公开(公告)号：US06174955B1

公开(公告)日：2001-01-16

申请号：US09139272

申请日：1998-08-25

申请人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Satoru Kobayashi ,  Kentaro Tsutsumi

发明人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Satoru Kobayashi ,  Kentaro Tsutsumi

IPC分类号： C08L2712

CPC分类号： C09D127/12 ,  C08G18/6279 ,  C08G18/706 ,  C08G18/718 ,  C08L75/04 ,  C08L2666/28 ,  C08L2666/14

摘要： The invention provides a first water-based fluorine-containing paint including a water-based emulsion containing a fluorine-containing copolymer dispersed therein, and 1-50 parts by weight of a hardener per 100 parts by weight of the copolymer. The copolymer is prepared by copolymerizing 30-65 mol % of a fluoroolefin, 14-69 mol % of a copolymerizable vinyl-containing compound, and 1-30 mol % of a hydroxyl-containing compound and/or a polymerizable carboxyl-containing compound. The hardener is prepared by mixing 1 part by weight of a self-emulsifiable polyisocyanate with 0.01-1 part by weight of a compound containing in the molecule an oxyethylene unit and an alkoxysilyl group. When mixed with the emulsion, the hardener becomes well dispersed therein. The invention further provides a second water-based fluorine-containing paint including a water-based emulsion containing a fluorine-containing copolymer dispersed therein, and a hardener which is a compound containing in the molecule at least two hydrazino groups. The fluorine-containing copolymer is prepared by emulsion polymerization of 30-65 mol % of a fluoroolefin, 0.1-20 mol % of a polymerizable unsaturated carboxylic acid, 1-30 mol % of a polymerizable acetoacetylallyl compound, and 20-65 mol % of one of a vinyl ester and a vinyl ether. The second paint does not cure at ambient temperature, even after the hardener has been added thereto, and thus is usable as a one-package paint.

摘要翻译： 本发明提供第一种水性含氟涂料，其包含含有分散在其中的含氟共聚物的水性乳液和每100份重量共聚物1-50份重量的硬化剂。 该共聚物通过使30-65mol％的氟烯烃，14-69mol％的可共聚的含乙烯基化合物和1-30mol％的含羟基化合物和/或可聚合的含羧基化合物共聚而制备。 通过将1重量份的自乳化多异氰酸酯与0.01-1重量份在分子中含有氧化乙烯单元和烷氧基甲硅烷基的化合物混合来制备固化剂。 当与乳液混合时，固化剂变得很好地分散在其中。 本发明还提供了包含分散在其中的含有含氟共聚物的水性乳液的第二水性含氟涂料，以及分子中含有至少两个肼基的化合物的固化剂。 含氟共聚物通过30-65mol％的氟代烯烃，0.1-20mol％的可聚合不饱和羧酸，1-30mol％的可聚合乙酰乙烯基化合物和20-65mol％的可聚合乙酰乙烯基化合物的乳液聚合制备， 乙烯基酯和乙烯基醚之一。 第二种涂料即使在加入固化剂之后也不能在环境温度下固化，因此可用作单组分涂料。

公开(公告)号：US5880234A

公开(公告)日：1999-03-09

申请号：US831305

申请日：1997-04-01

申请人： Kazuhiko Maeda ,  Yukio Ikeda ,  Kentaro Tsutsumi ,  Yutaka Maruyama ,  Shuyo Akama ,  Michitaka Ohtani

发明人： Kazuhiko Maeda ,  Yukio Ikeda ,  Kentaro Tsutsumi ,  Yutaka Maruyama ,  Shuyo Akama ,  Michitaka Ohtani

