JP2000191673A - New phosphoric acid ester and mold releasing agent comprising the compound - Google Patents
New phosphoric acid ester and mold releasing agent comprising the compoundInfo
- Publication number
- JP2000191673A JP2000191673A JP10368562A JP36856298A JP2000191673A JP 2000191673 A JP2000191673 A JP 2000191673A JP 10368562 A JP10368562 A JP 10368562A JP 36856298 A JP36856298 A JP 36856298A JP 2000191673 A JP2000191673 A JP 2000191673A
- Authority
- JP
- Japan
- Prior art keywords
- propoxy
- phosphoric acid
- propyl
- butoxy
- mono
- 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.)
- Pending
Links
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は離型剤として有用な
燐酸エステルとその製造方法、並びにそれらの燐酸エス
テルを含んだ透明樹脂、透明光学材料、プラスチックレ
ンズに関する。The present invention relates to a phosphoric ester useful as a mold release agent, a method for producing the same, and a transparent resin, a transparent optical material, and a plastic lens containing the phosphoric ester.
【0002】[0002]
【従来の技術】いわゆる透明樹脂は、一般にガラス並の
透明性とガラスよりも高い衝撃性を有しており、例え
ば、航空機用窓ガラス、自動車用ヘッドライトカバー、
飲料水容器、封止剤、液晶パネル、光ディスク、光ファ
イバー、プラスチックレンズなどの分野に使用されてい
る。2. Description of the Related Art A transparent resin generally has a transparency comparable to that of glass and a higher impact strength than glass. For example, a window glass for an aircraft, a headlight cover for an automobile,
It is used in fields such as drinking water containers, sealants, liquid crystal panels, optical disks, optical fibers, and plastic lenses.
【0003】一般的な透明樹脂の種類としては、ポリ塩
化ビニル、ポリプロピレン、PMMA、(メタ)アクリ
ル樹脂等のオレフィン樹脂、ポリエン−ポリチオール樹
脂、ポリエステル樹脂、ポリカーボネート樹脂、エポキ
シ樹脂、ポリウレタン樹脂などが挙げられる。通常、こ
れらの透明樹脂は射出成型又は注型重合によって成型さ
れる。何れの成型方法によっても、樹脂を成形型から離
型させなければ製品は得られない。[0003] Types of general transparent resins include olefin resins such as polyvinyl chloride, polypropylene, PMMA, and (meth) acrylic resins, polyene-polythiol resins, polyester resins, polycarbonate resins, epoxy resins, and polyurethane resins. Can be Usually, these transparent resins are molded by injection molding or cast polymerization. In either case, a product cannot be obtained unless the resin is released from the mold.
【0004】ところが、離型剤無しでそれらの樹脂を成
型すると、離型の際に過大な応力がかかることにより、
成型物が反る等の変形を起こしたり、内部に光学歪みを
発生する等の好ましくない結果を与える場合が多かっ
た。However, when such resins are molded without a mold release agent, excessive stress is applied at the time of mold release.
In many cases, undesirable results such as deformation of the molded product, such as warpage, and generation of optical distortion inside, are given.
【0005】さらに、エポキシ樹脂とウレタン樹脂は、
接着剤にも用いられている事からも判る通り、極めて接
着力の強い樹脂として知られ、金属やガラス製成形型を
使用した場合、通常、離型剤の使用は必須である[0005] Further, epoxy resin and urethane resin are
As can be seen from the fact that it is also used for adhesives, it is known as an extremely strong resin, and when using a metal or glass mold, the use of a mold release agent is usually essential
【0006】離型剤は、成形型表面にスプレー等を利用
して塗布する外部離型剤と、原料モノマーに予め添加し
ておく内部離型剤がある。外部離型剤は、操作が煩雑で
あるばかりでなく、離型膜が一定になりにくく面精度が
低下するといった問題点があるため、内部離型剤が好ま
しく用いられる。The release agent includes an external release agent which is applied to the surface of a molding die by using a spray or the like, and an internal release agent which is previously added to a raw material monomer. As the external release agent, not only the operation is complicated, but also there is a problem that the release film is difficult to be constant and the surface accuracy is reduced. Therefore, the internal release agent is preferably used.
【0007】これら内部離型剤として、従来知られてい
る化合物としては、脂肪族アルコール、脂肪酸エステ
ル、トリグリセリド類、フッ素系界面活性剤、高級脂肪
酸金属塩等があるが、これらを使用した場合、離型し難
かったり、樹脂内部及び表面に濁りを発生し易く樹脂本
来の透明性を損ない易いといった欠点があった。[0007] As these internal release agents, conventionally known compounds include aliphatic alcohols, fatty acid esters, triglycerides, fluorinated surfactants, metal salts of higher fatty acids, and the like. There are drawbacks such as difficulty in releasing from the mold, turbidity inside the resin and on the surface, and easily impairing the original transparency of the resin.
【0008】透明性を損なう事は、高い透明性を利用し
た透明樹脂製成型物では、特に問題で、そのなかでも通
常の目視では到底判断できない程の僅かな曇りでもスペ
ックアウトになるプラスチックレンズに代表される光学
材料の分野では、極めて致命的な欠点となっていた。[0008] Impairing transparency is a problem especially in a molded article made of a transparent resin utilizing high transparency. Among them, a plastic lens which can be out of spec even with a slight cloudiness which cannot be judged by ordinary eyes. In the field of optical materials typified by, there has been a very fatal drawback.
【0009】この問題を解決する方法として、種々の提
案が行なわれている。例えば、アルコキシアルキル燐酸
エステルを用いる方法(特公平6−20752号公報,
特開平3−287641号公報)、ホスフィン酸エステ
ルを用いる方法(特開昭58−49747号公報)等が
挙げられる。本発明者らも、酸性燐酸エステルを用いる
方法(特公平7−77733号公報)、チオ燐酸エステ
ル類を用いる方法(特開平5−306320号公報)、
酸性ホスホン酸誘導体を用いる方法(特開平8−578
64号公報)等を提案している。Various proposals have been made to solve this problem. For example, a method using an alkoxyalkyl phosphate (Japanese Patent Publication No. 6-20754,
JP-A-3-287641), a method using a phosphinic ester (JP-A-58-49747), and the like. The present inventors have also proposed a method using an acid phosphate (Japanese Patent Publication No. 7-77733), a method using a thiophosphate (Japanese Patent Application Laid-Open No. 5-306320),
A method using an acidic phosphonic acid derivative (JP-A-8-578)
No. 64 gazette).
【0010】しかしながら、これらの方法を用いても、
透明性が厳密にはまだ不充分であったり、着色したり、
離型剤自身の粘度が高い為に使いずらかったり、不快臭
がしたり、接着力の極めて強い樹脂の場合には、通常の
量では離型性が悪かったり、離型性を向上させる為に離
型剤量を多く使用して樹脂が濁ったりする問題等があっ
た。また、着色性、離型性、透明性等をクリアーできた
離型剤でも、品質的に使用できる範囲が極めて狭いため
に、ロット間の僅かな品質ブレによって使用できなくな
るロットが発生し、煩雑なロット選定を行わなければな
らないものもあった。さらには、染色ムラ、ハードコー
トの密着性低下等の二次加工時に問題が発生することも
あった。通常、酸性ホスホン酸誘導体を用いれば、より
良好な結果を与える事が多い。しかしながらこの酸性ホ
スホン酸誘導体も、例えば、ルイス酸と3級アミンを併
用してウレタン化重合を均一に短時間で行なう特別な方
法(特開平8−208792号公報)に使用した場合、
透明性が損なわれ易くなるといった傾向があり、従来の
方法では、充分に満足できるとは言い難かった。However, even if these methods are used,
Transparency is still strictly insufficient or colored,
If the release agent itself has a high viscosity, it is difficult to use, has an unpleasant odor, and in the case of a resin with extremely strong adhesive strength, the usual amount of the release agent is not good or the release property is improved. There is a problem that the resin becomes cloudy when a large amount of the release agent is used. In addition, even with a release agent that has cleared coloring, release properties, transparency, etc., the range in which it can be used in terms of quality is extremely narrow. In some cases, it was necessary to select a suitable lot. Furthermore, problems may occur during secondary processing, such as uneven dyeing and reduced adhesion of the hard coat. Usually, better results are often obtained with the use of acidic phosphonic acid derivatives. However, when this acidic phosphonic acid derivative is used in a special method for uniformly and urethane polymerization in a short time by using a Lewis acid and a tertiary amine in combination (Japanese Patent Application Laid-Open No. 8-208792),
Transparency tends to be impaired, and it has been difficult to say that conventional methods are sufficiently satisfactory.
【0011】[0011]
【発明が解決しようとする課題】即ち、本発明が解決し
ようとする課題は、従来の離型剤よりも透明性と離型性
に優れた離型剤と、透明性に優れた高品質の透明樹脂を
提供する事にある。That is, an object of the present invention is to provide a release agent which is more excellent in transparency and releasability than a conventional release agent, and a high-quality release agent which is excellent in transparency. It is to provide a transparent resin.
【0012】[0012]
【課題を解決するための手段】本発明者らは、かかる課
題に鑑み、鋭意検討を行った結果、新規化合物である燐
酸エステルを見出すとともに、燐酸エステル並びにその
組成物を透明樹脂の離型剤として使用すれば、上記の問
題点は解決され、高品質の透明樹脂が得られる事を見出
し、本発明に到達した。Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies, and as a result, have found a novel compound, a phosphoric ester, and used the phosphoric ester and its composition as a releasing agent for a transparent resin. Using the above, the above problem was solved, a high-quality transparent resin was found to be obtained, and the present invention was reached.
