JP3305472B2 - Pigment dispersion resin for electrodeposition paint and pigment dispersion paste containing the same - Google Patents
Pigment dispersion resin for electrodeposition paint and pigment dispersion paste containing the sameInfo
- Publication number
- JP3305472B2 JP3305472B2 JP00078494A JP78494A JP3305472B2 JP 3305472 B2 JP3305472 B2 JP 3305472B2 JP 00078494 A JP00078494 A JP 00078494A JP 78494 A JP78494 A JP 78494A JP 3305472 B2 JP3305472 B2 JP 3305472B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin
- pigment
- pigment dispersion
- electrodeposition paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、電着塗料に顔料分散樹
脂として好適に用いうるカチオン性樹脂およびこれを含
有する顔料分散ペーストに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic resin which can be suitably used as a pigment-dispersing resin in an electrodeposition paint and a pigment-dispersing paste containing the same.
【0002】[0002]
【従来の技術】電着塗装は水性塗料を槽中に満たし同じ
浴中にある被塗物体に塗料成分を電気泳動させ、被塗面
に電気析出させることで塗装を行う方法である。この塗
装法は自動車車体の防食塗装を主な用途としており、産
業上重要である。2. Description of the Related Art Electrodeposition coating is a method in which a coating is carried out by filling a water-based coating material in a tank, electrophoresing the coating components on an object to be coated in the same bath, and electrodepositing the components on the surface to be coated. This coating method is mainly used for anticorrosion coating of an automobile body and is industrially important.
【0003】一般に、電着塗料には顔料および顔料分散
剤が含有される。顔料を塗料に導入する際には、予め、
顔料を高濃度で水性媒体に分散させた顔料分散ペースト
を中間組成物として用いる。この顔料分散ペーストに十
分な保存安定性を付与するために分散剤が用いられるの
である。この分散剤には、顔料分散ペーストの分散安定
性を増大させる特性と共に、顔料分散ペーストを水性媒
体で希釈することにより電着塗料とした場合に、この塗
料を長期間安定に保つ性能が要求される。近年では電着
塗料用顔料分散剤にはカチオン性樹脂が一般に用いられ
ている。In general, a pigment and a pigment dispersant are contained in an electrodeposition paint. Before introducing the pigment into the paint,
A pigment dispersion paste in which a pigment is dispersed in an aqueous medium at a high concentration is used as an intermediate composition. A dispersant is used to impart sufficient storage stability to the pigment-dispersed paste. This dispersant is required to have the property of increasing the dispersion stability of the pigment dispersion paste and the ability to keep the paint stable for a long period of time when the pigment dispersion paste is diluted with an aqueous medium into an electrodeposition paint. You. In recent years, cationic resins have been generally used as pigment dispersants for electrodeposition paints.
【0004】例えば、特公昭53-47143号および同54-497
8号には、電着塗料用分散剤として利用されるカチオン
性樹脂が開示されている。また、特開平1-182377号には
α,β-不飽和カルボニル基と水酸基との硬化反応におけ
る触媒としても機能するカチオン性樹脂が開示されてい
る。ここでは触媒活性のための適度な塩基性および腐食
性環境下におけるインヒビター効果を有するカチオン性
樹脂として3級スルホニウム塩を有するものが開示され
ている。For example, JP-B-53-47143 and JP-B-54-497
No. 8 discloses a cationic resin used as a dispersant for an electrodeposition paint. JP-A-1-182377 discloses a cationic resin which also functions as a catalyst in a curing reaction between an α, β-unsaturated carbonyl group and a hydroxyl group. Here, a cationic resin having a tertiary sulfonium salt as a cationic resin having an inhibitory effect in a moderately basic and corrosive environment for catalytic activity is disclosed.
【0005】また、特開昭63-23919号には顔料粉砕展色
剤として有用なスルホニウム樹脂が開示されており、最
も好ましい例としてチオジエタノールから誘導された3
級スルホニウム塩を有するカチオン性樹脂が挙げられて
いる。Japanese Patent Application Laid-Open No. 63-23919 discloses a sulfonium resin useful as a pigment pulverizing vehicle. The most preferred example is a sulfonium resin derived from thiodiethanol.
Cationic resins having graded sulfonium salts are mentioned.
【0006】しかし、ここで開示の顔料分散樹脂は長期
保存下の顔料分散性に劣るので、保存安定性に優れる顔
料分散ペーストおよび電着塗料が得られないという問題
を有する。However, the pigment-dispersed resin disclosed herein is inferior in pigment dispersibility under long-term storage, and thus has a problem that a pigment-dispersed paste and an electrodeposition paint having excellent storage stability cannot be obtained.
【0007】[0007]
【発明が解決しようとする課題】本発明は上記従来の問
題を解決するものであり、その目的とするところは、経
時安定性に優れ、それを用いて良好な顔料分散性および
高防食性の電着塗料を調製可能な顔料分散樹脂、並びに
この樹脂を含有する経時安定性に優れた顔料分散ペース
トを提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a pigment having excellent stability over time and excellent pigment dispersibility and high corrosion resistance. An object of the present invention is to provide a pigment-dispersed resin capable of preparing an electrodeposition paint, and a pigment-dispersed paste containing this resin and having excellent temporal stability.
【0008】[0008]
【課題を解決するための手段】本発明は、式SUMMARY OF THE INVENTION The present invention provides an
【0009】[0009]
【化2】 Embedded image
【0010】[式中、Epは150〜2000のエポキシ当量を有
するエポキシ樹脂の残基であり、R1はヒドロキシメチ
ル、2-ヒドロキシエチル、2-ヒドロキシプロピル、3-ヒ
ドロキシプロピル、4-ヒドロキシブチルまたは2,3-ジヒ
ドロキシプロピル基であり、A-は対アニオンであり、そ
してmは0.1〜4.0の数値である。]で表わされる顔料分散
樹脂を提供するものであり、そのことにより上記目的が
達成される。Wherein Ep is a residue of an epoxy resin having an epoxy equivalent of 150 to 2000, and R 1 is hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl Or a 2,3-dihydroxypropyl group, A - is a counter anion, and m is a number from 0.1 to 4.0. And the above-mentioned object is achieved.