IPC分类号： C08F214/18 ,  C08F218/10 ,  C08F12/22

CPC分类号： C08F218/10 ,  C08F214/184 ,  C08F214/186

摘要： The invention relates to a curable fluorine-containing copolymer prepared by copolymerizing a monomer mixture. This monomer mixture is in an amount of 100 mol % in total and includes (a) 10-60 mol % of a first polymerizable monomer that is one of hexafluoroisobutene and hexafluoroacetone, each of which has one hexafluoroisopropylidene group; (b) 10-70 mol % of a fatty acid vinyl ester that is represented by a general formula of CH.sub.2 .dbd.CH--OC (.dbd.O) --R.sup.1 where R.sup.1 is one of an alkyl group and --(CH.sub.2).sub.m --R.sup.2 --(CH.sub.2).sub.n --H where R.sup.2 is one of a cycloalkylene group and a divalent aromatic group, and m and n are respectively integers each ranging from 0 to 12, the alkyl group having a carbon atom number of from 1 to 22 and an optional branched chain, each of the cycloalkylene group and the divalent aromatic group having an optional substituent; (c) 1-60 mol % of a second polymerizable monomer that has a cross-linkable functional group and a polymerizable double bond, the cross-linkable functional group being one selected from the group consisting of hydroxyl group, carboxyl group, hydrolyzable organosilyl groups, epoxy groups, .beta.-ketoester groups; and (d) 0-20 mol %, of a third polymerizable monomer that is different from the first and second monomers and the fatty acid vinyl ester and is free of a cross-linkable functional group. A coated film prepared by the application of a varnish containing the fluorine-containing copolymer is superior in water repellency and stain resistance.

摘要翻译： 本发明涉及通过共聚单体混合物制备的可固化含氟共聚物。 该单体混合物的总量为100摩尔％，包括（a）10-60摩尔％的作为六氟异丁烯和六氟丙酮之一的第一可聚合单体，每个具有一个六氟异丙烯基; （b）10-70mol％由通式CH 2 = CH-OC（= O）-R1表示的脂肪酸乙烯基酯，其中R1是烷基和 - （CH2）m -R2- （CH2）nH，其中R2是亚环烷基和二价芳族基团之一，m和n分别为0-12的整数，碳原子数为1至22的烷基和任选的支链 ，各环亚烷基和具有任选取代基的二价芳基; （c）1-60摩尔％具有可交联官能团和可聚合双键的第二可聚合单体，所述可交联官能团选自羟基，羧基，可水解的有机甲硅烷基 ，环氧基团，β-酮酯基团; 和（d）0-20摩尔％的不同于第一和第二单体和脂肪酸乙烯基酯并且不含可交联官能团的第三可聚合单体。 通过使用含有含氟共聚物的清漆制备的涂膜具有优异的防水性和耐污染性。

公开(公告)号：US5856394A

公开(公告)日：1999-01-05

申请号：US647853

申请日：1996-05-15

申请人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Satoru Kobayashi ,  Kentaro Tsutsumi

发明人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Satoru Kobayashi ,  Kentaro Tsutsumi

IPC分类号： C08G18/62 ,  C08G18/70 ,  C08G18/71 ,  C08L75/04 ,  C09D127/12 ,  C08L27/12

CPC分类号： C09D127/12 ,  C08G18/6279 ,  C08G18/706 ,  C08G18/718 ,  C08L75/04

摘要： The invention provides a first water-based fluorine-containing paint including a water-based emulsion containing a fluorine-containing copolymer dispersed therein, and 1-50 parts by weight of a hardener per 100 parts by weight of the copolymer. The copolymer is prepared by copolymerizing 30-65 mol % of a fluoroolefin, 14-69 mol % of a copolymerizable vinyl-containing compound, and 1-30 mol % of a hydroxyl-containing compound and/or a polymerizable carboxyl-containing compound. The hardener is prepared by mixing 1 part by weight of a self-emulsifiable polyisocyanate with 0.01-1 part by weight of a compound containing in the molecule an oxyethylene unit and an alkoxysilyl group. When mixed with the emulsion, the hardener becomes well dispersed therein. The invention further provides a second water-based fluorine-containing paint including a water-based emulsion containing a fluorine-containing copolymer dispersed therein, and a hardener which is a compound containing in the molecule at least two hydrazino groups. The fluorine-containing copolymer is prepared by emulsion polymerization of 30-65 mol % of a fluoroolefin, 0.1-20 mol % of a polymerizable unsaturated carboxylic acid, 1-30 mol % of a polymerizable acetoacetylallyl compound, and 20-65 mol % of one of a vinyl ester and a vinyl ether. The second paint does not cure at ambient temperature, even after the hardener has been added thereto, and thus is usable as a one-package paint.

