも同一の分子量に相当するピークを確認し、目的の化合物であることを同定した。

(Production of raw material phthalocyanine compound (Q-4))
In the production of the phthalocyanine compound (Q-3), 143 parts of the phthalocyanine compound (Q-4 ) were produced in the same manner as in the production of (Q-3) except that 108 parts of trichloroisocyanuric acid was changed to 186 parts of N-bromosuccinimide. ) Was manufactured. When the number of bromine substitutions was calculated, the average was 6.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum to identify the target compound.

（原料フタロシアニン化合物（Ｑ−５）の製造）
上記フタロシアニン化合物（Ｑ−３）の製造において、トリクロロイソシアヌル酸１０８部を１，３−ジブロモ−５，５−ジメチルヒダントイン２４９部に変更した以外は、（Ｑ−３）の製造と同様にして１８７部のフタロシアニン顔料（Ｑ−５）を製造した。臭素置換数を算出したところ、平均１０．３個であり、マススペクトラムからも同一の分子量に相当するピークを確認し、目的の化合物であることを同定した。

(Production of raw material phthalocyanine compound (Q-5))
In the production of the above phthalocyanine compound (Q-3), except that 108 parts of trichloroisocyanuric acid was changed to 249 parts of 1,3-dibromo-5,5-dimethylhydantoin, 187 was carried out in the same manner as in the production of (Q-3). Part of a phthalocyanine pigment (Q-5) was produced. When the number of bromine substitutions was calculated, the average was 10.3, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum to identify the target compound.

［実施例２〜３２、比較例１〜１３］
（顔料組成物Ａ−２〜Ａ−３２、Ｂ−１〜Ｂ−１３の製造）
フタロシアニン化合物、酸性化合物、樹脂を表３に記載した条件にそれぞれ変更した以外は顔料組成物Ａ−１と同様な操作を行い、それぞれ顔料組成物Ａ−２〜Ａ−３２、Ｂ−１〜Ｂ−１３を得た。収量、収率、ハロゲン原子Ｘ、ハロゲン置換基数ｎの結果を表３に示す。Ｂ−１〜Ｂ−１１は樹脂を含まない。

[Examples 2-32 and Comparative Examples 1-13]
(Production of pigment compositions A-2 to A-3 2 and B-1 to B-13)
Except for changing the phthalocyanine compound, acidic compound, and resin to the conditions described in Table 3, the same operations as in the pigment composition A-1 were performed, and the pigment compositions A-2 to A-32 and B-1 to B, respectively. -13 was obtained. Table 3 shows the results of yield, yield, halogen atom X, and halogen substituent number n. B-1 to B-11 do not contain a resin.

［実施例３９〜７６］［比較例１４〜２７］
（着色組成物Ｄ−２〜Ｄ−５３の調整）
表４に示す材料・配合比を用いた以外は実施例３８と同様にして、着色組成物Ｄ−２〜Ｄ−５３を得た。顔料組成物（Ａ−１）と微細化顔料（ＰＹ−２）、顔料組成物（Ａ−１）と微細化顔料（ＰＹ−３）とは塗布基板にした際に、Ｃ光源でｘ（ｃ）＝０．２９０、ｙ（ｃ）＝０．６００となる配合比で作製した。

[Examples 39 to 76] [Comparative Examples 14 to 27]
(Adjustment of colored compositions D- 2 to D-53)
Colored compositions D- 2 to D-53 were obtained in the same manner as in Example 38 except that the materials and blending ratios shown in Table 4 were used. When the pigment composition (A-1) and the micronized pigment (PY-2), and the pigment composition (A-1) and the micronized pigment (PY-3) are applied to the coated substrate, x (c ) = 0.290 and y (c) = 0.600.