【0011】本発明の顔料分散樹脂は、30〜500、特に5
0〜150の3級スルホニウム価を有することが好ましい。
3級スルホニウム価が500を上回ると耐食性が低下し、3
0を下回ると分散不良となるからである。なお、本発明
における3級スルホニウム価は、樹脂100g中のスルホニ
ウム基のミリ当量で表わされる。The pigment-dispersed resin of the present invention has a content of 30 to 500, especially 5
It preferably has a tertiary sulfonium value of 0 to 150.
If the tertiary sulfonium value exceeds 500, the corrosion resistance decreases,
This is because if it is less than 0, dispersion will be poor. The tertiary sulfonium value in the present invention is represented by the milliequivalent of the sulfonium group in 100 g of the resin.
【0012】好ましくは、本発明の顔料分散樹脂はエポ
キシ樹脂と上記3級スルホニウム基に対応するスルフィ
ドとを反応させることにより調製される。この反応は、
一般に、反応温度50〜80℃、好ましくは60〜75℃で、エ
ポキシ樹脂、スルフィド、酸および脱イオン水を混合撹
拌することによって行われる。好ましい反応比率は、ス
ルフィドはエポキシ樹脂のエポキシ基に対して1〜4当
量、酸はエポキシに対して同当量である。酸としては、
スルホニウムの対アニオンとなり得るものが使用でき
る。それらの例としては、蟻酸、乳酸、酢酸、プロピオ
ン酸、酪酸、ジメチロールプロピオン酸、ホウ酸、リン
酸、塩酸、硫酸などが挙げられるが、無機酸を用いる
と、耐食性低下につながるハロゲン化合物が混入する恐
れがあるので、蟻酸、乳酸、酢酸、プロピオン酸、酪
酸、ジメチロールプロピオン酸のようなカルボン酸が好
ましい。Preferably, the pigment-dispersed resin of the present invention is prepared by reacting an epoxy resin with a sulfide corresponding to the tertiary sulfonium group. This reaction is
Generally, the reaction is carried out at a reaction temperature of 50 to 80 ° C, preferably 60 to 75 ° C, by mixing and stirring the epoxy resin, sulfide, acid and deionized water. The preferred reaction ratio is 1 to 4 equivalents of sulfide based on the epoxy group of the epoxy resin, and the equivalent of acid is equivalent to epoxy. As the acid,
Any substance that can be a counter anion of sulfonium can be used. Examples thereof include formic acid, lactic acid, acetic acid, propionic acid, butyric acid, dimethylolpropionic acid, boric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.However, when an inorganic acid is used, a halogen compound that leads to a reduction in corrosion resistance is used. Carboxylic acids such as formic acid, lactic acid, acetic acid, propionic acid, butyric acid, and dimethylolpropionic acid are preferred because of the possibility of contamination.
【0013】本発明に用いうるエポキシ樹脂は、1分子
中に平均1個以上の1,2-エポキシ基を有するいわゆるポ
リエポキシドである。これらのエポキシ樹脂のエポキシ
当量は好ましくは150〜2000であり、さらに好ましくは4
00〜1500である。エポキシ当量が150を下回ると、電着
時に造膜できないので塗膜を得ることができず、2000を
上回ると1分子あたりのカチオン基の量が不足し、十分
な水溶性を得ることができない。また、このエポキシ樹
脂は300〜10000、好ましくは800〜5000の数平均分子量
を有する。数平均分子量が10000を上回ると高粘度化に
よる分散不良となり、300を下回ると耐食性を低下させ
る原因となる。The epoxy resin which can be used in the present invention is a so-called polyepoxide having an average of one or more 1,2-epoxy groups in one molecule. The epoxy equivalent of these epoxy resins is preferably 150 to 2000, more preferably 4 to 2000.
00 to 1500. When the epoxy equivalent is less than 150, a film cannot be formed at the time of electrodeposition because a film cannot be formed, and when it exceeds 2,000, the amount of cationic groups per molecule is insufficient, and sufficient water solubility cannot be obtained. The epoxy resin has a number average molecular weight of 300 to 10,000, preferably 800 to 5,000. When the number average molecular weight exceeds 10,000, dispersion becomes poor due to high viscosity, and when the number average molecular weight is less than 300, corrosion resistance is reduced.
【0014】このようなエポキシ樹脂の例には、ポリフ
ェノールのポリグリシジルエーテルおよび1,2-エポキシ
基をペンダント基として有するアクリル重合体が挙げら
れる。Examples of such epoxy resins include polyglycidyl ethers of polyphenols and acrylic polymers having 1,2-epoxy groups as pendant groups.
【0015】ポリフェノールのポリグリシジルエーテル
は、一般に、ポリフェノールとエピクロルヒドリンまた
はジクロルヒドリンとをアルカリ存在下で反応させるこ
とによって得られる。ポリフェノールの例としては、ビ
ス(4-ヒドロキシフェニル)-2,2-プロパン、4,4-ジヒド
ロキシベンゾフェノン、ビス(4-ヒドロキシフェニル)-
1,1-エタンおよびその類似物等が挙げられる。1,2-エポ
キシ基をペンダント基として有するアクリル重合体は、
一般に、1,2-エポキシ基を有するアクリルモノマー、例
えば、グリシジルメタクリレートなどを単独または他の
アクリルモノマーと共重合することによって得ることが
できる。[0015] The polyglycidyl ether of polyphenol is generally obtained by reacting polyphenol with epichlorohydrin or dichlorohydrin in the presence of an alkali. Examples of polyphenols include bis (4-hydroxyphenyl) -2,2-propane, 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl)-
1,1-ethane and the like can be mentioned. Acrylic polymer having a 1,2-epoxy group as a pendant group,
Generally, it can be obtained by copolymerizing an acrylic monomer having a 1,2-epoxy group, for example, glycidyl methacrylate alone or with another acrylic monomer.