摘要翻译： 本发明提供第一种水性含氟涂料，其包含含有分散在其中的含氟共聚物的水性乳液和每100份重量共聚物1-50份重量的硬化剂。 该共聚物通过使30-65mol％的氟烯烃，14-69mol％的可共聚的含乙烯基化合物和1-30mol％的含羟基化合物和/或可聚合的含羧基化合物共聚而制备。 通过将1重量份自乳化多异氰酸酯与0.01-1重量份在分子中含有氧化乙烯单元和烷氧基甲硅烷基的化合物混合来制备固化剂。 当与乳液混合时，固化剂变得很好地分散在其中。 本发明还提供了包含分散在其中的含有含氟共聚物的水性乳液的第二水性含氟涂料，以及分子中含有至少两个肼基的化合物的固化剂。 含氟共聚物通过30-65mol％的氟代烯烃，0.1-20mol％的可聚合不饱和羧酸，1-30mol％的可聚合乙酰乙烯基化合物和20-65mol％的可聚合乙酰乙烯基化合物的乳液聚合制备， 乙烯基酯和乙烯基醚之一。 第二种涂料即使在加入固化剂之后也不能在环境温度下固化，因此可用作单组分涂料。

公开(公告)号：US06176891B1

公开(公告)日：2001-01-23

申请号：US09048111

申请日：1998-03-26

申请人： Haruhiko Komoriya ,  Kazuhiko Maeda ,  Masayuki Shiota ,  Yoshi Hirashima ,  Kentaro Tsutsumi ,  Mikio Ootani ,  Yukio Ikeda

发明人： Haruhiko Komoriya ,  Kazuhiko Maeda ,  Masayuki Shiota ,  Yoshi Hirashima ,  Kentaro Tsutsumi ,  Mikio Ootani ,  Yukio Ikeda

IPC分类号： C05G500

CPC分类号： C08G18/36 ,  C05G3/0029 ,  C08G18/5021 ,  C08G18/8051

摘要： The invention relates to a coated granular fertilizer having a film covering fertilizer granules. This film comprises a polyurethane resin prepared by a method comprising the steps of (a) reacting an aromatic polyisocyanate with a first polyol component (i.e., castor oil or a castor oil derivative), thereby to obtain a prepolymer having terminal isocyanate groups in the molecule; and (b) reacting the prepolymer with a second polyol component (i.e., castor oil or a castor oil derivative) and a third polyol component which is an amine having at least two hydroxyl groups in the molecule, thereby to cure the prepolymer and thus to prepare the polyurethane resin. The invention relates to another coated granular fertilizer having a film covering fertilizer granules. This film comprises a urethane resin and aqueous-fluid-absorbing particles having a particle diameter of from 1 to 200 &mgr;m. This urethane resin may be the above polyurethane resin. This coated granular fertilizer can be produced by a method comprising the steps of (a) applying an aromatic polyisocyanate, a polyol component (i.e., castor oil or a castor oil derivative), an amine, and the aqueous-fluid-absorbing particles, at the same time or separately in no special order, while the fertilizer granules are kept fluidized or rolled, thereby to form a precursory film on the fertilizer granules; and (b) curing the precursory film into the film. Each coated granular fertilizer is substantially superior in regulation of the release of plant nutrient elements therefrom.

公开(公告)号：US06384182B2

公开(公告)日：2002-05-07

申请号：US09904529

申请日：2001-07-16

申请人： Kazuhiko Maeda ,  Yoshihiro Moroi ,  Michio Ishida ,  Kentaro Tsutsumi

发明人： Kazuhiko Maeda ,  Yoshihiro Moroi ,  Michio Ishida ,  Kentaro Tsutsumi

IPC分类号： C08G6926

CPC分类号： C08G73/22

摘要： The invention relates to a fluorine-containing polybenzoxazole including a structural unit represented by the general formula (1): where X is a tetravalent organic group containing an aromatic ring, and two sets of N and O are each bonded to the ortho positions of the aromatic ring of X such that two five-membered rings are formed next to the aromatic ring of X. This polybenzoxazole demonstrates low dielectric constant and low coefficient of thermal expansion while maintaining the properties of polybenzoxazole including mechanical strength and thermal stability.