【0013】即ち、本発明は、下記式(1)That is, the present invention provides the following formula (1)
【化3】 (式中、mは1または2を示し、nは2〜3の整数を示
し、R1はフェニル基を除いた炭素数1〜20の残基を
示し、R2、R3はそれぞれ水素原子、メチル基、エチル
基を示す。但し、R2、R3がともに水素原子である場合
を除く。)で表される燐酸エステルとその製造方法、該
燐酸エステルを含む離型剤、燐酸エステルを含む透明樹
脂並びに透明樹脂が透明光学材料、プラスチックレンズ
からなるものである。Embedded image (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R 1 represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R 2 and R 3 each represent a hydrogen atom , A methyl group and an ethyl group, except that both R 2 and R 3 are hydrogen atoms), a method for producing the same, a releasing agent containing the phosphoric ester, and a phosphoric ester. The transparent resin contained and the transparent resin are made of a transparent optical material and a plastic lens.
【0014】[0014]
【発明の実施の形態】以下、発明を詳細に説明する。本
発明の式(1)の燐酸エステルは、アルキルエチレング
リコール骨格を有する燐酸モノエステルまたは燐酸ジエ
ステルで、ここでmは1または2である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The phosphoric acid ester of the formula (1) of the present invention is a phosphoric acid monoester or a phosphoric acid diester having an alkylethylene glycol skeleton, wherein m is 1 or 2.
【0015】式(1)中のnは、アルキルエチレングリ
コール骨格の繰り返し数を表し、2〜3の範囲である。
nが1の場合は、モールドの形状等によって離型性にム
ラが発生する場合があり、4以上の場合は、原料が合成
しにくかったり、コスト高になったりする場合がある。N in the formula (1) represents the number of repetitions of the alkylethylene glycol skeleton, and is in the range of 2-3.
When n is 1, uneven releasability may occur depending on the shape of the mold, and when n is 4 or more, it may be difficult to synthesize the raw materials or the cost may be increased.
【0016】式(1)中のR2,R3は、水素、メチル
基、エチル基を表す(R2,R3が共に水素の場合を除
く。)。R2,R3が共に水素の場合は、少なくとも何れ
かがメチル基またはエチル基で置換された本発明の燐酸
エステルと比較して、離型性が低下する。R 2 and R 3 in the formula (1) represent hydrogen, a methyl group or an ethyl group (except when both R 2 and R 3 are hydrogen). When both R 2 and R 3 are hydrogen, the releasability is reduced as compared with the phosphate of the present invention in which at least one of them is substituted with a methyl group or an ethyl group.
【0017】式(1)で表されるR1残基は、フェニル
基を除いた炭素数1〜20で構成されるアルキル残基で
ある。フェニル基は樹脂を着色させる事がある。炭素数
が20を超えると透明性が低下する場合がある。好まし
くは3〜15の範囲である。The R 1 residue represented by the formula (1) is an alkyl residue having 1 to 20 carbon atoms excluding a phenyl group. Phenyl groups can cause the resin to color. If the number of carbon atoms exceeds 20, transparency may decrease. Preferably it is in the range of 3 to 15.
【0018】このR1で表される残基は、フェニル基を
除いて、炭素数が1〜20で構成されていることを必須
とするものである。従って、以下に代表的な残基の形態
を例示するが、本発明がこれらの形態のみに限定される
ものではない。残基の形態としては、例えば、直鎖状飽
和アルキル基、直鎖状不飽和アルキル基、分岐状飽和ア
ルキル基、分岐状不飽和アルキル基、直鎖状飽和アルキ
ルアリール基、直鎖状不飽和アルキルアリール基、アリ
ールアルキル基、アリールアルキレン基、アルキルアリ
ールアルキレン基等が挙げられる。また、上記残基中に
エーテル結合、チオエーテル結合、スルホキシ結合、ス
ルホン結合、エステル結合、カルボニル結合、アミド結
合、イミド結合、ヘテロ環、シクロアルキレン基環等の
異種原子、異種構造等も問題のない範囲で含んでも良
い。さらにはこれらの残基を構成する水素原子の一部を
同様に問題のない範囲で、フッ素、塩素、臭素等のハロ
ゲン原子で置換しても良い。The residue represented by R 1 must have at least 1 to 20 carbon atoms, except for the phenyl group. Therefore, typical forms of the residues will be described below, but the present invention is not limited to these forms. Examples of the form of the residue include a linear saturated alkyl group, a linear unsaturated alkyl group, a branched saturated alkyl group, a branched unsaturated alkyl group, a linear saturated alkylaryl group, and a linear unsaturated alkyl group. Examples thereof include an alkylaryl group, an arylalkyl group, an arylalkylene group, and an alkylarylalkylene group. In addition, there is no problem with heteroatoms and heterostructures such as an ether bond, a thioether bond, a sulfoxy bond, a sulfone bond, an ester bond, a carbonyl bond, an amide bond, an imide bond, a hetero ring, and a cycloalkylene group ring in the residue. It may be included in the range. Further, some of the hydrogen atoms constituting these residues may be replaced with halogen atoms such as fluorine, chlorine, and bromine as far as no problem occurs.
【0019】本発明の式(1)の燐酸エステルは、例え
ば、次のような方法で合成される。1,2−プロピレン
オキサイド、1,2−エポキシブタン、2,3−エポキ
シブタン、3,4−エポキシヘキサン等のエポキシ化合
物と、アルコール類、フェノールを除くフェノール類に
代表されるヒドロキシ化合物類とを反応させて得られる
オキシアルコール類と、オキシハロゲン化燐を反応させ
て、下記式(2)The phosphoric ester of the formula (1) of the present invention is synthesized, for example, by the following method. Epoxy compounds such as 1,2-propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and 3,4-epoxyhexane, and alcohols and hydroxy compounds represented by phenols other than phenol By reacting an oxyalcohol obtained by the reaction with a phosphorus oxyhalide, the following formula (2)
【化4】 (式中、mは1または2を示し、nは2〜3の整数を示
し、R1はフェニル基を除いた炭素数1〜20の残基を
示し、R2、R3はそれぞれ水素原子、メチル基、エチル
基を示す。但し、R2、R3がともに水素原子である場合
を除く。Xはハロゲン原子を表す。)で表される燐酸エ
ステルハライドを合成し、次いで加水分解することによ
って得られる。PH=8以下で加水分解を行った場合、
好ましい結果を与える。Embedded image (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R 1 represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R 2 and R 3 each represent a hydrogen atom , A methyl group and an ethyl group, provided that R 2 and R 3 are not both hydrogen atoms, and X represents a halogen atom.) Obtained by When hydrolysis is performed at PH = 8 or less,
Gives favorable results.
【0020】ジエステル体(m=2)を選択的に合成し
たい場合には、オキシハロゲン化燐の代わりに三塩化燐
等の三ハロゲン化燐類とオキシアルコール類とを反応さ
せて、亜燐酸ジエステル体を合成する。次いで、副生し
たオキシハロゲライドを減圧蒸留等の精製操作によって
系外に留去除去した後、塩素等のハロゲン類を反応させ
て、ハロゲノ亜燐酸ジエステルを生成せしめ、最後にオ
キシハロゲン化燐を用いた場合と同様に加水分解するこ
とによって得られる。一般式(2)におけるR1〜R3、
n、mの意味は一般式(1)におけるものと同様であ
る。When it is desired to selectively synthesize a diester (m = 2), a phosphorus trihalide such as phosphorus trichloride is reacted with an oxyalcohol instead of phosphorus oxyhalide to obtain a phosphorous diester. Synthesize the body. Next, by-produced oxyhalogenide is distilled off and removed from the system by a purification operation such as distillation under reduced pressure, and then reacted with halogens such as chlorine to produce a halogenophosphorous diester. It is obtained by hydrolysis in the same manner as when used. R 1 to R 3 in the general formula (2),
The meanings of n and m are the same as those in the general formula (1).
【0021】以下に、具体的な一例を挙げて、各工程の
製造方法を述べる。Hereinafter, the production method of each step will be described with reference to a specific example.
【化5】 Embedded image
【0022】アルコール類である式(A)の1−ブタノ
ールに式(B)の1,2−プロピレンオキサイドを反応
させて式(C)の1−ブトキシ−2−プロパノールを合
成し、もう一度式(B)の1,2−プロピレンオキサイ
ドを反応させて、オキシアルコール類である式(D)の
1−(1−ブトキシ−2−プロポキシ)−2−プロパノ
ールを合成する。このオキシアルコール類を合成する付
加反応の反応温度は、例えば、ヒドロキシ基がアルコー
ル性であるか、フェノール性であるか等の酸性度の差等
によってもかなり異なるが、0〜200℃が好ましく、
30〜150℃が特に好ましい。The 1-butanol of the formula (A), which is an alcohol, is reacted with the 1,2-propylene oxide of the formula (B) to synthesize 1-butoxy-2-propanol of the formula (C). By reacting 1,2-propylene oxide of B), 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D), which is an oxyalcohol, is synthesized. The reaction temperature of the addition reaction for synthesizing the oxyalcohols varies considerably depending on, for example, the difference in acidity such as whether the hydroxy group is alcoholic or phenolic, and is preferably 0 to 200 ° C.
30-150 ° C is particularly preferred.
【0023】反応速度を向上させる目的で、水酸化ナト
リウム、炭酸ナトリウム、水酸化カリウム、炭酸カリウ
ム、トリエチルアミン、ピリジン等の塩基類を触媒とし
て加えても良い。添加量は、反応液に対して0.001
〜5wt%の範囲が好ましく、0.05〜3wt%の範
囲であればさらに好ましい。For the purpose of improving the reaction rate, a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine or the like may be added as a catalyst. The addition amount is 0.001 to the reaction solution.
The range is preferably from 5 to 5% by weight, and more preferably from 0.05 to 3% by weight.