【0016】本発明で用いうるスルフィドは、式 R1SCH2CH(OH)CH2OH [式中、R1は上記と同意義である。]で示される。このよ
うなスルフィドは、一般に、チオールとエポキシ化合物
とを反応させることによって得られる。The sulfide which can be used in the present invention has the formula R 1 SCH 2 CH (OH) CH 2 OH, wherein R 1 is as defined above. ]. Such a sulfide is generally obtained by reacting a thiol with an epoxy compound.
【0017】本発明に用いうるスルフィドの具体例に
は、1-(2-ヒドロキシエチルチオ)-2,3-メタンジオー
ル、1-(2-ヒドロキシエチルチオ)-2,3-エタンジオー
ル、1-(2-ヒドロキシエチルチオ)-2,3-プロパンジオー
ル、1-(2-ヒドロキシエチルチオ)-2,3-ブタンジオー
ル、2,2'-チオビス(2,3-プロパンジオール)、1-(2-ヒド
ロキシプロピルチオ)-2,3-プロパンジオール等が挙げら
れる。Specific examples of the sulfide which can be used in the present invention include 1- (2-hydroxyethylthio) -2,3-methanediol, 1- (2-hydroxyethylthio) -2,3-ethanediol, -(2-hydroxyethylthio) -2,3-propanediol, 1- (2-hydroxyethylthio) -2,3-butanediol, 2,2′-thiobis (2,3-propanediol), 1- (2-hydroxypropylthio) -2,3-propanediol and the like.
【0018】このようにして得られる本発明の顔料分散
樹脂と顔料とをその重量比が1:0.05〜1:10、好まし
くは1:0.1〜1:0.5となる割合で当業者に周知の方法
で配合することにより、本発明の顔料分散ペーストを調
製することができる。The pigment dispersion resin of the present invention thus obtained and the pigment are mixed in a weight ratio of 1: 0.05 to 1:10, preferably 1: 0.1 to 1: 0.5, by a method well known to those skilled in the art. The pigment dispersion paste of the present invention can be prepared by blending with the above.
【0019】顔料としては、通常使用されるものであれ
ば特に限定されず、例えば酸化鉄、クロム酸ストロンチ
ウム、カーボンブラック、二酸化チタン、タルク、硫酸
バリウム、カドミウムイエロー、カドミウムレッド、ク
ロミックイエロー、リンモリブデン酸アルミ、リンモリ
ブデン酸亜鉛およびこれらの組み合わせなどが挙げられ
る。The pigment is not particularly limited as long as it is commonly used, and examples thereof include iron oxide, strontium chromate, carbon black, titanium dioxide, talc, barium sulfate, cadmium yellow, cadmium red, chromic yellow, and phosphomolybdenum. Aluminum acid, zinc phosphomolybdate and combinations thereof.
【0020】また、得られた顔料分散ペーストを脱イオ
ン水およびカチオン性樹脂と混合し、さらに補助剤とし
て、他の樹脂、溶媒、酸化防止剤、界面活性剤および電
着工程に用いられる他の補助剤のような当業者に周知の
添加剤を加えることによって電着塗料が得られる。The obtained pigment-dispersed paste is mixed with deionized water and a cationic resin, and further, as an auxiliary, other resins, solvents, antioxidants, surfactants, and other additives used in the electrodeposition step. The electrodeposition coating is obtained by adding additives known to those skilled in the art, such as auxiliaries.
【0021】[0021]
【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明はこれらに限定されない。尚、特に断ら
ない限り「部」は重量基準である。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” are based on weight.
【0022】調製例1 ポリウレタン架橋剤の調製 撹拌装置、冷却管、窒素導入管および温度計を備え付け
た反応容器に、ヘキサメチレンジイソシアヌレート199.
1部を入れ、メチルイソブチルケトン(以下、MIBKと略
す)31.6部で希釈した後、ジブチルスズジラウレート0.2
部を加えた。50℃に昇温後、メチルエチルケトオキシム
87部を撹拌しながら乾燥窒素雰囲気中で滴下し、反応温
度を50℃に維持した。赤外吸収スペクトルによりイソシ
アネート基が消失するまで70℃に保ち、その後MIBK35.8
部、n-ブタノール4.0部で希釈してポリウレタン架橋剤
を得た。 Preparation Example 1 Preparation of Polyurethane Crosslinking Agent Hexamethylene diisocyanurate was placed in a reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer.
1 part, diluted with 31.6 parts of methyl isobutyl ketone (hereinafter, abbreviated as MIBK), dibutyltin dilaurate 0.2
Parts were added. After heating to 50 ° C, methyl ethyl ketoxime
87 parts were added dropwise with stirring in a dry nitrogen atmosphere, and the reaction temperature was maintained at 50 ° C. Maintain at 70 ° C. until the isocyanate group disappears by the infrared absorption spectrum.
And 4.0 parts of n-butanol to obtain a polyurethane crosslinking agent.
【0023】調製例2 アミノ化エポキシ樹脂の調製 撹拌装置、冷却管、窒素導入管および温度計を備え付け
た反応容器に、エピコート1001(油化シェルエポキシ社
製、エポキシ当量475のビスフェノールA型エポキシ樹
脂)99.8部、エピコート1004(油化シェルエポキシ社製、
エポキシ当量950のビスフェノールA型エポキシ樹脂)85
0.2部、ノニルフェノール55部、MIBK193.3部
およびベンジルジメチルアミン4.5gを加え、140℃
で4時間反応し、エポキシ当量1175を有する樹脂を得
た。ここにエチレングリコールn-ヘキシルエーテル69.1
部、2-アミノエチルエタノールアミンのMIBKケチミン化
物のMIBK溶液(固形分78重量%)35.4部、N-メチルエタノ
ールアミン26.5部およびジエタノールアミン37.1部を加
えた。これを120℃で2時間反応させ、目的とする樹脂
を得た。 Preparation Example 2 Preparation of Aminated Epoxy Resin A reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe and a thermometer was charged with Epicoat 1001 (a bisphenol A type epoxy resin having an epoxy equivalent of 475, manufactured by Yuka Shell Epoxy). ) 99.8 parts, Epicoat 1004 (Yuika Shell Epoxy,
(A bisphenol A type epoxy resin with an epoxy equivalent of 950) 85
0.2 part, 55 parts of nonylphenol, 193.3 parts of MIBK and 4.5 g of benzyldimethylamine were added, and 140 ° C.
