JP3844789B2 - Novel alicyclic diol and process for producing the same - Google Patents
Novel alicyclic diol and process for producing the same Download PDFInfo
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- JP3844789B2 JP3844789B2 JP00267194A JP267194A JP3844789B2 JP 3844789 B2 JP3844789 B2 JP 3844789B2 JP 00267194 A JP00267194 A JP 00267194A JP 267194 A JP267194 A JP 267194A JP 3844789 B2 JP3844789 B2 JP 3844789B2
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- tricyclo
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Description
【０００１】
【産業上の利用分野】
本発明は式〔１〕で表される
【０００２】
【化４】
新規脂環式ジオール及びその製造法に関する。式〔１〕で表される脂環式ジオールは高分子、特にポリエステルの原料として利用できる。
【０００４】
【従来の技術】
従来の脂環式ジオールとしては、ペルヒドロ−１，４：５，８−ジメタナフタレン−８，９−ジメタノールをモノマーとするポリエステルがガラス転移温度が高く、寸法安定性に優れ、写真用フィルムのベース等に用いられることが知られている（米国防衛特許第８９６０３３号）。しかし、そのジオールの製造収率は低く、実用的な問題点を抱えていた。
【０００５】
本発明者らは、すでに工業的に安価なジシクロペンタジエンから高収率で、ノルボルナン骨格を有するトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸誘導体を製造する方法を見出している。（特公平４−６０１００，特公平２−３２２６７，特公平５−２６７４）
即ち、以下の反応式で示すように安価な原料であるジシクロペンタジエン（ＤＣＰＤ）、一酸化炭素及びアルコールを触媒及び酸化剤の存在下に反応させることによって、高収率でトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸ジエステル（ＴＣＤＥ）を得ることができる。
【０００６】
又、このジエステル化反応に於て特定のアルコール、例えば第３級アルコール、アリルアルコール、エチレングリコールを用いることによって一挙にジシクロペンタジエン（ＤＣＰＤ）よりトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸無水物（ＴＣＤＡ）が得られる。
ＴＣＤＥは、加水分解することによってトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸（ＴＣＤＣ）が得られる。ＴＣＤＣは、脱水することによってＴＣＤＡが得られる。又、ＴＣＤＣは、エステル化することによって種々のＴＣＤＥに誘導できる。
【０００７】
【化５】
更に本発明者らは特願平５−２０１４４９号に於いて、上述のＴＣＤＥ、ＴＣＤＣ及びＴＣＤＡを還元し同様に高収率でトリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸誘導体を得ることを見出している。
【０００９】
【化６】
【発明が解決しようとする課題】
本発明者らは先に述べた従来より公知の脂環式ジオールの製造における収率が低いという実用的な問題点が無い、脂環式ジオールを見出すことを課題とした。
その結果、本発明者らは上述したＴＣＤＥ或いはＤＨ−ＴＣＤＥ等を用い、新規な脂環式ジオールを高収率に得る方法を見出した。即ち、本発明の目的はポリエステル樹脂等の原料として有用な新規な脂環式ジオールを提供することにある。
【００１１】
【課題を解決するための手段】
即ち、本発明は、式〔１〕で表される
【００１２】
【化７】
８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンに関する。
更に、式〔２〕で表される化合物
【００１４】
【化８】
（Ａは、−ＯＨ基、−ＯＲ基（Ｒはアルキル基、不飽和アルキル基、シクロアルキル基、ベンゼン置換アルキル、ベンゼン置換不飽和アルキルでアルキル及び不飽和アルキルはＯ，Ｎ原子を含んでいてよい。）又は、一緒になって＞Ｏ（酸素原子）を表す。）
トリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸誘導体、又は式〔３〕で表されるトリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸誘導体を還元することを特徴とする上記式〔１〕で表される８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンの製造法に関する。
【００１６】
以下、本発明をさらに詳細に説明する。本発明に用いられる原料としては、先に述べたジシクロペンタジエン（ＤＣＰＤ）をジエステル化反応によって得られるトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸ジエステル、そのジエステルを加水分解によって得られるトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸、前記カルボン酸の酸ハライドであるトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸ハライド、或いは前記ジカルボン酸を脱水して得られるトリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸無水物、さらにこれらの化合物の水素化物であるトリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸ジエステル、トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸ハライド及びトリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸無水物が挙げられる。