【0024】反応溶媒は、使用しなくても良いが、使用
する場合はアセトニトリル、トルエン、ジクロロエタ
ン、クロロベンゼン、ジメチルホルムアミド等の非プロ
トン性溶媒が好ましい。選択率の向上や急激な内温上昇
抑制を目的として、原料である1−ブタノール、1−ブ
トキシ−2−プロパノール、または1,2−プロピレン
オキサイドの何れかまたは両方を滴下しても良い。こう
して得られた式(D)の1−(1−ブトキシ−2−プロ
ポキシ)−2−プロパノールは、そのまま次の反応に用
いても構わないが、通常、蒸留によって精製されること
が多い。The reaction solvent may not be used, but when used, an aprotic solvent such as acetonitrile, toluene, dichloroethane, chlorobenzene, dimethylformamide and the like is preferable. Raw material 1-butanol, 1-butoxy-2-propanol, and / or 1,2-propylene oxide may be added dropwise for the purpose of improving selectivity and suppressing a rapid increase in internal temperature. The thus obtained 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D) may be used in the next reaction as it is, but is usually often purified by distillation.
【0025】本発明に関わる式(2)の燐酸エステルハ
ライド類に属する式(F)モノ(1−(1−ブトキシ−
2−プロポキシ)−2−プロピル)燐酸ジハライドは、
式(D)の1−(1−ブトキシ−2−プロポキシ)−2
−プロパノールを、オキシ塩化燐、オキシ臭化燐等に代
表される式(E)のオキシハロゲン化燐と反応させるこ
とによって得られる。オキシハロゲン化燐の中では、経
済的に有利なオキシ塩化燐が好ましく用いられる。The formula (F) mono (1- (1-butoxy-) which belongs to the phosphate halides of the formula (2) according to the present invention.
2-propoxy) -2-propyl) phosphoric dihalide is
1- (1-butoxy-2-propoxy) -2 of the formula (D)
-Propanol is obtained by reacting with phosphorus oxyhalide of the formula (E) represented by phosphorus oxychloride, phosphorus oxybromide and the like. Among the phosphorus oxyhalides, economically advantageous phosphorus oxychloride is preferably used.
【0026】式(D)の1−(1−ブトキシ−2−プロ
ポキシ)−2−プロパノールと式(E)のオキシハロゲ
ン化燐類とのモル比は、所望する燐酸エステルの組成に
よってほぼ決定されるが、好ましくは0.5〜2.5
(D/E)、特に好ましくは0.9〜2.1(D/E)
である。The molar ratio of 1- (1-butoxy-2-propoxy) -2-propanol of formula (D) to phosphorus oxyhalides of formula (E) is largely determined by the desired composition of the phosphate ester. But preferably 0.5 to 2.5
(D / E), particularly preferably 0.9 to 2.1 (D / E).
It is.
【0027】反応温度は0〜100℃が好ましく、10
〜50℃であればさらに好ましい。100℃を超えた場
合、著しく着色する場合がある。The reaction temperature is preferably from 0 to 100 ° C., preferably from 10 to 100 ° C.
It is more preferable that the temperature is from 50 ° C to 50 ° C. If it exceeds 100 ° C., it may be markedly colored.
【0028】反応速度を向上させる目的で、水酸化ナト
リウム、炭酸ナトリウム、水酸化カリウム、炭酸カリウ
ム、トリエチルアミン、ピリジン等の塩基類をハロゲン
化水素キャチ剤として加えても良い。中でもトリエチル
アミン、ピリジン等の三級アミンを用いた場合、好まし
い結果を与える。塩基の使用量は、オキシアルコール類
である式(D)の1−(1−ブトキシ−2−プロポキ
シ)−2−プロパノールのヒドロキシ基に対して、0.
5〜2.0当量が好ましく、0.9〜1.5当量であれ
ばさらに好ましい。For the purpose of improving the reaction rate, bases such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine and the like may be added as a hydrogen halide catching agent. In particular, when a tertiary amine such as triethylamine or pyridine is used, preferable results are obtained. The amount of the base used is 0.1 to the hydroxy group of 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D) which is an oxy alcohol.
Preferably 5 to 2.0 equivalents, more preferably 0.9 to 1.5 equivalents.
【0029】塩基を使用しない場合、反応溶媒も使用し
ない方が好ましい。塩基を使用する場合は、反応溶媒を
使用した方が都合がよい場合が多く、例えば、ベンゼ
ン、トルエン、ジクロロエタン、クロロベンゼン、ジク
ロロベンゼン、酢酸ブチル、メチルイソブチルケトン等
の水と分離する溶媒が好ましく用いられる。中でもジク
ロロエタン、クロロベンゼン、ジクロロベンゼン等のハ
ロゲン溶媒がさらに好ましい。When no base is used, it is preferable not to use a reaction solvent. When a base is used, it is often convenient to use a reaction solvent.For example, a solvent that separates from water such as benzene, toluene, dichloroethane, chlorobenzene, dichlorobenzene, butyl acetate, and methyl isobutyl ketone is preferably used. Can be Of these, halogen solvents such as dichloroethane, chlorobenzene, and dichlorobenzene are more preferable.
【0030】選択率の向上や急激な内温上昇抑制等を目
的として、オキシアルコール類である式(D)の1−
(1−ブトキシ−2−プロポキシ)−2−プロパノール
と塩基を同時に滴下するか、若しくはオキシハロゲン化
燐類、1−(1−ブトキシ−2−プロポキシ)−2−プ
ロパノール、塩基の三種類全てを同時に滴下しても良
い。For the purpose of improving selectivity and suppressing a rapid rise in internal temperature, oxyalcohols of the formula (D) 1-
(1-butoxy-2-propoxy) -2-propanol and a base are simultaneously added dropwise, or phosphorus oxyhalides, 1- (1-butoxy-2-propoxy) -2-propanol, and all three kinds of bases are used. It may be dropped at the same time.
【0031】本発明に関わる式(1)の燐酸エステルに
属する式(G)モノ(1−(1−ブトキシ−2−プロポ
キシ)−2−プロピル)燐酸は、式(F)モノ(1−
(1−ブトキシ−2−プロポキシ)−2−プロピル)燐
酸ジハライドを加水分解することによって得られる。The mono (1- (1-butoxy-2-propoxy) -2-propyl) phosphoric acid of the formula (G) belonging to the phosphoric ester of the formula (1) according to the present invention is represented by the formula (F):
It is obtained by hydrolyzing (1-butoxy-2-propoxy) -2-propyl) phosphoric dihalide.
【0032】加水分解は、水酸化ナトリウム水、炭酸ナ
トリウム水、炭酸水素ナトリウム水、水酸化カリウム
水、炭酸カリウム水、燐酸ナトリウム水、酢酸ナトリウ
ム水、アンモニア水、水、酢酸水、塩酸、硫酸等の各種
塩基及び酸が使用できるが、加水分解のPHは8以下、
特に7以下が好ましい。PHが8を超えた状態で加水分
解を行っても、離型剤の性能としては十分満足できるも
のが得られるが、得られる製品が着色したり、加水分解
以外の副反応が起こったりする傾向がある。加水分解剤
の種類としては、経済性、品質、及び操作性の面から、
水が好ましい。さらに加水分解は、反応液を窒素バブリ
ングしながら行った方が、好ましい結果を与える場合が
多い。Hydrolysis includes aqueous sodium hydroxide, aqueous sodium carbonate, aqueous sodium hydrogen carbonate, aqueous potassium hydroxide, aqueous potassium carbonate, aqueous sodium phosphate, aqueous sodium acetate, aqueous ammonia, water, aqueous acetic acid, hydrochloric acid, sulfuric acid, and the like. Although various bases and acids can be used, the pH of the hydrolysis is 8 or less,
Particularly, it is preferably 7 or less. Even if the hydrolysis is carried out in a state where the pH exceeds 8, a satisfactory release agent performance can be obtained, but the obtained product tends to be colored and side reactions other than hydrolysis occur. There is. As the type of hydrolyzing agent, from the viewpoint of economy, quality, and operability,
Water is preferred. Further, it is often the case that the hydrolysis is carried out while bubbling the reaction solution with nitrogen to give a preferable result.
【0033】反応温度は0〜100℃が好ましく、30
〜70℃であればさらに好ましい。加水分解の場合も、
急激な内温上昇抑制等を目的として、例えば、水等の加
水分解剤に、式(F)モノ(1−(1−ブトキシ−2−
プロポキシ)−2−プロピル)燐酸ジハライドまたはそ
の反応液を滴下するといった形態の方が、より好ましい
結果を与えることが多い。The reaction temperature is preferably from 0 to 100 ° C.,
It is more preferable that the temperature is 70 ° C. In the case of hydrolysis,
For the purpose of suppressing a rapid increase in the internal temperature, for example, a hydrolyzing agent such as water is added to a mono (1- (1-butoxy-2-)-formula (F).
A form in which propoxy) -2-propyl) phosphoric acid dihalide or a reaction solution thereof is added dropwise often gives more favorable results.
【0034】こうして得られた反応液は、必要に応じ
て、洗浄、濾過、活性炭処理等に代表される吸着処理
等、及び脱溶媒等の蒸留操作によって精製され、式
(G)のモノ(1−(1−ブトキシ−2−プロポキシ)
−2−プロピル)燐酸が得られる。The reaction liquid thus obtained is purified, if necessary, by an adsorption treatment typified by washing, filtration, activated carbon treatment and the like, and a distillation operation such as desolvation. -(1-butoxy-2-propoxy)
-2-propyl) phosphoric acid is obtained.
【0035】別法として、本発明に関わる式(1)の燐
酸エステルは、ヒドロキシ化合物類と五酸化二燐を反応
させることによっても得ることができる。Alternatively, the phosphoric ester of formula (1) according to the present invention can be obtained by reacting hydroxy compounds with diphosphorus pentoxide.