For 4 hours to obtain a resin having an epoxy equivalent of 1175. Here, ethylene glycol n-hexyl ether 69.1
35.4 parts of a MIBK solution (solid content 78% by weight) of MIBK ketimine compound of 2-aminoethylethanolamine, 26.5 parts of N-methylethanolamine and 37.1 parts of diethanolamine were added. This was reacted at 120 ° C. for 2 hours to obtain a desired resin.
【0024】実施例1 ハーフブロック化ジイソシアネートの調製 撹拌機、窒素導入管、冷却管を備えた反応容器にイソホ
ロンジイソシアネート(以下、IPDIと略す)222.2部を入
れ、メチルイソブチルケトン(以下、MIBKと略す)39.1部
で希釈した後にジブチルスズジラウレート0.2部を加え
た。50℃に昇温後、2-エチルヘキサノール131.5部を撹
拌しながら乾燥窒素雰囲気中で2時間かけて滴下反応さ
せた。反応温度を50℃に維持し、2-エチルヘキサノール
ハーフブロック化IPDI(固形分90%)を得た。 Example 1 Preparation of half-blocked diisocyanate In a reaction vessel equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 222.2 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI) were placed, and methyl isobutyl ketone (hereinafter abbreviated as MIBK) was placed. ) After dilution with 39.1 parts, 0.2 parts of dibutyltin dilaurate was added. After the temperature was raised to 50 ° C., 131.5 parts of 2-ethylhexanol was dropped and reacted in a dry nitrogen atmosphere over 2 hours while stirring. The reaction temperature was maintained at 50 ° C. to obtain 2-ethylhexanol half-blocked IPDI (solid content: 90%).
【0025】顔料分散樹脂の調製 撹拌機、窒素導入管、冷却管を備えた反応容器にエポン
828(シェル化学社製エポキシ樹脂、エポキシ当量:190)
351.6部およびビスフェノールA 99.2部を仕込み、窒素
雰囲気下130℃まで加熱し、ベンジルジメチルアミン1.4
1部を添加し、170℃で約1時間反応させることにより、
エポキシ当量445のビスフェノール型エポキシ樹脂を得
た。次いで、140℃まで冷却した後、上で調製した2-エ
チルヘキサノールハーフブロック化IPDI218.3部(固形分
量196.5部)を加え反応させた。Preparation of Pigment-Dispersed Resin Epon
828 (Shell Chemical Co., Ltd. epoxy resin, epoxy equivalent: 190)
351.6 parts and 99.2 parts of bisphenol A were charged and heated to 130 ° C. in a nitrogen atmosphere to give benzyldimethylamine 1.4
By adding 1 part and reacting at 170 ° C. for about 1 hour,
A bisphenol type epoxy resin having an epoxy equivalent of 445 was obtained. Next, after cooling to 140 ° C., 218.3 parts (solid content: 196.5 parts) of 2-ethylhexanol half-blocked IPDI prepared above was added and reacted.
【0026】これを140℃に1時間保った後、ジプロピ
レングリコールモノブチルエーテル172.3部を加えて希
釈した後に、反応混合物を100℃に冷却し、1-(2-ヒドロ
キシエチルチオ)-2,3-プロパンジオール408.0部(固形分
量136.0部)、ジメチロールプロピオン酸134.0部および
脱イオン水144.0部を加えた。これを70〜75℃で酸価2.0
以下になるまで反応させ、3級スルホニウム化率72%の
顔料分散樹脂を得た。これをジプロピレングリコールモ
ノブチルエーテル324.8部で希釈し、顔料分散樹脂を得
た(樹脂固形分50%)。After maintaining this at 140 ° C. for 1 hour, 172.3 parts of dipropylene glycol monobutyl ether was added for dilution, and the reaction mixture was cooled to 100 ° C. and 1- (2-hydroxyethylthio) -2,3 -408.0 parts of propanediol (136.0 parts of solid content), 134.0 parts of dimethylolpropionic acid and 144.0 parts of deionized water were added. The acid value is 2.0 at 70-75 ° C.
The reaction was continued until the content became as follows, to obtain a pigment dispersion resin having a tertiary sulfonium conversion rate of 72%. This was diluted with 324.8 parts of dipropylene glycol monobutyl ether to obtain a pigment-dispersed resin (resin solid content: 50%).
【0027】実施例2 実施例1で、1-(2-ヒドロキシエチルチオ)-2,3-プロパ
ンジオール408.0部(固形分量182.0部)を2,2'-チオビス
(2,3-プロパンジオール)546.0部に変更したほかは同様
にして、反応を行い、3級スルホニウム化率82%の顔料
分散樹脂を得た。これをジプロピレングリコールモノブ
チルエーテル324.8部で希釈し、顔料分散樹脂を得た(樹
脂固形分50%)。 Example 2 In Example 1, 408.0 parts of 1- (2-hydroxyethylthio) -2,3-propanediol (solid content: 182.0 parts) was replaced with 2,2'-thiobis
(2,3-Propanediol) The reaction was carried out in the same manner except that the amount was changed to 546.0 parts to obtain a pigment-dispersed resin having a tertiary sulfonium conversion of 82%. This was diluted with 324.8 parts of dipropylene glycol monobutyl ether to obtain a pigment-dispersed resin (resin solid content: 50%).
【0028】実施例3 実施例1で、1-(2-ヒドロキシエチルチオ)-2,3-プロパ
ンジオール408.0部を1-(2-ヒドロキシプロピルチオ)2,3
-プロパンジオール498.0部(固形分量166.0部)に変更し
たほかは同様にして、反応を行い、3級スルホニウム化
率70%の顔料分散樹脂を得た。これをジプロピレングリ
コールモノブチルエーテル324.8部で希釈し、顔料分散
樹脂を得た(樹脂固形分50%)。 Example 3 In Example 1, 408.0 parts of 1- (2-hydroxyethylthio) -2,3-propanediol was added to 1- (2-hydroxypropylthio) 2,3
The reaction was carried out in the same manner except that the amount of propanediol was changed to 498.0 parts (solid content: 166.0 parts) to obtain a pigment-dispersed resin having a tertiary sulfonium conversion of 70%. This was diluted with 324.8 parts of dipropylene glycol monobutyl ether to obtain a pigment-dispersed resin (resin solid content: 50%).