【００１７】
次に、本発明に適用できる還元方法としては、以下に述べる還元方法が適用出来る。
（１）金属水素化物を用いる方法
金属水素化物としては、ＡｌＨ3 、ＬｉＡｌＨ4 、ＬｉＡｌＨ4 −ＡｌＣｌ3 、ＬｉＡｌＨ（ＯＣＨ3 ）3 、ＮａＡｌＨ2 （ＯＣＨ2 ＣＨ2 ＯＣＨ3 ）3 、ＡｌＨ（ｎ−Ｃ4 Ｈ9 ）2 、ＡｌＨ（ｉ−Ｃ4 Ｈ9 ）2 、ＢＨ3 、ＮａＢＨ4 、ＮａＢＨ4 −ＡｌＣｌ3 及びＮａＢＨ（ＯＣＨ3 ）3 等が挙げられる。
（２）接触水素化法
触媒としては、銅クロマイト、酸化レニウム、酸化ロジウム、パラジウム、ニッケル、ルテニウム及びクロム等が挙げられる。
（３）ナトリウム還元法
アルコールの存在下にナトリウムにより還元する方法。
（４）電解還元法
カルボン酸は電解還元法によりアルコールを合成することができる。
【００１８】
金属水素化物を用いる場合は、通常行われる方法が適用できる。金属水素化物の使用量は基質に対して金属水素化物を理論量に対し０．５〜１．５倍量用いる。反応は、ヘキサン、トルエン、テトラヒドロフラン、ジオキサン等を溶媒として用い、−４０℃から５０℃、好ましくは氷冷下から室温の温度範囲で行う。
工業的な方法としては、触媒の存在下に水素による接触還元法が好ましく、触媒としては銅クロマイト触媒が一般的であり、他の金属、例えばパラジウム、ルテニウム及びロジウム等を含む触媒系も有効である。
【００１９】
上記触媒を用いる水素による接触還元反応は、１００〜３００℃の範囲、好ましくは１５０〜２５０℃の範囲で、水素圧力は４０，０００ｋＰａ以下、好ましくは５，０００〜３５，０００ｋＰａの範囲である。反応時間は、温度、水素圧の条件により異なるが、２０分〜５０時間の範囲で、好ましいくは３０分〜１０時間の範囲である。
【００２０】
また、接触還元反応は原料を溶解し、触媒との分離が容易で、反応に関与しない有機溶媒を用いることが好ましい。有機溶媒としては、ジオキサン、テトラヒドロフラン及び１，２−ジメトキシエタン等のエーテル類、シクロヘキサンやヘプタン等の炭化水素類、メタノール、エタノール等のアルコール類等が挙げられる。触媒の使用量は、基質に対し１〜３０重量％、好ましくは３〜２０重量％である。
【００２１】
以下、実施例により本発明をさらに具体的に説明するが本発明はこれらによって限定されるものではない。
【００２２】
【実施例】
実施例１
テトラヒドロフラン（ＴＨＦ）３０ｍｌ中に氷冷下、リチウムアルミニウムハイドライド１．０ｇ（２６ｍｍｏｌ）を懸濁させた。その攪拌液へ、トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸ジメチルエステル５．０ｇ（２０ｍｍｏｌ）をＴＨＦ２０ｍｌに溶解した溶液を１０℃以下で滴下した。その後ゆっくり室温に戻し、２５℃で３時間攪拌を行った。反応終了後再び氷冷し、６Ｎ塩酸１２ｍｌを注意深く滴下した。続いてろ過により残査を除去した後、ろ液に酢酸エチルを加え抽出した。この溶液を水洗後、無水芒硝で脱水した後、濃縮乾燥すると純白結晶３．４ｇが得られた。この結晶をガスクロマトグラフィーで分析の結果単一のピークであった。
【００２３】
更に以下の分析を行った。
マススペクトル（ｍ／ｅ（％））：１９７〔Ｍ＋Ｈ〕+ （７７）、１７７（９１）、１６１（１００）
1Ｈ−ＮＭＲ（ＣＤＣｌ3 ）：４．０６、３．７９、３．７７、３．７５、３．５５、３．５４、３．５３、３．５２、２．３７、２．２２、２．２０、１．８４、１．６５、１．６４、１．６２、１．６０、１．５７、１．４８、１．４６、１．３１、１．２９
13Ｃ−ＮＭＲ（ＣＤＣｌ3 ）：７７．３、７７．０、７６．８、６４．４、４５
．７、４１．１、３９．７、２９．０、２６．７
融点： １１５〜１１７℃
以上から本結晶は、目的とする８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンであることが判明した。
実施例２
トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸ジメチルエステル５．０ｇ（２０ｍｍｏｌ）、銅クロマイト触媒０．５ｇとジオキサン５０ｍｌを１００ｍｌのオートクレーブに仕込み、窒素置換後水素圧を２００００ｋＰａにし反応温度２００℃で４時間攪拌を行った。
【００２４】
冷却後、ろ過により触媒を除去し、そのろ液を濃縮、乾燥すると粗結晶３．３ｇが得られた。この結晶をガスクロマトグラフィーで分析の結果、純度９６．８％の目的とする８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンの結晶であることが判った。
【図面の簡単な説明】
【図１】 実施例１で得られた８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンの 1Ｈ−ＮＭＲによるチャート
【図２】 実施例１で得られた８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンの13Ｃ−ＮＭＲによるチャート[0001]
[Industrial application fields]
The present invention is represented by the formula [1].