【0036】式(G)も含めた本発明の燐酸エステル
は、例えば、以下の化合物が挙げられる。代表的な化合
物として、例えば、(モノ,ジ)(1−(1−メトキシ
−2−プロポキシ)−2−プロピル)燐酸、(モノ,
ジ)(1−(1−エトキシ−2−プロポキシ)−2−プ
ロピル)燐酸、(モノ,ジ)(1−(1−プロポキシ−
2−プロポキシ)−2−プロピル)燐酸、(モノ,ジ)
(1−(1−ブトキシ−2−プロポキシ)−2−プロピ
ル)燐酸、(モノ,ジ)(1−(1−ヘキシロキシ−2
−プロポキシ)−2−プロピル)燐酸、(モノ,ジ)
(1−(1−オクチロキシ−2−プロポキシ)−2−プ
ロピル)燐酸、(モノ,ジ)(1−(1−ノニロキシ−
2−プロポキシ)−2−プロピル)燐酸、(モノ,ジ)
(1−(1−デカロキシ−2−プロポキシ)−2−プロ
ピル)燐酸、(1−(1−ドデカノキシ−2−プロポキ
シ)−2−プロピル)燐酸、(モノ,ジ)(1−(1−
テトラデカロキシ−2−プロポキシ)−2−プロピル)
燐酸、(モノ,ジ)(1−(1−ヘキサデカロキシ−2
−プロポキシ)−2−プロピル)燐酸、(モノ,ジ)
(1−(1−ステアロキシ−2−プロポキシ)−2−プ
ロピル)燐酸、(モノ,ジ)(1−(1−エイコサロキ
シ−2−プロポキシ)−2−プロピル)燐酸、(モノ,
ジ)(1−(1−ベンジロキシ−2−プロポキシ)−2
−プロピル)燐酸、(モノ,ジ)(1−(1−ブチルフ
ェノキシ−2−プロポキシ)−2−プロピル)燐酸、
(モノ,ジ)(1−(1−ヘキシルフェノキシ−2−プ
ロポキシ)−2−プロピル)燐酸、(モノ,ジ)(1−
(1−オクチルフェノキシ−2−プロポキシ)−2−プ
ロピル)燐酸、(モノ,ジ)(1−(1−ノニルフェノ
キシ−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−ブトキシ−2−ブチロキシ)−2
−ブチル)燐酸、(モノ,ジ)(2−(2−ブトキシ−
3−ブチロキシ)−3−ブチル)燐酸、(モノ,ジ)
(1−(1−ノニルフェノキシ−2−ブチロキシ)−2
−ブチル)燐酸、(モノ,ジ)(2−(2−ノニルフェ
ノキシ−3−ブチロキシ)−3−ブチル)燐酸、(モ
ノ,ジ)(1−(1−(1−メトキシ−2−プロポキ
シ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−プロポキシ−2−プロポキ
シ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−ブトキシ−2−プロポキ
シ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−ヘキシロキシ−2−プロポ
キシ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−オクチロキシ−2−プロポ
キシ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−ノニロキシ−2−プロポキ
シ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−ステアロキシ−2−プロポ
キシ)−2−プロポキシ)−2−プロピル)燐酸、(モ
ノ,ジ)(1−(1−(1−ノニルフェノキシ−2−プ
ロポキシ)−2−プロポキシ)−2−プロピル)燐酸、
(モノ,ジ)(1−(1−(1−ブトキシ−2−ブチロ
キシ)−2−ブチロキシ)−2−ブチル)燐酸、(モ
ノ,ジ)(2−(2−(2−ブトキシ−3−ブチロキ
シ)−3−ブチロキシ)−3−ブチル)燐酸、(モノ,
ジ)(1−(1−(1−ノニルフェノキシ−2−ブチロ
キシ)−2−ブチロキシ)−2−ブチル)燐酸、(モ
ノ,ジ)(2−(2−(2−ノニルフェノキシ−3−ブ
チロキシ)−3−ブチロキシ)−3−ブチル)燐酸等の
他にこれら燐酸エステルのフッ素置換体、塩素置換体、
臭素置換体等のハロゲン置換体等も挙げられる。本発明
の燐酸エステルが、これら列記化合物のみに限定される
ものではない。Examples of the phosphoric acid ester of the present invention including the formula (G) include the following compounds. Representative compounds include, for example, (mono, di) (1- (1-methoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di)
Di) (1- (1-ethoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-propoxy-
2-propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-butoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-hexyloxy-2)
-Propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-octyloxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-nonyloxy-
2-propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-decaloxy-2-propoxy) -2-propyl) phosphoric acid, (1- (1-dodecanoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-
Tetradecaloxy-2-propoxy) -2-propyl)
Phosphoric acid, (mono, di) (1- (1-hexadecaloxy-2)
-Propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-stearoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-eicosaloxy-2-propoxy) -2-propyl) phosphoric acid, (mono,
Di) (1- (1-benzyloxy-2-propoxy) -2
-Propyl) phosphoric acid, (mono, di) (1- (1-butylphenoxy-2-propoxy) -2-propyl) phosphoric acid,
(Mono, di) (1- (1-hexylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1-
(1-octylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-nonylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-butoxy-2-butyroxy) -2
-Butyl) phosphoric acid, (mono, di) (2- (2-butoxy-
3-butyroxy) -3-butyl) phosphoric acid, (mono, di)
(1- (1-nonylphenoxy-2-butyroxy) -2
-Butyl) phosphoric acid, (mono, di) (2- (2-nonylphenoxy-3-butyroxy) -3-butyl) phosphoric acid, (mono, di) (1- (1- (1-methoxy-2-propoxy)) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1-propoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) ( 1- (1- (1-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1-hexyloxy-2-propoxy) -2-propoxy) ) -2-Propyl) phosphoric acid, (mono, di) (1- (1- (1-octyloxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1 -(1-nonyloxy-2-propoxy) -2-propoxy) -2- (Ropyl) phosphoric acid, (mono, di) (1- (1- (1-stearoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1- Nonylphenoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid,
(Mono, di) (1- (1- (1-butoxy-2-butoxy) -2-butoxy) -2-butyl) phosphoric acid, (mono, di) (2- (2- (2-butoxy-3-) Butyroxy) -3-butyroxy) -3-butyl) phosphoric acid, (mono,
Di) (1- (1- (1-nonylphenoxy-2-butyroxy) -2-butyroxy) -2-butyl) phosphoric acid, (mono, di) (2- (2- (2-nonylphenoxy-3-butyroxy) ) -3-butyroxy) -3-butyl) phosphoric acid and the like, as well as a fluorine-substituted or chlorine-substituted product of these phosphates,
Halogen-substituted products such as bromine-substituted products are also included. The phosphate ester of the present invention is not limited only to these listed compounds.
【0037】本発明の離型剤は、式(1)であらわされ
る燐酸エステル体を、少なくとも含むことを必須とする
燐酸エステル組成物である。例えば、式(1)であらわ
される燐酸エステル体以外に、問題の無い範囲でトリエ
ステル体、燐酸、ヒドロキシ化合物類、水、金属、金属
塩、有機金属塩、及びその他の燐酸エステル等を含んで
いても良く、さらに、粘度を下げて操作性及び分散性を
向上したり、モノマー並びにポリマーへの溶解性を高め
る目的等で、例えばヘキサン等に代表される炭化水素系
溶媒、アルキル(アリル)アルコール及びアルコキシ
(アリロキシ)アルキル(アリル)アルコール類とその
エーテル並びにエステル類、トルエン、キシレン等に代
表されるベンゼン誘導体類、ジクロロメタン、クロロホ
ルム、ジクロロエタン、クロロベンゼン、ジクロロベン
ゼン等のハロゲン溶媒類、アセトン、メチルエチルケト
ン、テトラヒドロフラン、N,N−ジメチルホルムアミ
ド、N,・N−ジメチルイミダゾリジノン等に代表され
る非プロトン性極性溶媒類なども同様に問題の無い範囲
で含んでも一向に差し支えない。The release agent of the present invention is a phosphoric ester composition essentially including at least the phosphoric ester represented by the formula (1). For example, in addition to the phosphoric ester represented by the formula (1), a triester, a phosphoric acid, a hydroxy compound, water, a metal, a metal salt, an organic metal salt, other phosphoric esters, and the like are included as long as there is no problem. In addition, for the purpose of lowering viscosity to improve operability and dispersibility, and increasing solubility in monomers and polymers, for example, hydrocarbon solvents represented by hexane and the like, alkyl (allyl) alcohol And alkoxy (allyloxy) alkyl (allyl) alcohols and their ethers and esters, benzene derivatives represented by toluene, xylene, etc., halogen solvents such as dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, acetone, methyl ethyl ketone, Tetrahydrofuran, N, N-dimethylform Amide, N, at all no problem include with no range problem similarly like aprotic polar solvents represented by · N-dimethyl-imidazolidinone.
【0038】本発明の離型剤の使用形態は、モノマーに
予め添加する内部離型剤方式でも、成形型に予め塗布し
ておく外部離型剤方式で良いが、煩雑な操作の少ない内
部離型剤方式が好ましく用いられる。The release agent of the present invention may be used in the form of an internal release agent which is previously added to a monomer or an external release agent which is previously applied to a molding die. A mold system is preferably used.
【0039】本発明の透明樹脂は、有機化合物を主成分
とする透明樹脂であり、例えば、オレフィン樹脂、エポ
キシ樹脂、ウレタン樹脂、カーボネート樹脂、エステル
樹脂、オレフィン−チオール樹脂、エポキシ−チオール
樹脂、並びにそれらの併用透明樹脂等が挙げられが、本
発明が以上に列記した樹脂のみに限定されるものではな
いが、特にポリチオウレタン樹脂の場合は効果的であ
る。The transparent resin of the present invention is a transparent resin containing an organic compound as a main component, for example, olefin resin, epoxy resin, urethane resin, carbonate resin, ester resin, olefin-thiol resin, epoxy-thiol resin, and These include transparent resins used in combination, but the present invention is not limited to only the resins listed above, but is particularly effective in the case of polythiourethane resins.
【0040】本発明の離型剤の使用は、例えば、次のよ
うに行う。成型形態は、大まかに射出成型法、インジェ
クションキュアー法、注型重合法の凡そ3種類に分類さ
れるが、3種類とも行われる操作について、まず説明す
る。The release agent of the present invention is used, for example, as follows. The molding modes are roughly classified into approximately three types: an injection molding method, an injection cure method, and a casting polymerization method. Operations performed for all three types will be described first.