【0029】実施例4 撹拌機、窒素導入管、冷却管を備えた反応容器にエチレ
ングリコールモノブチルエーテル500部を仕込み、撹拌
しながら120℃に加熱した。これにグリシジルメタクリ
レート285.0部、スチレン205.0部、2-ヒドロキシエチル
メタクリレート250.0部、n-ブチルアクリレート250.0部
およびt-ブチルパーオキシオクトエート28.0部の混合物
を3時間かけて滴下した。その後、エチレングリコール
モノブチルエーテル210部、1-(2-ヒドロキシエチルチ
オ)-2,3-プロパンジオール500部、ジメチロールプロピ
オン酸134.0部を加え、70℃でさらに反応させた。次い
で、ジプロピレングリコールモノブチルエーテル324.8
部で希釈し、顔料分散樹脂を得た(樹脂固形分50%)。 Example 4 500 parts of ethylene glycol monobutyl ether was charged into a reactor equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and heated to 120 ° C. with stirring. A mixture of 285.0 parts of glycidyl methacrylate, 205.0 parts of styrene, 250.0 parts of 2-hydroxyethyl methacrylate, 250.0 parts of n-butyl acrylate and 28.0 parts of t-butyl peroxyoctoate was added dropwise over 3 hours. Thereafter, 210 parts of ethylene glycol monobutyl ether, 500 parts of 1- (2-hydroxyethylthio) -2,3-propanediol and 134.0 parts of dimethylolpropionic acid were added, and further reacted at 70 ° C. Then, dipropylene glycol monobutyl ether 324.8
The resulting mixture was diluted with 1 part to obtain a pigment-dispersed resin (resin solid content: 50%).
【0030】比較例1 チオジエタノールから得られる顔料分散樹脂の調製 撹拌機、窒素導入管、冷却管を備えた反応容器にエポン
828 533.2部、ビスフェノールA 199.6部、ノニルフェ
ノール19.2部を仕込み、窒素雰囲気下130℃まで加熱し
た。ここに、ヨウ化エチルトリフェニルホスホニウム0.
75部を添加し、170℃で約1時間反応させることにより
エポキシ当量490のビスフェノールA型エポキシ樹脂を得
た。次いで140℃まで冷却した後、2-エチルヘキサノー
ルハーフブロック化イソホロンジイソシアネート198.4
部(固形分量178.6部)を加え、140℃で1時間保った。こ
うして得られたエポキシ樹脂にエチレングリコールモノ
ブチルエーテル161.8部を加えて希釈後、100℃に冷却
し、2,2'-チオビス(エタノール)122.1部、ジメチロール
プロピオン酸134.0部および脱イオン水144.0部を加え
た。この混合物を70〜75℃で酸価5.0になるまで反応さ
せ、3級スルホニウム化率82%の樹脂を得た。次いでエ
チレングリコールモノブチルエーテル353.5部で希釈
し、顔料分散樹脂を得た(樹脂固形分50%)。 Comparative Example 1 Preparation of Pigment Dispersion Resin Obtained from Thiodiethanol Epon was placed in a reaction vessel equipped with a stirrer, a nitrogen inlet tube, and a cooling tube.
828 533.2 parts, bisphenol A 199.6 parts and nonylphenol 19.2 parts were charged and heated to 130 ° C. under a nitrogen atmosphere. Here, ethyltriphenylphosphonium iodide 0.
By adding 75 parts and reacting at 170 ° C. for about 1 hour, a bisphenol A type epoxy resin having an epoxy equivalent of 490 was obtained. Then, after cooling to 140 ° C., 2-ethylhexanol half-blocked isophorone diisocyanate 198.4
(Solid content: 178.6 parts) and kept at 140 ° C. for 1 hour. The epoxy resin thus obtained was diluted by adding 161.8 parts of ethylene glycol monobutyl ether, cooled to 100 ° C., 122.1 parts of 2,2′-thiobis (ethanol), 134.0 parts of dimethylolpropionic acid and 144.0 parts of deionized water were added. added. The mixture was reacted at 70 to 75 ° C. until the acid value reached 5.0 to obtain a resin having a tertiary sulfonium conversion of 82%. Subsequently, the mixture was diluted with 353.5 parts of ethylene glycol monobutyl ether to obtain a pigment-dispersed resin (resin solid content: 50%).
【0031】比較例2 4級化剤の調製 撹拌機、窒素導入管、冷却管を備えた反応容器にトリレ
ンジイソシアネート(以下、TDIと略す)174.0部を入れ、
MIBK33.9部で希釈した後にジブチルスズジラウレート0.
2部を加えた。50℃に昇温後、2-エチルヘキサノール13
1.5部を撹拌しながら乾燥窒素雰囲気中で2時間かけて
滴下反応させた。反応温度を50℃に維持し、2-エチルヘ
キサノールハーフブロック化TDIを得た。この2-エチル
ヘキサノールハーフブロック化TDI320.0部(固形分量30
4.0部)をジメチルエタノールアミン87.2部に室温で加え
たところ、発熱が認められた。これを80℃で1時間撹拌
した後、75%乳酸水溶液117.6部(固形分量88.2部)を加
え、さらにエチレングリコールモノブチルエーテル39.2
部を加えた。反応混合物を65℃で約半時間撹拌し、4級
化剤を得た。 Comparative Example 2 Preparation of quaternizing agent 174.0 parts of tolylene diisocyanate (hereinafter abbreviated as TDI) was placed in a reaction vessel equipped with a stirrer, a nitrogen inlet tube, and a cooling tube.
After diluting with MIBK 33.9 parts dibutyltin dilaurate 0.