[Formula 4]
The present invention relates to a novel alicyclic diol and a method for producing the same. The alicyclic diol represented by the formula [1] can be used as a raw material for polymers, particularly polyesters.
[0004]
[Prior art]
As a conventional alicyclic diol, a polyester having perhydro-1,4: 5,8-dimethanaphthalene-8,9-dimethanol as a monomer has a high glass transition temperature, excellent dimensional stability, and a photographic film. It is known to be used for the base of the US (US Pat. No. 896033). However, the production yield of the diol was low and had practical problems.
[0005]
The present inventors have already obtained tricyclo [5.2.1.0 2,6 ] dec-3-ene-8,9-dicarboxylic acid having a norbornane skeleton in high yield from industrially inexpensive dicyclopentadiene. A method for producing acid derivatives has been found. (Japanese Patent Publication 4-60100, Japanese Patent Publication 2-32267, Japanese Patent Publication 5-2674)
That is, as shown in the following reaction formula, tricyclo [5.2] is produced in a high yield by reacting dicyclopentadiene (DCPD), which is an inexpensive raw material, carbon monoxide and alcohol in the presence of a catalyst and an oxidizing agent. 1.0 2,6 ] Dece-3-ene-8,9-dicarboxylic acid diester (TCDE) can be obtained.
[0006]
In this diesterification reaction, by using a specific alcohol such as tertiary alcohol, allyl alcohol, or ethylene glycol, tricyclo [5.2.1.0 2,6 ] can be obtained at once from dicyclopentadiene (DCPD). Dece-3-ene-8,9-dicarboxylic anhydride (TCDA) is obtained.
TCDE is hydrolyzed to give tricyclo [5.2.1.0 2,6 ] dec-3-ene-8,9-dicarboxylic acid (TCDC). TCDC is obtained by dehydrating TCDC. TCDC can also be derived into various TCDEs by esterification.
[0007]
[Chemical formula 5]
Furthermore, the present inventors reduced the above-mentioned TCDE, TCDC and TCDA in Japanese Patent Application No. 5-2014449, and similarly obtained tricyclo [5.2.1.0 2,6 ] decane-8, It has been found that 9-dicarboxylic acid derivatives are obtained.
[0009]
[Chemical 6]
[Problems to be solved by the invention]
The present inventors made it a subject to find the alicyclic diol which does not have the practical problem that the yield in manufacture of the conventionally well-known alicyclic diol mentioned above was low.
As a result, the present inventors have found a method for obtaining a novel alicyclic diol in high yield using the above-described TCDE or DH-TCDE. That is, an object of the present invention is to provide a novel alicyclic diol useful as a raw material for polyester resins and the like.
[0011]
[Means for Solving the Problems]
That is, the present invention is represented by the formula [1].
[Chemical 7]
It relates to 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane.
Furthermore, a compound represented by the formula [2]
[Chemical 8]
(A is an -OH group, -OR group (R is an alkyl group, an unsaturated alkyl group, a cycloalkyl group, a benzene-substituted alkyl, a benzene-substituted unsaturated alkyl, and the alkyl and unsaturated alkyl contain O, N atoms. Or together represent> O (oxygen atom).)