摘要翻译： 本发明涉及包含由通式（1）表示的结构单元的含氟聚苯并恶唑：其中X是含有芳香环的四价有机基团，并且两组N和O各自键合到 X的芳环，使得在X的芳香环上形成两个五元环。该聚苯并恶唑表现出低的介电常数和低的热膨胀系数，同时保持聚苯并恶唑的性质，包括机械强度和热稳定性。

公开(公告)号：US06322606B1

公开(公告)日：2001-11-27

申请号：US09665123

申请日：2000-09-20

申请人： Haruhiko Komoriya ,  Kazuhiko Maeda ,  Masayuki Shiota ,  Yoshi Hirashima ,  Kentaro Tsutsumi ,  Mikio Ootani ,  Yukio Ikeda

发明人： Haruhiko Komoriya ,  Kazuhiko Maeda ,  Masayuki Shiota ,  Yoshi Hirashima ,  Kentaro Tsutsumi ,  Mikio Ootani ,  Yukio Ikeda

IPC分类号： C05G500

CPC分类号： C08G18/36 ,  C05G3/0029 ,  C08G18/5021 ,  C08G18/8051

摘要： The invention relates to a coated granular fertilizer having a film covering fertilizer granules. This film comprises a polyurethane resin prepared by a method comprising the steps of (a) reacting an aromatic polyisocyanate with a first polyol component (i.e., castor oil or a castor oil derivative), thereby to obtain a prepolymer having terminal isocyanate groups in the molecule; and (b) reacting the prepolymer with a second polyol component (i.e., castor oil or a castor oil derivative) and a third polyol component which is an amine having at least two hydroxyl groups in the molecule, thereby to cure the prepolymer and thus to prepare the polyurethane resin. The invention relates to another coated granular fertilizer having a film covering fertilizer granules. This film comprises a urethane resin and aqueous-fluid-absorbing particles having a particle diameter of from 1 to 200 &mgr;m. This urethane resin may be the above polyurethane resin. This coated granular fertilizer can be produced by a method comprising the steps of (a) applying an aromatic polyisocyanate, a polyol component (i.e., castor oil or a castor oil derivative), an amine, and the aqueous-fluid-absorbing particles, at the same time or separately in no special order, while the fertilizer granules are kept fluidized or rolled, thereby to form a precursory film on the fertilizer granules; and (b) curing the precursory film into the film. Each coated granular fertilizer is substantially superior in regulation of the release of plant nutrient elements therefrom.

摘要翻译： 本发明涉及具有覆盖肥料颗粒的薄膜的涂覆颗粒肥料。 该膜包括通过包括以下步骤的方法制备的聚氨酯树脂：（a）使芳族多异氰酸酯与第一多元醇组分（即蓖麻油或蓖麻油衍生物）反应，由此得到分子中具有末端异氰酸酯基团的预聚物 ; 和（b）使预聚物与第二多元醇组分（即蓖麻油或蓖麻油衍生物）和第三多元醇组分反应，所述第三多元醇组分是分子中具有至少两个羟基的胺，从而固化预聚物，从而使 制备聚氨酯树脂。 本发明涉及具有覆盖肥料颗粒的膜的另一种涂覆颗粒肥料。 该膜包含聚氨酯树脂和粒径为1〜200μm的水溶液吸收性粒子。 该聚氨酯树脂可以是上述聚氨酯树脂。 该涂覆的颗粒肥料可以通过以下方法制备：（a）将芳族多异氰酸酯，多元醇组分（即蓖麻油或蓖麻油衍生物），胺和水性流体吸收颗粒施用于 同时或以特殊顺序分开，同时将肥料颗粒保持流化或滚动，从而在肥料颗粒上形成前体膜; 和（b）将前体膜固化成膜。 每个涂覆的颗粒肥料在调节植物营养元素的释放方面基本上都是优异的。