【0041】原料のモノマー、オリゴマー、またはポリ
マーペレットに本発明の燐酸エステルまたは離型剤を添
加し、必要な場合は加熱して、混合溶解する。離型剤の
添加量は原料によって大きく変化するため限定出来ない
が、凡そ0.0001〜30重量%である。次に、必要
に応じ減圧などの適当な方法で脱泡を行い、成形型に注
入し、硬化させて透明樹脂成型物を取り出す。得られた
透明樹脂は、歪みを取ったり、より完全に重合を完結さ
せる目的で、通常凡そ100℃以上の温度でアニールを
行なう。以下、上記した3形態について、各々個別に簡
単に説明を行う。The phosphoric ester or the release agent of the present invention is added to the raw material monomer, oligomer, or polymer pellet, and if necessary, mixed and dissolved by heating. The amount of the release agent varies greatly depending on the raw material and cannot be limited, but is generally about 0.0001 to 30% by weight. Next, if necessary, defoaming is performed by an appropriate method such as decompression, and the resulting mixture is poured into a molding die and cured to take out a transparent resin molded product. The obtained transparent resin is usually annealed at a temperature of about 100 ° C. or higher for the purpose of removing distortion and completing polymerization more completely. Hereinafter, each of the above-described three embodiments will be briefly described individually.
【0042】オレフィン、ポリカーボネート、ポリエス
テル樹脂等の場合に良く用いられる射出成型の場合は、
ペレットに離型剤を添加し凡そ100〜400℃で加熱
溶解した後、主に金属製の成形型に溶融液を注入し冷却
して、透明樹脂を硬化させる。In the case of injection molding often used in the case of olefin, polycarbonate, polyester resin, etc.,
After adding a release agent to the pellets and heating and dissolving them at about 100 to 400 ° C., the molten liquid is poured into a metal mold mainly and cooled to harden the transparent resin.
【0043】一部のウレタン樹脂及びエポキシ樹脂等に
良く用いられるインジェクションキュアー法の場合も、
主に金属製の成形型が用いられ、モノマー組成物に離型
剤、硬化剤等を添加し、減圧等によって脱泡を行なった
後、樹脂が硬化する前に直ちに成形型に注入し熱硬化さ
せる。In the case of the injection cure method often used for some urethane resins and epoxy resins,
A metal mold is mainly used, a mold release agent, a curing agent, etc. are added to the monomer composition, defoaming is performed under reduced pressure, etc., and then immediately injected into the mold before the resin is cured, followed by thermosetting. Let it.
【0044】ウレタン、オレフィン樹脂をはじめとして
大部分の樹脂の精密成型に良く用いられる注型重合は、
モノマー組成物に離型剤を添加し、減圧等によって脱泡
を行なった後、主にガラスモールドと樹脂製のガスケッ
トまたはテープからなるガラス製モールドに脱泡液を注
入し、熱または放射線によって重合硬化させる。加熱重
合の場合の条件は、凡そ0〜200℃の温度範囲で低温
から高温迄徐々に昇温を行い、凡そ1〜100時間で終
了させる。放射線重合の場合は、主に400nm以下の
紫外線が良く用いられる。紫外線の量は凡そ1〜100
0mJ/secの強度で1〜7200sec照射される
場合が多く、時には除熱や光学的に均一は成型物を得る
目的で、照射前に冷却したり、照射を数回に分けて行な
ったりする。また、熱重合と放射線重合を組み合わせて
行なう場合もある。本発明は、この注型重合の場合に、
より効果的になる。Casting polymerization often used for precision molding of most resins including urethane and olefin resins is as follows:
After adding a release agent to the monomer composition and defoaming by decompression etc., the defoaming liquid is poured into a glass mold consisting mainly of a glass mold and a resin gasket or tape, and polymerized by heat or radiation Let it cure. In the case of heat polymerization, the temperature is gradually raised from a low temperature to a high temperature in a temperature range of about 0 to 200 ° C., and the polymerization is completed in about 1 to 100 hours. In the case of radiation polymerization, ultraviolet rays of 400 nm or less are mainly used. The amount of UV light is about 1-100
In many cases, irradiation is performed at an intensity of 0 mJ / sec for 1 to 7200 sec, and sometimes cooling or irradiation is performed several times before irradiation in order to remove heat or obtain a molded product having optical uniformity. In some cases, thermal polymerization and radiation polymerization are combined. The present invention provides, in this casting polymerization,
Be more effective.
【0045】以上の成形法において、熱触媒、光触媒、
UV吸収剤、酸化防止剤、重合禁止剤、油溶染料、充填
剤、可塑剤、その他の離型剤、溶剤等の原料以外の有機
化合物、無機化合物も問題の無い範囲で加える事ができ
る。In the above molding method, a thermal catalyst, a photocatalyst,
Organic compounds and inorganic compounds other than raw materials such as UV absorbers, antioxidants, polymerization inhibitors, oil-soluble dyes, fillers, plasticizers, other release agents, and solvents can be added within a range without any problem.
【0046】また、得られた透明樹脂、透明光学材料、
及びプラスチックレンズは、必要に応じ反射防止、高硬
度付与、耐摩耗性向上、耐薬品性向上、防曇性付与、あ
るいはファッション性付与等の改良を行うため、表面研
磨、帯電防止処理、ハードコート処理、無反射コート処
理、調光処理等の物理的あるいは化学的処理を施すこと
ができる。Further, the obtained transparent resin, transparent optical material,
In addition, plastic lenses have surface polishing, antistatic treatment, hard coating, etc. to improve anti-reflection, high hardness, abrasion resistance, chemical resistance, anti-fog, or fashion, if necessary. Physical or chemical treatment such as treatment, anti-reflection coating treatment, and light control treatment can be performed.
【0047】[0047]
【実施例】以下、本発明を実施例及び比較例により具体
的に説明する。なお、得られた透明樹脂の屈折率、アッ
ベ数、着色度、透明度、離型性、及び表面状態は、以下
の試験方法により評価した。The present invention will be described below in more detail with reference to examples and comparative examples. The refractive index, Abbe number, degree of coloring, transparency, releasability, and surface state of the obtained transparent resin were evaluated by the following test methods.
【0048】屈折率、アッベ数;プルフリッヒ屈折計を
用い、20℃で測定した。 着色度;9mm平板を作成し、ミノルタ色彩色差計にて
YIを測定し、4.5以下を(○)、4.5を越えたも
のを(×)とした。 透明度;厚さ9mm、Φ75mmの円形平板を作成し、
濃淡画像装置で測定を行なった。C輝度平均で50以下
を(○)50を越えた物を(×)とした。 離型性;外径84mm高さ17mmと外径84mm高さ
11mmのガラスモールドとテープで作製した凸型成型
モールドを用いて評価した。 各々5セット仕込み、重合終了後、室温まで放冷して、
3枚以上が自然に離型した場合を(○)、3枚以上が無
理な力を必要としたり、ガラスモールドが破損又は剥離
した場合を(×)とした。Refractive index, Abbe number: Measured at 20 ° C. using a Pulfrich refractometer. Coloring degree: A 9 mm flat plate was prepared and YI was measured with a Minolta colorimeter, and 4.5 or less was evaluated as (○) and 4.5 or more as (X). Transparency; 9mm thick, Φ75mm circular plate is made,
The measurement was performed with a gray-scale image device. C: A value of 50 or less in average brightness was evaluated as (○), and a product exceeding 50 was evaluated as (x). Releasability: evaluated using a glass mold having an outer diameter of 84 mm and a height of 17 mm, an outer diameter of 84 mm and a height of 11 mm, and a convex mold made of tape. After charging 5 sets each, after the polymerization is completed, it is allowed to cool to room temperature,
A case where three or more sheets were naturally released from the mold was rated as (○), and a case where three or more sheets required excessive force, or the case where the glass mold was broken or peeled was rated as (x).
【0049】実施例1(燐酸エステルの合成―1) 3l反応フラスコに、オキシ塩化燐600.0g(3.
91モル)とモノクロロベンゼン1000mlを仕込
み、1−(1−n−ブトキシ−2−プロポキシ)−2−
プロパノール743.3g(3.91モル)とピリジン
324.0g(4.10モル)の混合液を氷冷下で攪拌
を行いながら内温2〜10℃で4時間で滴下し、20〜
25℃で5時間熟成した。得られた反応液を濾過して、
濾塊をモノクロロベンゼン800mlで洗浄した。濾液
と洗液の混合液を減圧下で脱溶媒し、粗モノ(1−(1
−n−ブトキシ−2−プロポキシ)−2−プロピル)燐
酸ジクロライド1226gを得た。次に、水900gが
仕込まれた3l反応フラスコに窒素バブリングを行いな
がら、得られた粗モノ(1−(1−n−ブトキシ−2−
プロポキシ)−2−プロピル)燐酸ジクロライド122
6gを内温50〜60℃で3.5時間かけて滴下し、6
0℃で3時間熟成した(PH=1以下)。室温に冷却さ
れるまで窒素バブリングを続行した後、モノクロロベン
ゼン1800mlと岩塩140gを加えて抽出分液し
た。下層の有機層を、5%の塩酸水400mlで洗浄
し、次いで水400mlで水洗した。次に、下層の有機
層に活性炭(白鷺C)30gを加えて、室温で1時間攪
拌後、濾過した。得られた濾液を、さらに水400ml
で2回水洗し、減圧下で脱溶媒トッピングを行った。最
後に、残渣を室温で濾過(3μm)して、889.2g
(粗収率84%)のモノ(1−(1−n−ブトキシ−2
−プロポキシ)−2−プロピル)燐酸を得た。得られた
燐酸エステルの組成は、以下の通りであった。Example 1 (Synthesis of Phosphoric Ester-1) 600.0 g of phosphorus oxychloride (3.