Two parts were added. After heating to 50 ° C, 2-ethylhexanol 13
While stirring 1.5 parts, a dropping reaction was performed in a dry nitrogen atmosphere over 2 hours. The reaction temperature was maintained at 50 ° C. to obtain 2-ethylhexanol half-blocked TDI. 320.0 parts of this 2-ethylhexanol half-blocked TDI (solid content 30
4.0 parts) was added to 87.2 parts of dimethylethanolamine at room temperature, and exotherm was observed. This was stirred at 80 ° C. for 1 hour, 117.6 parts of a 75% lactic acid aqueous solution (solid content 88.2 parts) was added, and ethylene glycol monobutyl ether 39.2 was added.
Parts were added. The reaction mixture was stirred at 65 ° C. for about half an hour to obtain a quaternizing agent.
【0032】4級アンモニウム基を有する顔料分散樹脂
の調製 撹拌機、窒素導入管、冷却管を備えた反応容器にエポン
828(油化シェル社製エポキシ当量190のビスフェノールA
型エポキシ樹脂)681.2部およびビスフェノールA 289.6
部を仕込み、窒素雰囲気下150〜160℃で約1時間反応さ
せ、次いで120℃に冷却後、2-エチルヘキサノールハー
フブロック化TDI406.4部(固形分量386.1部)を加えた。
次いで85〜95℃に冷却し、均一化し、さらに上で調製し
た4級化剤496.3部(固形分量421.9部)および脱イオン水
71.2部を加えた。酸価が1以下になるまで反応混合物を
80〜85℃に保持し、エチレングリコールモノブチルエー
テル85.6部を加えて希釈し、顔料分散樹脂を得た。Preparation of Pigment Dispersion Resin Having Quaternary Ammonium Group Eponne was placed in a reaction vessel equipped with a stirrer, a nitrogen inlet tube, and a cooling tube.
828 (Yusuka Shell Co., Ltd. Bisphenol A with an epoxy equivalent of 190
681.2 parts and bisphenol A 289.6 parts
Then, the mixture was reacted under a nitrogen atmosphere at 150 to 160 ° C. for about 1 hour, and then cooled to 120 ° C., and then 406.4 parts of 2-ethylhexanol half-blocked TDI (solid content 386.1 parts) was added.
It is then cooled to 85-95 ° C., homogenized and furthermore the quaternizing agent prepared above, 496.3 parts (solids 421.9 parts) and deionized water
71.2 parts were added. The reaction mixture until the acid value is less than 1
The mixture was maintained at 80 to 85 ° C. and diluted with 85.6 parts of ethylene glycol monobutyl ether to obtain a pigment-dispersed resin.
【0033】実施例5 顔料分散ペーストの調製1 実施例1で調製した顔料分散樹脂30.0部(固形分15.0
部)、脱イオン水75.4部、二酸化チタンR-900P 68.9
部、カオリン14.4部、リンモリブデン酸アルミ15.0部お
よびカーボンブラック1.7部を、サンドグラインドミル
で分散し、粒度10μ以下まで粉砕した顔料分散ペースト
を調製した。この顔料分散ペーストは、総固形分56.0
%、樹脂固形分7.3%、顔料固形分48.7%であった。 Example 5 Preparation 1 of Pigment Dispersion Paste 30.0 parts (solid content: 15.0 parts) of the pigment dispersion resin prepared in Example 1
Parts), 75.4 parts of deionized water, titanium dioxide R-900P 68.9
, 14.4 parts of kaolin, 15.0 parts of aluminum phosphomolybdate and 1.7 parts of carbon black were dispersed in a sand grind mill to prepare a pigment dispersion paste ground to a particle size of 10 μm or less. This pigment dispersion paste has a total solid content of 56.0
%, Resin solid content 7.3%, and pigment solid content 48.7%.
【0034】実施例6 顔料分散ペーストの調製2 実施例1の顔料分散樹脂に代えて実施例2の顔料分散樹
脂を用いること以外は実施例5と同様にして、顔料分散
ペーストを調製した。 Example 6 Preparation of Pigment Dispersion Paste A pigment dispersion paste was prepared in the same manner as in Example 5 except that the pigment dispersion resin of Example 2 was used instead of the pigment dispersion resin of Example 1.
【0035】実施例7 顔料分散ペーストの調製3 実施例1の顔料分散樹脂に代えて実施例3の顔料分散樹
脂を用いること以外は実施例5と同様にして、顔料分散
ペーストを調製した。 Example 7 Preparation of Pigment Dispersion Paste A pigment dispersion paste was prepared in the same manner as in Example 5 except that the pigment dispersion resin of Example 3 was used instead of the pigment dispersion resin of Example 1.
【0036】比較例3 顔料分散ペーストの調製4 実施例1の顔料分散樹脂に代えて比較例1の顔料分散樹
脂を用いること以外は実施例5と同様にして、顔料分散
ペーストを調製した。 Comparative Example 3 Preparation of Pigment Dispersion Paste A pigment dispersion paste was prepared in the same manner as in Example 5 except that the pigment dispersion resin of Comparative Example 1 was used instead of the pigment dispersion resin of Example 1.
【0037】比較例4 顔料分散ペーストの調製5 実施例1の顔料分散樹脂に代えて比較例2の顔料分散樹
脂を用いること以外は実施例5と同様にして、顔料分散
ペーストを調製した。 Comparative Example 4 Preparation of Pigment Dispersion Paste A pigment dispersion paste was prepared in the same manner as in Example 5 except that the pigment dispersion resin of Comparative Example 2 was used instead of the pigment dispersion resin of Example 1.
【0038】実施例8 顔料分散ペーストの分散安定性の評価 実施例5〜7、および比較例3および4で調製した顔料
分散ペーストについて、40℃で2週間静置貯安した後の
沈降状態を観察し、降伏値を測定することにより、顔料
分散ペーストの分散安定性を評価した。これらの評価結
果を表1に示す。 Example 8 Evaluation of Dispersion Stability of Pigment-Dispersed Paste The pigment-dispersed pastes prepared in Examples 5 to 7 and Comparative Examples 3 and 4 were allowed to stand at 40.degree. By observing and measuring the yield value, the dispersion stability of the pigment dispersion paste was evaluated. Table 1 shows the results of these evaluations.