公开(公告)号：US6166141A

公开(公告)日：2000-12-26

申请号：US873231

申请日：1997-06-11

申请人： Kazuhiko Maeda ,  Yukio Ikeda ,  Kentaro Tsutsumi ,  Seiji Hasegawa

发明人： Kazuhiko Maeda ,  Yukio Ikeda ,  Kentaro Tsutsumi ,  Seiji Hasegawa

IPC分类号： C08F259/08 ,  C08L51/00 ,  C09D127/16 ,  C09D151/00 ,  C08L27/12 ,  C08F214/18

CPC分类号： C09D151/003 ,  C08F259/08 ,  C08L51/003 ,  C09D127/16 ,  C08L2666/24

摘要： The invention relates to a fluorine-containing resin (graft copolymer) used for preparing a paint. This resin is prepared by a graft copolymerization of a fluorine-containing copolymer with a first monomer composition. The fluorine-containing copolymer comprises a first constitutional unit derived from a fluoroolefin and at least one of second and third constitutional units. The second constitutional unit is derived from a particular carboxylic acid vinyl ester represented by a general formula of R--C(.dbd.O)OCH.dbd.CH.sub.2 where R is a special group. The third constitutional unit is derived from a first monomer which is at least one compound selected from vinyl ethers and allyl ethers. The first monomer is represented by a general formula of R--O--(CH.sub.2)n--CH.dbd.CH.sub.2. The first monomer composition for preparing the resin contains a second monomer which is at least one compound selected from methacrylic acid esters and acrylic esters. The second monomer is represented by a general formula of CH.sub.2 .dbd.C(--R')C(.dbd.O)O--R where R' is hydrogen atom or methyl group. A composition prepared by mixing the resin with vinylidene fluoride resin or with a combination of vinylidene fluoride resin and acrylic resin is capable of providing a coated film having high gloss, high weather resistance, and good results in bending test for a long time. Another composition prepared by mixing the resin with a hardener is capable of providing a coated film having high hardness, good adhesion to various other coated films, high weather resistance, and high stain resistance.

摘要翻译： 本发明涉及用于制备涂料的含氟树脂（接枝共聚物）。 该树脂通过含氟共聚物与第一单体组合物的接枝共聚而制备。 含氟共聚物包含衍生自氟代烯烃的第一结构单元和第二和第三结构单元中的至少一个。 第二结构单元衍生自由通式R-C（= O）OCH = CH 2表示的特定羧酸乙烯基酯，其中R是特殊基团。 第三结构单元衍生自作为至少一种选自乙烯基醚和烯丙基醚的化合物的第一单体。 第一单体由通式R-O-（CH 2）n -CH = CH 2表示。 用于制备树脂的第一单体组合物含有作为至少一种选自甲基丙烯酸酯和丙烯酸酯的化合物的第二单体。 第二单体由通式CH 2 = C（-R'）C（= O）O-R表示，其中R'是氢原子或甲基。 通过将树脂与偏氟乙烯树脂或偏二氟乙烯树脂和丙烯酸树脂的组合混合而制备的组合物能够提供长时间具有高光泽，高耐候性和良好的弯曲试验结果的涂膜。 通过将树脂与硬化剂混​​合而制备的另一组合物能够提供具有高硬度，对各种其它涂膜的良好粘附性，高耐候性和高耐污性的涂膜。

公开(公告)号：US5859123A

公开(公告)日：1999-01-12

申请号：US749698

申请日：1996-11-15

申请人： Satoru Kobayashi ,  Kazuhiko Maeda ,  Yoshi Hirashima ,  Seiji Hasegawa ,  Kentaro Tsutsumi

发明人： Satoru Kobayashi ,  Kazuhiko Maeda ,  Yoshi Hirashima ,  Seiji Hasegawa ,  Kentaro Tsutsumi

IPC分类号： C08F214/18 ,  C08F214/24 ,  C08F214/26 ,  C09D143/04 ,  C08L27/12

CPC分类号： C08F214/18 ,  C08F214/245 ,  C08F214/265 ,  C09D143/04 ,  C08L2201/52

摘要： The present invention relates to a water-based fluorine-containing emulsion. This emulsion contains a fluorine-containing copolymer in a disperse phase thereof This copolymer is prepared by copolymerizing: (A) a fluoroolefin, (B) an organosilicon compound containing an olefinic unsaturated bond and an alkoxysilyl group, (C) an unsaturated carboxylic acid represented by a general formula of CH.sub.2 .dbd.CH--(CH.sub.2).sub.n --COOH where n is an integer of from 3 to 15, and (D) at least one other copolymerizable monomer. A paint prepared from the emulsion is superior in storage stability and mechanical stability, although this paint belongs to a one-package paint. A coated film formed by applying the paint is superior in water resistance in its early stages, stain resistance, and weather resistance.