91 mol) and 1000 ml of monochlorobenzene, and 1- (1-n-butoxy-2-propoxy) -2-
A mixture of 743.3 g (3.91 mol) of propanol and 324.0 g (4.10 mol) of pyridine was added dropwise at 4 to 4 hours at an internal temperature of 2 to 10 ° C. while stirring under ice cooling.
Aged at 25 ° C. for 5 hours. The obtained reaction solution is filtered,
The filter cake was washed with 800 ml of monochlorobenzene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure to obtain a crude mono (1- (1
1,226 g of -n-butoxy-2-propoxy) -2-propyl) phosphoric dichloride were obtained. Next, while performing nitrogen bubbling on a 3 l reaction flask charged with 900 g of water, the obtained crude mono (1- (1-n-butoxy-2-) was obtained.
Propoxy) -2-propyl) phosphoric dichloride 122
6 g was dropped at an internal temperature of 50 to 60 ° C. over 3.5 hours.
Aged at 0 ° C. for 3 hours (PH = 1 or less). After continuing nitrogen bubbling until the temperature was cooled to room temperature, 1800 ml of monochlorobenzene and 140 g of rock salt were added thereto to carry out extraction and separation. The lower organic layer was washed with 400 ml of 5% hydrochloric acid and then with 400 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the lower organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate was further added to 400 ml of water.
, And the solvent was removed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give 889.2 g
(Crude yield 84%) of mono (1- (1-n-butoxy-2)
-Propoxy) -2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.
【表1】 シリカゲルカラムクロマトグラフィーで精製して収得し
た同定データを以下に記載する。 <MSスペクトル(FAB(Pos.))>m/z=271(M+H)+ < 1H−NMR> → 図1参照 < 13C−NMR> → 図2参照[Table 1] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 271 (M + H) + < 1 H-NMR> → see FIG. 1 < 13 C-NMR> → see FIG. 2
【0050】実施例2(燐酸エステルの合成―2) 3l反応フラスコに、オキシ塩化燐383.3g(2.
50モル)とトルエン1800mlを仕込み、1−(1
−n−ブトキシ−2−プロポキシ)−2−プロパノール
951.4g(5.00モル)とピリジン553.7g
(7.00モル)の混合液を氷冷下で攪拌を行いながら
内温25〜30℃で2.5時間かけて滴下し、21〜6
0℃で22時間熟成した。得られた反応液を濾過して、
濾塊をトルエン500mlで洗浄した。濾液と洗液の混
合液を減圧下で脱溶媒し、粗ジ(1−(1−n−ブトキ
シ−2−プロポキシ)−2−プロピル)燐酸クロライド
1142.2gを得た。次に、水1000mlが仕込ま
れた3l反応フラスコに窒素バブリングを行いながら、
得られた粗ジ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸クロライドを内温50〜60
℃で0.5時間かけて滴下し、60℃で5時間熟成し
た。室温に冷却されるまで窒素バブリングを続行した
後、トルエン1000mlを加えて抽出分液した。上層
の有機層を、5%の塩酸水500mlで洗浄し、次いで
水500mlで水洗した。次に、上層の有機層に活性炭
(白鷺C)30gを加えて、室温で1時間攪拌後、濾過
した。得られた濾液を、さらに水500mlで2回水洗
し、減圧下で脱溶媒トッピングを行った。最後に、残渣
を室温で濾過(3μm)して、1022.3g(粗収率
92%)のジ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸を得た。得られた燐酸エステ
ルの組成は、以下の通りであった。Example 2 (Synthesis of Phosphate Ester-2) 383.3 g of phosphorus oxychloride (2.
50 mol) and 1800 ml of toluene.
-N-butoxy-2-propoxy) -2-propanol 951.4 g (5.00 mol) and pyridine 553.7 g
(7.00 mol) was added dropwise over 2.5 hours at an internal temperature of 25 to 30 ° C. while stirring under ice cooling.
Aged at 0 ° C. for 22 hours. The obtained reaction solution is filtered,
The filter cake was washed with 500 ml of toluene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure to obtain 1142.2 g of crude di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid chloride. Next, while performing nitrogen bubbling on a 3 liter reaction flask charged with 1000 ml of water,
The obtained crude di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid chloride was treated at an internal temperature of 50 to 60.
The mixture was added dropwise at 0.5 ° C. over 0.5 hours, and aged at 60 ° C. for 5 hours. After continuing nitrogen bubbling until it was cooled to room temperature, 1000 ml of toluene was added thereto to carry out extraction and separation. The upper organic layer was washed with 500 ml of 5% hydrochloric acid and then with 500 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the upper organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate was further washed twice with 500 ml of water and subjected to desolvation topping under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to obtain 1022.3 g (92% crude yield) of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid. The composition of the obtained phosphoric ester was as follows.
【表2】 シリカゲルカラムクロマトグラフィーで精製して収得し
た同定データを以下に記載する。 <MSスペクトル(FAB(Pos.))>m/z=443(M+H)+ < 1H−NMR> → 図3参照 < 13C−NMR> → 図4参照[Table 2] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 443 (M + H) + < 1 H-NMR> → see FIG. 3 < 13 C-NMR> → see FIG.
【0051】実施例3(燐酸エステルの合成―3) 500ml反応フラスコに、オキシ塩化燐76.6g
(0.50モル)と酢酸ブチル200mlを仕込み、1
−(1−(1−n−ブトキシ−2−プロポキシ)−2−
プロポキシ)−2−プロパノール124.2g(0.5
0モル)とトリエチルアミン50.6g(0.50モ
ル)の混合液を氷冷下で攪拌を行いながら内温15〜2
0℃で0.5時間かけて滴下し、25℃で3時間熟成し
た。得られた反応液を濾過して、濾塊を酢酸ブチル10
0mlで洗浄した。濾液と洗液の混合液を減圧下で脱溶
媒し、粗モノ(1−(1−(1−n−ブトキシ−2−プ
ロポキシ)−2−プロポキシ)−2−プロピル)燐酸ジ
クロライドを得た。次に、水200mlが仕込まれた1
l反応フラスコに窒素バブリングを行いながら、得られ
た粗モノ(1−(1−(1−n−ブトキシ−2−プロポ
キシ)−2−プロポキシ)−2−プロピル)燐酸ジクロ
ライドを内温50〜60℃で0.5時間かけて滴下し、
60℃で5時間熟成した。室温に冷却されるまで窒素バ
ブリングを続行した後、酢酸ブチル300mlを加えて
抽出分液した。上層の有機層を、5%の塩酸水200m
lで洗浄し、次いで水200mlで水洗した。次に、上
層の有機層に活性炭(白鷺C)5gを加えて、室温で1
時間攪拌後、濾過した。得られた濾液を、さらに水20
0mlで2回水洗し、減圧下で脱溶媒トッピングを行っ
た。最後に、残渣を室温で濾過(3μm)して、15
6.0g(粗収率95%)のモノ(1−(1−(1−n
−ブトキシ−2−プロポキシ)−2−プロポキシ)−2
−プロピル)燐酸を得た。得られた燐酸エステルの組成
は、以下の通りであった。Example 3 (Synthesis of phosphoric ester-3) 76.6 g of phosphorus oxychloride was placed in a 500 ml reaction flask.
(0.50 mol) and 200 ml of butyl acetate,
-(1- (1-n-butoxy-2-propoxy) -2-
124.2 g (0.5) of propoxy) -2-propanol
0 mol) and 50.6 g (0.50 mol) of triethylamine while stirring under ice-cooling at an internal temperature of 15 to 2 g.
The mixture was added dropwise at 0 ° C over 0.5 hours, and aged at 25 ° C for 3 hours. The obtained reaction solution was filtered, and the filter cake was washed with 10% butyl acetate.
Washed with 0 ml. The mixture of the filtrate and the washing was desolvated under reduced pressure to obtain crude mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride. Next, 1 was charged with 200 ml of water.
While performing bubbling of nitrogen through the reaction flask, the obtained crude mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride was added at an internal temperature of 50 to 60. At 0.5 ° C over 0.5 hours,
Aged at 60 ° C. for 5 hours. After continuing nitrogen bubbling until it was cooled to room temperature, 300 ml of butyl acetate was added thereto to carry out extraction and separation. The upper organic layer is made of 5% hydrochloric acid water 200 m
1 and then with 200 ml of water. Next, 5 g of activated carbon (Shirasagi C) was added to the upper organic layer, and the mixture was added at room temperature for 1 hour.
After stirring for an hour, the mixture was filtered. The obtained filtrate is further added to water 20
After washing twice with 0 ml of water, desolvation topping was performed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give
6.0 g (crude yield 95%) of mono (1- (1- (1-n
-Butoxy-2-propoxy) -2-propoxy) -2
-Propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.
【表3】 シリカゲルカラムクロマトグラフィーで精製して収得し
た同定データを以下に記載する。 <MSスペクトル(FAB(Pos.))>m/z=329(M+H)+ < 1H−NMR> → 図5参照 < 13C−NMR> → 図6参照[Table 3] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 329 (M + H) + < 1 H-NMR> → see FIG. 5 < 13 C-NMR> → see FIG.
【0052】実施例4(燐酸エステルの合成―4) 3l反応フラスコに、オキシ塩化燐411.6g(2.