Tricyclo [5.2.1.0 2,6 ] dec-3-en-8,9-dicarboxylic acid derivative or tricyclo [5.2.1.0 2,6 ] represented by the formula [3] A process for producing 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane represented by the above formula [1], characterized by reducing a decane-8,9-dicarboxylic acid derivative About.
[0016]
Hereinafter, the present invention will be described in more detail. As a raw material used in the present invention, tricyclo [5.2.1.0 2,6 ] dec-3-ene-8,9- obtained by diesterification of the above-mentioned dicyclopentadiene (DCPD). Dicarboxylic acid diester, tricyclo [5.2.1.0 2,6 ] dec-3-ene-8,9-dicarboxylic acid obtained by hydrolysis of the diester, tricyclo [5 which is an acid halide of the carboxylic acid .2.1.0 2,6 ] dec-3-ene-8,9-dicarboxylic acid halide, or tricyclo [5.2.1.0 2,6 ] dece obtained by dehydrating the dicarboxylic acid. -3-ene-8,9-dicarboxylic anhydride, and tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid diester, tricyclo [5. 2.1.0 2,6] decane 8,9-dicarboxylic acid halide and tricyclo [5.2.1.0 2,6] decane-8,9-dicarboxylic acid anhydride.
[0017]
Next, as a reduction method applicable to the present invention, the following reduction methods can be applied.
(1) Method using metal hydride As the metal hydride, AlH 3 , LiAlH 4 , LiAlH 4 —AlCl 3 , LiAlH (OCH 3 ) 3 , NaAlH 2 (OCH 2 CH 2 OCH 3 ) 3 , AlH (n— C 4 H 9) 2, AlH (i-C 4 H 9) 2,
(2) Examples of the catalytic hydrogenation catalyst include copper chromite, rhenium oxide, rhodium oxide, palladium, nickel, ruthenium and chromium.
(3) Sodium reduction method A method of reducing with sodium in the presence of alcohol.
(4) Electrolytic reduction method Carboxylic acid can synthesize alcohol by electrolytic reduction method.
[0018]
In the case of using a metal hydride, a conventionally performed method can be applied. The amount of metal hydride used is 0.5 to 1.5 times the theoretical amount of metal hydride with respect to the substrate. The reaction is carried out using hexane, toluene, tetrahydrofuran, dioxane or the like as a solvent in a temperature range of −40 ° C. to 50 ° C., preferably under ice cooling to room temperature.
As an industrial method, a catalytic reduction method using hydrogen in the presence of a catalyst is preferable. A copper chromite catalyst is generally used as the catalyst, and a catalyst system containing other metals such as palladium, ruthenium and rhodium is also effective. is there.
[0019]
The catalytic reduction reaction with hydrogen using the above catalyst is in the range of 100 to 300 ° C., preferably in the range of 150 to 250 ° C., and the hydrogen pressure is 40,000 kPa or less, preferably in the range of 5,000 to 35,000 kPa. While the reaction time varies depending on the temperature and hydrogen pressure conditions, it is in the range of 20 minutes to 50 hours, preferably in the range of 30 minutes to 10 hours.
[0020]
In the catalytic reduction reaction, it is preferable to use an organic solvent that dissolves the raw material, is easily separated from the catalyst, and does not participate in the reaction. Examples of the organic solvent include ethers such as dioxane, tetrahydrofuran and 1,2-dimethoxyethane, hydrocarbons such as cyclohexane and heptane, alcohols such as methanol and ethanol, and the like. The amount of the catalyst used is 1 to 30% by weight, preferably 3 to 20% by weight, based on the substrate.
[0021]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[0022]
【Example】
Example 1
Lithium aluminum hydride 1.0 g (26 mmol) was suspended in 30 ml of tetrahydrofuran (THF) under ice cooling. A solution prepared by dissolving 5.0 g (20 mmol) of tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid dimethyl ester in 20 ml of THF was added dropwise to the stirring solution at 10 ° C. or lower. Thereafter, the temperature was slowly returned to room temperature, and the mixture was stirred at 25 ° C. for 3 hours. After completion of the reaction, the mixture was ice-cooled again, and 12 ml of 6N hydrochloric acid was carefully added dropwise. Subsequently, the residue was removed by filtration, and the filtrate was extracted with ethyl acetate. This solution was washed with water, dehydrated with anhydrous sodium sulfate, and concentrated to dryness to obtain 3.4 g of pure white crystals. This crystal was analyzed by gas chromatography and found to have a single peak.