【0039】[0039]
【表1】実施例番号 沈降状態1) 粘度変化2) 実施例5 ○ ○ 実施例6 ○ ○ 実施例7 ○ ○ 比較例3 △ ×比較例4 △ ○ 1)40℃で2週間静置貯安した後、ペーストの沈降状態を
以下の評価基準で目視評価した。 ○:沈降なし △:ソフト沈降 ×:ハード沈降 2)40℃で2週間静置貯安した後、ペーストの粘度変化を
以下の評価基準で目視評価した。 ○:増粘無し △:僅かに増粘 ×:著しく増粘[Table 1] Example No. Sedimentation state 1) Change in viscosity 2) Example 5 ○ ○ Example 6 ○ ○ Example 7 ○ ○ Comparative example 3 △ × Comparative example 4 △ ○ 1) Store at 40 ° C for 2 weeks. After the temperature decreased, the sedimentation state of the paste was visually evaluated according to the following evaluation criteria. :: no sedimentation △: soft sedimentation ×: hard sedimentation 2) After standing and storing at 40 ° C. for 2 weeks, the change in viscosity of the paste was visually evaluated according to the following evaluation criteria. :: no thickening Δ: slight thickening ×: markedly thickened
【0040】実施例9 カチオン電着塗料の調製1 調製例1で得られたポリウレタン架橋剤331.9部および
調製例2で得られたアミノ化エポキシ樹脂576.0部をn-
ヘキシルセロソルブ30.3部と混合し、氷酢酸12.3部で中
和した後、脱イオン水1067.0部でゆっくり希釈した。次
いで、これを固形分36.0%になるまで減圧下で有機溶媒
を除去した。ここへ実施例5で調製した顔料分散ペース
ト546.8部を加えて均一に混合し、脱イオン水2598.2部
を加えて固形分20.0%のカチオン電着塗料を得た。 Example 9 Preparation 1 of a cationic electrodeposition coating composition 331.9 parts of the polyurethane crosslinking agent obtained in Preparation Example 1 and 576.0 parts of the aminated epoxy resin obtained in Preparation Example 2 were n-
It was mixed with 30.3 parts of hexyl cellosolve, neutralized with 12.3 parts of glacial acetic acid, and then slowly diluted with 1067.0 parts of deionized water. Then, the organic solvent was removed under reduced pressure until the solid content became 36.0%. To this, 546.8 parts of the pigment dispersion paste prepared in Example 5 was added and mixed uniformly, and 2598.2 parts of deionized water was added to obtain a cationic electrodeposition paint having a solid content of 20.0%.
【0041】実施例10 カチオン電着塗料の調製2 顔料分散ペーストを実施例5で調製したものを実施例6
で調製したものに代えた以外は、実施例9と同様にして
カチオン電着塗料を得た。 Example 10 Preparation of cationic electrodeposition paint 2 The pigment dispersion paste prepared in Example 5 was used in Example 6
A cationic electrodeposition paint was obtained in the same manner as in Example 9 except that the preparation was carried out in the same manner as in Example 9.
【0042】実施例11 カチオン電着塗料の調製3 顔料分散ペーストを実施例5で調製したものを実施例7
で調製したものに代えた以外は、実施例9と同様にして
カチオン電着塗料を得た。 Example 11 Preparation of cationic electrodeposition paint 3 The pigment dispersion paste prepared in Example 5 was used in Example 7
A cationic electrodeposition paint was obtained in the same manner as in Example 9 except that the preparation was carried out in the same manner as in Example 9.
【0043】比較例5 カチオン電着塗料の調製4 顔料分散ペーストを実施例5で調製したものを参考例3
で調製したものに代えた以外は、実施例9と同様にして
カチオン電着塗料を得た。 Comparative Example 5 Preparation of cationic electrodeposition coating material 4 A pigment dispersion paste prepared in Example 5 was used as a reference example 3.
A cationic electrodeposition paint was obtained in the same manner as in Example 9 except that the preparation was carried out in the same manner as in Example 9.
【0044】比較例6 カチオン電着塗料の調製5 顔料分散ペーストを実施例5で調製したものを参考例4
で調製したものに代えた以外は、実施例9と同様にして
カチオン電着塗料を得た。 Comparative Example 6 Preparation of cationic electrodeposition paint 5 Reference example 4 was prepared by preparing a pigment dispersion paste in Example 5.
A cationic electrodeposition paint was obtained in the same manner as in Example 9 except that the preparation was carried out in the same manner as in Example 9.
【0045】実施例12 カチオン電着塗料の経時安定性の評価 実施例9〜11および比較例5、6で得られたカチオン電
着塗料を、撹拌下40℃で4週間貯安した後の380メッシ
ュ網濾過性及び残渣量を評価することにより、経時安定
性を評価した。結果を表2に示す。 Example 12 Evaluation of Stability of Cationic Electrodeposition Coating over Time The cationic electrocoatings obtained in Examples 9 to 11 and Comparative Examples 5 and 6 were stored at 40 ° C. for 4 weeks with stirring and then stored for 380 days. The stability over time was evaluated by evaluating the mesh network filterability and the amount of residue. Table 2 shows the results.
【0046】カチオン電着塗料の耐塩水防食性の評価 上記各カチオン電着塗料を冷延鋼板(リン酸亜鉛処理な
し)に、10μの膜厚で電着を行い、160℃で10分焼付けた
後にクロスカットを入れ、次いで塩水噴霧試験(SST)を1
20時間行った。この試験後の試料に幅2.4cmの粘着テー
プ(ニチバン社製、商品名「セロテープ」)を指で確実に貼
りつけた後に急激に粘着テープを剥離し、鋼板からの塗
膜の剥離幅を測定することにより、電着塗料の耐塩水防
食性を評価した。結果を表2に示す。Evaluation of salt water corrosion resistance of cationic electrodeposition paint Each of the above cationic electrodeposition paints was electrodeposited on a cold-rolled steel sheet (without zinc phosphate treatment) at a film thickness of 10 μm and baked at 160 ° C. for 10 minutes. Make a cross cut and then run a salt spray test (SST)
We went for 20 hours. A 2.4 cm wide adhesive tape (Nichiban, product name "Cellotape") was firmly attached to the sample after this test with a finger, then the adhesive tape was rapidly peeled off, and the peeling width of the coating film from the steel plate was measured. In this way, the salt water corrosion resistance of the electrodeposition paint was evaluated. Table 2 shows the results.