68モル)とモノクロロベンゼン1500mlを仕込
み、1−(1−(1−n−ブトキシ−2−プロポキシ)
−2−プロポキシ)−2−プロパノール1000.0g
(4.03モル)とピリジン424.6g(5.37モ
ル)の混合液を氷水冷下で攪拌を行いながら内温25〜
30℃で3時間かけて滴下し、30〜40℃で15時間
熟成した。得られた反応液を濾過して、濾塊をモノクロ
ロベンゼン500mlで洗浄した。濾液と洗液の混合液
を減圧下で脱溶媒し、モノ(1−(1−(1−n−ブト
キシ−2−プロポキシ)−2−プロポキシ)−2−プロ
ピル)燐酸ジクロライドと、ジ(1−(1−(1−n−
ブトキシ−2−プロポキシ)−2−プロポキシ)−2−
プロピル)燐酸クロライドの混合液を得た。次に、水1
000mlが仕込まれた3l反応フラスコに窒素バブリ
ングを行いながら、得られたモノ(1−(1−(1−n
−ブトキシ−2−プロポキシ)−2−プロポキシ)−2
−プロピル)燐酸ジクロライドと、ジ(1−(1−(1
−n−ブトキシ−2−プロポキシ)−2−プロポキシ)
−2−プロピル)燐酸クロライドの混合液を内温50〜
60℃で1時間かけて滴下し、60℃で5時間熟成し
た。反応終了後、室温に冷却されるまで窒素バブリング
を続行した後、モノクロロベンゼン1000mlを加え
て抽出分液した。得られた有機層を、5%の塩酸水50
0mlで洗浄し、次いで水500mlで水洗した。次
に、有機層に活性炭(白鷺C)30gを加えて、室温で
1時間攪拌後、濾過した。得られた濾液を、さらに水5
00mlで2回水洗し、減圧下で脱溶媒トッピングを行
った。最後に、残渣を室温で濾過(3μm)して、10
54.9g(粗収率94%)のモノ(1−(1−(1−
n−ブトキシ−2−プロポキシ)−2−プロポキシ)−
2−プロピル)燐酸と、ジ(1−(1−(1−n−ブト
キシ−2−プロポキシ)−2−プロポキシ)−2−プロ
ピル)燐酸の混合液を得た。得られた燐酸エステルの組
成は、以下の通りであった。Example 4 (Synthesis of phosphoric acid ester-4) 411.6 g of phosphorus oxychloride (2.
68 mol) and 1500 ml of monochlorobenzene, and 1- (1- (1-n-butoxy-2-propoxy)
-2-propoxy) -2-propanol 1000.0 g
(4.03 mol) and a mixed solution of 424.6 g (5.37 mol) of pyridine were stirred under ice-water cooling while the internal temperature was 25 to 25 mol / min.
The solution was added dropwise at 30 ° C over 3 hours, and aged at 30 to 40 ° C for 15 hours. The obtained reaction solution was filtered, and the filter cake was washed with 500 ml of monochlorobenzene. The mixture of the filtrate and the washing solution was desolvated under reduced pressure, and mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride and di (1 -(1- (1-n-
Butoxy-2-propoxy) -2-propoxy) -2-
A mixed solution of propyl) phosphoric acid chloride was obtained. Next, water 1
While performing nitrogen bubbling on a 3 l reaction flask charged with 000 ml, the obtained mono (1- (1- (1-n
-Butoxy-2-propoxy) -2-propoxy) -2
-Propyl) phosphoric acid dichloride and di (1- (1- (1
-N-butoxy-2-propoxy) -2-propoxy)
-2-propyl) phosphoric acid chloride mixture at an internal temperature of 50 to
The solution was added dropwise at 60 ° C. over 1 hour and aged at 60 ° C. for 5 hours. After completion of the reaction, nitrogen bubbling was continued until the mixture was cooled to room temperature, and then 1000 ml of monochlorobenzene was added to carry out extraction and separation. The obtained organic layer was washed with a 5% aqueous hydrochloric acid solution (50%).
It was washed with 0 ml and then with 500 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate is further added to water 5
After washing twice with 00 ml, desolvation topping was performed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature and 10
54.9 g (crude yield 94%) of mono (1- (1- (1-
n-butoxy-2-propoxy) -2-propoxy)-
A mixed solution of 2-propyl) phosphoric acid and di (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.
【表4】 [Table 4]
【0053】実施例5(燐酸エステルの調整) 実施例1で得られたモノ(1−(1−n−ブトキシ−2
−プロポキシ)−2−プロピル)燐酸400gと、実施
例2で得られたジ(1−(1−n−ブトキシ−2−プロ
ポキシ)−2−プロピル)燐酸600gを混合して、モ
ノエステルとジエステルの混合燐酸エステルを1000
g調整した。得られた混合燐酸エステルの組成は、以下
の通りであった。Example 5 (Preparation of Phosphoric Ester) The mono (1- (1-n-butoxy-2) obtained in Example 1 was obtained.
(Propoxy) -2-propyl) phosphoric acid (400 g) and di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid obtained in Example 2 (600 g) were mixed to obtain a monoester and a diester. 1000 mixed phosphate esters
g was adjusted. The composition of the obtained mixed phosphate was as follows.
【表5】 [Table 5]
【0054】実施例6(燐酸エステルの合成―5) 1000ml反応フラスコに、オキシ塩化燐137.1
g(0.89モル)とモノクロロベンゼン500mlを
仕込み、1−(1−(1−メトキシ−2−プロポキシ)
−2−プロポキシ)−2−プロパノール368.8g
(1.79モル)とピリジン169.7g(2.15モ
ル)の混合液を氷水冷下で攪拌を行いながら内温0〜2
5℃で2時間かけて滴下し、25〜30℃で8時間熟成
した。得られた反応液を濾過して、濾塊をモノクロロベ
ンゼン800mlで洗浄した。濾液と洗液の混合液を減
圧下で脱溶媒し、粗ジ(1−(1−(1−メトキシ−2
−プロポキシ)−2−プロポキシ)−2−プロピル)燐
酸クロライド550.0gを得た。次に、水500ml
が仕込まれた2l反応フラスコに窒素バブリングを行い
ながら、得られた粗ジ(1−(1−(1−メトキシ−2
−プロポキシ)−2−プロポキシ)−2−プロピル)燐
酸クロライドを、内温50〜55℃で1時間かけて滴下
し、60℃で5時間熟成した。反応終了後、室温に冷却
されるまで窒素バブリングを続行した後、モノクロロベ
ンゼン500mlを加えて抽出分液した。更にこの抽出
操作をもう一度行った。得られた有機層を、5%の塩酸
水200mlで洗浄し、次いで水200mlで水洗し
た。次に、有機層に活性炭(白鷺C)10gを加えて、
室温で1時間攪拌後、濾過した。得られた濾液を、さら
に水200mlで2回水洗し、減圧下で脱溶媒トッピン
グを行った。最後に、残渣を室温で濾過(3μm)し
て、318.4g(粗収率75%)のジ(1−(1−
(1−メトキシ−2−プロポキシ)−2−プロポキシ)
−2−プロピル)燐酸を得た。得られた燐酸エステルの
組成は、以下の通りであった。Example 6 (Synthesis of phosphoric acid ester-5) Phosphorus oxychloride 137.1 was placed in a 1000 ml reaction flask.
g (0.89 mol) and 500 ml of monochlorobenzene were charged, and 1- (1- (1-methoxy-2-propoxy)) was added.
-3-propoxy) -2-propanol 368.8 g
(1.79 mol) and a mixture of pyridine (169.7 g, 2.15 mol) and an inner temperature of 0 to 2 while stirring under ice-water cooling.
The solution was dropped at 5 ° C over 2 hours, and aged at 25 to 30 ° C for 8 hours. The obtained reaction solution was filtered, and the filter cake was washed with 800 ml of monochlorobenzene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure, and crude di (1- (1- (1-methoxy-2)
550.0 g of -propoxy) -2-propoxy) -2-propyl) phosphoric acid chloride were obtained. Next, 500 ml of water
While performing nitrogen bubbling on the 2 l reaction flask charged with, the crude di (1- (1- (1-methoxy-2) -2
-Propoxy) -2-propoxy) -2-propyl) phosphoric acid chloride was added dropwise at an internal temperature of 50 to 55 ° C over 1 hour, and the mixture was aged at 60 ° C for 5 hours. After completion of the reaction, nitrogen bubbling was continued until the mixture was cooled to room temperature, and then 500 ml of monochlorobenzene was added to carry out extraction and separation. This extraction operation was performed again. The obtained organic layer was washed with 200 ml of 5% hydrochloric acid and then with 200 ml of water. Next, 10 g of activated carbon (Shirasagi C) was added to the organic layer,
After stirring at room temperature for 1 hour, the mixture was filtered. The obtained filtrate was further washed twice with 200 ml of water and subjected to desolvation topping under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give 318.4 g (75% crude yield) of di (1- (1-
(1-methoxy-2-propoxy) -2-propoxy)
(-2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.
【表6】 シリカゲルカラムクロマトグラフィーで精製して収得し
た同定データを以下に記載する。 <MSスペクトル(FAB(Pos.))>m/z=475(M+H)+ < 1H−NMR> → 図7参照 < 13C−NMR> → 図8参照[Table 6] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 475 (M + H) + < 1 H-NMR> → see FIG. 7 < 13 C-NMR> → see FIG. 8
【0055】実施例7 m−キシリレンジイソシアナート364g(1.93モ
ル)とジブチル錫ジクロリド0.070g(100pp
m)の混合液に、実施例5の燐酸エステルを0.70g
(1000ppm)加えて窒素下で混合溶解した。次い
で、この液に1,2−ビス(2−メルカプトエチルチ
オ)−3−プロパンチオール336g(1.29モル)
を加えて混合し、減圧下で混合脱泡を行った。脱泡終了
後、あらかじめ用意しておいた成型モールドに注入し、
室温から120℃まで徐々昇温し、20時間かけて加熱
硬化させた。冷却後、離型して得られたレンズは無色透
明で、屈折率Nd=1.660、アッベ数νd=32で
あった。離型剤の評価結果は表7に示す。Example 7 364 g (1.93 mol) of m-xylylene diisocyanate and 0.070 g (100 pp) of dibutyltin dichloride were used.
0.70 g of the phosphoric ester of Example 5 in the mixture of m)
(1000 ppm) and mixed and dissolved under nitrogen. Next, 336 g (1.29 mol) of 1,2-bis (2-mercaptoethylthio) -3-propanethiol was added to this solution.
Was added and mixed, and mixed and defoamed under reduced pressure. After defoaming, inject into the prepared mold beforehand,
The temperature was gradually increased from room temperature to 120 ° C., and the composition was cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold was colorless and transparent, and had a refractive index Nd of 1.660 and an Abbe number νd of 32. Table 7 shows the evaluation results of the release agents.