摘要翻译： 本发明涉及水性含氟乳液。 该乳液在分散相中含有含氟共聚物。该共聚物通过共聚以下物质制备：（A）氟烯烃，（B）含有烯属不饱和键的有机硅化合物和烷氧基甲硅烷基，（C）不饱和羧酸 通式为CH 2 = CH-（CH 2）n -COOH，其中n为3至15的整数，和（D）至少一种其它可共聚单体。 由乳液制备的油漆在储存稳定性和机械稳定性方面是优异的，尽管这种油漆属于单组分涂料。 通过涂覆涂料形成的涂膜在其早期的耐水性，耐污染性和耐候性方面都是优异的。

公开(公告)号：US5684074A

公开(公告)日：1997-11-04

申请号：US548062

申请日：1995-10-25

申请人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Kentaro Tsutsumi

发明人： Yoshi Hirashima ,  Kazuhiko Maeda ,  Kentaro Tsutsumi

IPC分类号： C08K5/5415 ,  C08K5/54

CPC分类号： C08K5/5415

摘要： The invention provides a novel coating composition comprising a first component (i.e. 100 parts by weight of a fluorine-containing copolymer), a second component (i.e. 0.1-20 parts by weight of an alkyl silicate), and a third component (i.e. 0.05-3 parts by weight of a water-soluble polyether-modified silicone oil and/or 1-25 parts by weight of a polyoxytetramethylene glycol). The fluorine-containing copolymer has a hydroxyl value of 80-200 mg KOH per 1g thereof and is prepared by copolymerizing 40-65 mol % of a fluoroolefin, 14-50 mo1% of a copolymerizable vinyl-containing compound, 12-25 mol % of a polymerizable hydroxyl-containing compound, and 0.1-12 mol % of at least one other copolymerizable compound. A cured coated film prepared from the coating composition is superior in elasticity and weathering and stain resistances.

摘要翻译： 本发明提供一种新型涂料组合物，其包含第一组分（即100重量份的含氟共聚物），第二组分（即0.1-20重量份的烷基硅酸盐）和第三组分（即0.05- 3重量份水溶性聚醚改性硅油和/或1-25重量份聚氧四亚甲基二醇）。 含氟共聚物的羟值为每1g 1g的80-200mg KOH，通过使40-65mol％的氟烯烃，14-50mol％的可共聚的含乙烯基化合物，12-25mol％ 的可聚合羟基化合物和0.1-12mol％的至少一种其它可共聚的化合物。 由涂料组合物制备的固化涂膜具有优异的弹性和耐候性和耐污染性。

公开(公告)号：US07417100B2

公开(公告)日：2008-08-26

申请号：US11252580

申请日：2005-10-19

申请人： Haruhiko Komoriya ,  Sunao Koga ,  Kentaro Tsutsumi ,  Kazuhiko Maeda

发明人： Haruhiko Komoriya ,  Sunao Koga ,  Kentaro Tsutsumi ,  Kazuhiko Maeda

IPC分类号： C08F18/20

CPC分类号： C08F220/22

摘要： The present invention relates to a fluorine-containing copolymer. This fluorine-containing copolymer includes (a) a first unit derived from α-trifluoromethyl acrylic ester represented by the following general formula (1); and (b) a second unit derived from a vinyl monomer, where R1 is an organic group containing at least one fluorine atom.

摘要翻译： 本发明涉及含氟共聚物。 该含氟共聚物包括（a）由以下通式（1）表示的α-三氟甲基丙烯酸酯衍生的第一单元; 和（b）衍生自乙烯基单体的第二单元，其中R 1是含有至少一个氟原子的有机基团。