【0047】[0047]
【表2】実施例番号 経時安定性1) 耐塩水防食性2) 実施例9 ○(3mg) ○ 実施例10 ○(5mg) ○ 実施例11 ○(5mg) ○ 比較例5 △(48mg) ○比較例6 △(35mg) ○ 1)電着塗料を撹拌下40℃で4週間貯安した後の380メ
ッシュ網濾過性及び残渣量で、以下の基準により塗料の
経時安定性を評価した。括弧内は濾過残渣量を示す。 ○:良く通る △:通りづらい ×:つまって通らない 2)耐塩水防食性の評価基準 ○:剥離幅2mm未満 △:剥離幅2〜3mm ×:剥離幅
3mm以上[Table 2] Example No. Stability with time 1) Corrosion and corrosion resistance 2) Example 9 ○ (3 mg) ○ Example 10 ○ (5 mg) ○ Example 11 ○ (5 mg) ○ Comparative Example 5 △ (48 mg) ○ Comparison Example 6 Δ (35 mg) ○ 1) The aging stability of the paint was evaluated according to the following criteria based on the filterability of 380 mesh net and the amount of residue after storing the electrodeposited paint at 40 ° C. for 4 weeks with stirring. The figures in parentheses indicate the amount of the filtration residue. :: Passes well △: Difficult to pass ×: Does not pass through 2) Evaluation criteria for saltwater corrosion protection ○: Peel width less than 2 mm △: Peel width 2-3 mm ×: Peel width 3 mm or more
【0048】[0048]
【発明の効果】本発明の顔料分散樹脂は、スルホニウム
基に結合している水酸基の数が従来のものに比べて多
く、樹脂の親水性が増加した。これにより、経時安定性
に優れ、良好な顔料分散性および高防食性を有する顔料
分散樹脂を提供することができた。The pigment-dispersed resin of the present invention has a larger number of hydroxyl groups bonded to the sulfonium group than the conventional one, and the hydrophilicity of the resin is increased. As a result, it was possible to provide a pigment-dispersed resin having excellent stability over time and having good pigment dispersibility and high anticorrosion properties.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−86735(JP,A) 特開 昭63−179983(JP,A) 特開 平2−11668(JP,A) 特開 平6−128351(JP,A) 特開 平6−157711(JP,A) 特開 平6−329758(JP,A) 特開 平7−33848(JP,A) 特開 平7−206969(JP,A) 特開 平7−206968(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 59/14 C09D 5/44 C09D 17/00 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-86735 (JP, A) JP-A-63-179983 (JP, A) JP-A-2-11668 (JP, A) 128351 (JP, A) JP-A-6-157711 (JP, A) JP-A-6-329758 (JP, A) JP-A-7-33848 (JP, A) JP-A-7-206969 (JP, A) JP-A-7-206968 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 59/14 C09D 5/44 C09D 17/00 CA (STN) REGISTRY (STN)
Claims (4)
樹脂の残基であり、R1はヒドロキシメチル、2-ヒドロキ
シエチル、2-ヒドロキシプロピル、3-ヒドロキシプロピ
ル、4-ヒドロキシブチルまたは2,3-ジヒドロキシプロピ
ル基であり、A-は対アニオンであり、そしてmは0.1〜4.
0の数値である。]で表わされる電着塗料用顔料分散樹
脂。(1) Formula (1) Wherein Ep is the residue of an epoxy resin having an epoxy equivalent of 150-2000, and R 1 is hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl or 2, A 3-dihydroxypropyl group, A - is a counter anion, and m is 0.1-4.
Numeric value of 0. ] A pigment dispersion resin for electrodeposition paint represented by the formula:
キシ樹脂と、式 R1SCH2CH(OH)CH2OH [式中、R1は前記と同意義である。]で示すスルフィドと
を、酸の存在下で反応させて得られる請求項1記載の電
着塗料用顔料分散樹脂。2. An epoxy resin having an epoxy equivalent of 150 to 2000 and a compound represented by the formula R 1 SCH 2 CH (OH) CH 2 OH wherein R 1 is as defined above. The pigment-dispersed resin for an electrodeposition paint according to claim 1, which is obtained by reacting a sulfide represented by the formula [1] with an acid in the presence of an acid.
請求項1記載の電着塗料用顔料分散樹脂。3. The pigment-dispersed resin according to claim 1, which has a tertiary sulfonium value of 30 to 500.
量に対して0.05〜10の割合で含有する電着塗料用顔料分
散ペースト。4. A pigment dispersion paste for an electrodeposition paint, comprising the pigment dispersion resin according to claim 1 in a ratio of 0.05 to 10 based on the weight of the pigment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00078494A JP3305472B2 (en) | 1994-01-10 | 1994-01-10 | Pigment dispersion resin for electrodeposition paint and pigment dispersion paste containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00078494A JP3305472B2 (en) | 1994-01-10 | 1994-01-10 | Pigment dispersion resin for electrodeposition paint and pigment dispersion paste containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07207195A JPH07207195A (en) | 1995-08-08 |
JP3305472B2 true JP3305472B2 (en) | 2002-07-22 |
Family
ID=11483331
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP00078494A Expired - Lifetime JP3305472B2 (en) | 1994-01-10 | 1994-01-10 | Pigment dispersion resin for electrodeposition paint and pigment dispersion paste containing the same |
Country Status (1)
Country | Link |
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JP (1) | JP3305472B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113372250B (en) * | 2017-02-15 | 2023-12-08 | Ks试验研究株式会社 | Polythiol compound, process for producing the same, transparent urethane resin produced from the same, and optical body |
-
1994
- 1994-01-10 JP JP00078494A patent/JP3305472B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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JPH07207195A (en) | 1995-08-08 |
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