【0056】実施例8〜12、比較例1〜7 離型剤の添加量と種類を変えて、実施例6と同様の試験
を行なった。結果を表7に示す。Examples 8 to 12 and Comparative Examples 1 to 7 The same tests as in Example 6 were carried out by changing the amount and type of the release agent. Table 7 shows the results.
【0057】[0057]
【表7】 [Table 7]
【0058】(ゼレック UN の構造) (JP−506Hの構造と組成) (プライサーフ A212E の構造) (Structure of Zelek UN) (Structure and composition of JP-506H) (Structure of Plysurf A212E)
【0059】実施例13 ビス(イソシアナトメチル)ノルボルナン348g
(1.69モル)とジブチル錫ジクロリド0.28g
(400ppm)の混合液に、実施例4の燐酸エステル
を0.7g(1000ppm)加えて窒素下で混合溶解
した。次いで、この液にペンタエリスリトールテトラキ
ス(3−メルカプトプロピオネート)171g(0.3
5モル)と4,8−ビス(メルカプトメチル)−3,
6,9−トリチア−1,11−ウンデカンジチオール1
81g(0.49モル)を加えて混合し、減圧下で混合
脱泡を行った。脱泡終了後、あらかじめ用意しておいた
成型モールドに注入し、室温から130℃まで徐々昇温
し、20時間かけて加熱硬化させた。冷却後、離型して
得られたレンズは無色透明で、屈折率Nd=1.59
4、アッベ数νd=43であった。離型剤の評価結果は
表8に示す。Example 13 Bis (isocyanatomethyl) norbornane 348 g
(1.69 mol) and 0.28 g of dibutyltin dichloride
(400 ppm) was mixed with 0.7 g (1000 ppm) of the phosphoric acid ester of Example 4 under nitrogen. Next, 171 g of pentaerythritol tetrakis (3-mercaptopropionate) (0.3 g) was added to the solution.
5 mol) and 4,8-bis (mercaptomethyl) -3,
6,9-trithia-1,11-undecanedithiol 1
81 g (0.49 mol) was added and mixed, and mixed and defoamed under reduced pressure. After the defoaming was completed, the mixture was poured into a molding mold prepared in advance, gradually heated from room temperature to 130 ° C., and cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold is colorless and transparent, and has a refractive index Nd of 1.59.
4, Abbe number νd = 43. Table 8 shows the evaluation results of the release agents.
【0060】実施例14〜17 離型剤の種類と量を変えて、実施例13と同様の試験を
行なった。結果を表8に示す。Examples 14 to 17 The same tests as in Example 13 were carried out, except that the type and amount of the release agent were changed. Table 8 shows the results.
【0061】[0061]
【表8】 [Table 8]
【0062】実施例19 ビス(イソシアナトメチルチオ)メタン425g(2.
23モル)とジブチル錫ジクロリド0.035g(50
ppm)の混合液に、実施例5の燐酸エステルを0.7
g(1000ppm)加えて窒素下で混合溶解した。次
いで、この液に2,4−ビス(メルカプトメチル)−3
−チア−1,5−ペンタンジチオール275g(1.1
2モル)を加えて混合し、減圧下で混合脱泡を行った。
脱泡終了後、あらかじめ用意しておいた成型モールドに
注入し、室温から120℃まで徐々昇温し、20時間か
けて加熱硬化させた。冷却後、離型して得られたレンズ
は無色透明で、屈折率Nd=1.694、アッベ数νd
=33であった。着色度、透明性、離型性は、全く問題
なかった。Example 19 425 g of bis (isocyanatomethylthio) methane (2.
23 mol) and 0.035 g of dibutyltin dichloride (50
ppm) of the phosphoric acid ester of Example 5
g (1000 ppm) and mixed and dissolved under nitrogen. Next, 2,4-bis (mercaptomethyl) -3 was added to this solution.
275 g of thia-1,5-pentanedithiol (1.1
2 mol) were added and mixed, and mixed and defoamed under reduced pressure.
After the defoaming was completed, the mixture was poured into a molding mold prepared in advance, gradually heated from room temperature to 120 ° C., and cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold is colorless and transparent, has a refractive index Nd of 1.694, and an Abbe number νd.
= 33. There were no problems with the degree of coloring, transparency, and releasability.
【0063】[0063]
【発明の効果】本発明によれば、成形型から容易に透明
樹脂が離型し、なおかつ極めて透明性の高い製品が得ら
れる。According to the present invention, a transparent resin is easily released from a molding die, and a product having extremely high transparency can be obtained.
【図1】モノ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸の 1H−NMRFIG. 1. 1 H-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid
【図2】モノ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸の 13C−NMRFIG. 2: 13 C-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid
【図3】ジ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸の 1H−NMRFIG. 3 1 H-NMR of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid
【図4】ジ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロピル)燐酸の 13C−NMRFIG. 4: 13 C-NMR of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid
【図5】モノ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロポキシ)燐酸の 1H−NMRFIG. 5 1 H-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propoxy) phosphoric acid
【図6】モノ(1−(1−n−ブトキシ−2−プロポキ
シ)−2−プロポキシ)燐酸の 13C−NMRFIG. 6: 13 C-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propoxy) phosphoric acid
【図7】ジ(1−(1−メトキシ−2−プロポキシ)−
2−プロポキシ)プロピル)燐酸の 1H−NMRFIG. 7: Di (1- (1-methoxy-2-propoxy)-
1 H-NMR of 2-propoxy) propyl) phosphoric acid
【図8】ジ(1−(1−メトキシ−2−プロポキシ)−
2−プロポキシ)プロピル)燐酸の 13C−NMRFIG. 8: Di (1- (1-methoxy-2-propoxy)-
13 C-NMR of 2-propoxy) propyl) phosphoric acid
───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4F202 AA42 AB07 AH73 AH74 CA01 CA11 CM55 4H050 AA01 AA02 AA03 AB99 WA15 WA23 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F202 AA42 AB07 AH73 AH74 CA01 CA11 CM55 4H050 AA01 AA02 AA03 AB99 WA15 WA23
Claims (6)
し、R1はフェニル基を除いた炭素数1〜20の残基を
示し、R2、R3はそれぞれ水素原子、メチル基、エチル
基を示す。但し、R2、R3がともに水素原子である場合
を除く。)で表される燐酸エステル。[Claim 1] The following formula (1) (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R 1 represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R 2 and R 3 each represent a hydrogen atom , A methyl group and an ethyl group, provided that R 2 and R 3 are not both hydrogen atoms).
し、R1はフェニル基を除いた炭素数1〜20の残基を
示し、R2、R3はそれぞれ水素原子、メチル基、エチル
基を示す。但し、R2、R3がともに水素原子である場合
を除く。Xはハロゲン原子を表す。)で表される燐酸エ
ステルハライドを、加水分解することを特徴とする請求
項1記載の燐酸エステルの製造方法。2. The following formula (2): (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R 1 represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R 2 and R 3 each represent a hydrogen atom , A methyl group and an ethyl group, except that both R 2 and R 3 are hydrogen atoms, and X represents a halogen atom.) The method for producing a phosphate according to claim 1.
剤。3. A release agent containing the phosphoric ester according to claim 1.
記載の透明樹脂。5. The transparent resin is a transparent optical material.
The transparent resin described.
求項4記載の透明樹脂。6. The transparent resin according to claim 4, wherein the transparent resin is a plastic lens.
Priority Applications (1)
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JP10368562A JP2000191673A (en) | 1998-12-25 | 1998-12-25 | New phosphoric acid ester and mold releasing agent comprising the compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10368562A JP2000191673A (en) | 1998-12-25 | 1998-12-25 | New phosphoric acid ester and mold releasing agent comprising the compound |
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---|---|
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Family
ID=18492152
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JP10368562A Pending JP2000191673A (en) | 1998-12-25 | 1998-12-25 | New phosphoric acid ester and mold releasing agent comprising the compound |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016104744A1 (en) * | 2014-12-26 | 2016-06-30 | 三井化学株式会社 | Internal release agent, composition including internal release agent, and plastic lens production method using said composition |
EP3530684A1 (en) | 2018-02-23 | 2019-08-28 | SKC Co., Ltd. | Phosphorus-based releasing agent, optical polymerizable composition comprising same and preparation thereof |
US11267953B2 (en) | 2015-03-12 | 2022-03-08 | Hoya Lens Thailand Ltd. | Iso(thio)cyanate composition, and resin composition including same for optical member |
-
1998
- 1998-12-25 JP JP10368562A patent/JP2000191673A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016104744A1 (en) * | 2014-12-26 | 2016-06-30 | 三井化学株式会社 | Internal release agent, composition including internal release agent, and plastic lens production method using said composition |
JP6009722B1 (en) * | 2014-12-26 | 2016-10-19 | 三井化学株式会社 | Internal mold release agent, composition containing the internal mold release agent, and method for producing a plastic lens using the composition |
KR101788522B1 (en) | 2014-12-26 | 2017-10-19 | 미쯔이가가꾸가부시끼가이샤 | Internal release agent, composition including internal release agent, and process for producing a plastic lens using same composition |
US10239239B2 (en) | 2014-12-26 | 2019-03-26 | Mitsui Chemicals, Inc. | Internal release agent, composition including internal release agent, and process for producing a plastic lens using same composition |
US11267953B2 (en) | 2015-03-12 | 2022-03-08 | Hoya Lens Thailand Ltd. | Iso(thio)cyanate composition, and resin composition including same for optical member |
EP3530684A1 (en) | 2018-02-23 | 2019-08-28 | SKC Co., Ltd. | Phosphorus-based releasing agent, optical polymerizable composition comprising same and preparation thereof |
US11248011B2 (en) | 2018-02-23 | 2022-02-15 | Skc Co., Ltd. | Phosphorus-based releasing agent, optical polymerizable composition comprising same and preparation thereof |
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