[0023]
Furthermore, the following analysis was performed.
Mass spectrum (m / e (%)): 197 [M + H] + (77), 177 (91), 161 (100)
1 H-NMR (CDCl 3 ): 4.06, 3.79, 3.77, 3.75, 3.55, 3.54, 3.53, 3.52, 2.37, 2.22, 2 .20, 1.84, 1.65, 1.64, 1.62, 1.60, 1.57, 1.48, 1.46, 1.31, 1.29
13 C-NMR (CDCl 3 ): 77.3, 77.0, 76.8, 64.4, 45
. 7, 41.1, 39.7, 29.0, 26.7
Melting point: 115-117 ° C
From the above, this crystal was found to be the desired 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane.
Example 2
Tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid dimethyl ester (5.0 g, 20 mmol), copper chromite catalyst (0.5 g) and dioxane (50 ml) were charged into a 100 ml autoclave, and after nitrogen substitution, hydrogen was added. The pressure was set to 20000 kPa, and the mixture was stirred at a reaction temperature of 200 ° C. for 4 hours.
[0024]
After cooling, the catalyst was removed by filtration, and the filtrate was concentrated and dried to obtain 3.3 g of crude crystals. As a result of analysis by gas chromatography, the crystal was found to be the desired 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane crystal having a purity of 96.8%.
[Brief description of the drawings]
1 is a chart by 1 H-NMR of 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane obtained in Example 1. FIG. 2 is obtained in Example 1. 13 C-NMR chart of 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane
Claims (2)
トリシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸誘導体、又は式〔３〕で表される
トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジカルボン酸誘導体を還元することを特徴とする請求項１記載の式〔１〕で表される８，９−ジヒドロキシメチル−トリシクロ〔５．２．１．０2,6 〕デカンの製造法Represented by equation [2]
Tricyclo [5.2.1.0 2,6 ] dec-3-ene-8,9-dicarboxylic acid derivative, or represented by the formula [3]
A tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid derivative is reduced, wherein 8,9-dihydroxymethyl- represented by the formula [1] according to claim 1 is reduced. Method for producing tricyclo [5.2.1.0 2,6 ] decane
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00267194A JP3844789B2 (en) | 1994-01-14 | 1994-01-14 | Novel alicyclic diol and process for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00267194A JP3844789B2 (en) | 1994-01-14 | 1994-01-14 | Novel alicyclic diol and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07206740A JPH07206740A (en) | 1995-08-08 |
| JP3844789B2 true JP3844789B2 (en) | 2006-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP00267194A Expired - Lifetime JP3844789B2 (en) | 1994-01-14 | 1994-01-14 | Novel alicyclic diol and process for producing the same |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1112995B1 (en) | 1998-09-11 | 2007-04-11 | Nissan Chemical Industries, Ltd. | Alicyclic compounds and curable resin composition |
| JP4774802B2 (en) * | 2005-05-16 | 2011-09-14 | セントラル硝子株式会社 | Reduction method using lithium aluminum hydride |
| EP2436366B1 (en) | 2010-09-30 | 2015-07-29 | VOCO GmbH | Composite material comprising a monomer with a polyalicyclic structure as sealing material |
| US8697769B2 (en) | 2010-09-30 | 2014-04-15 | Voco Gmbh | Lacquer composition comprising a monomer with a polyalicyclic structure element |
| EP2436668B1 (en) | 2010-09-30 | 2012-09-12 | VOCO GmbH | Polymerisable compounds comprising a polyalicyclic structure element |
| EP2436365B1 (en) | 2010-09-30 | 2017-03-08 | VOCO GmbH | Composite material comprising a monomer with a polyalicyclic structure element |
| US8915736B2 (en) | 2010-09-30 | 2014-12-23 | Voco Gmbh | Composition comprising a monomer with a polyalicyclic structure element for filling and/or sealing a root canal |
| EP2450025B1 (en) | 2010-11-08 | 2012-11-28 | VOCO GmbH | Polymerisable phosphoric acid derivatives comprising a polyalicyclic structure element |
| EP2578200B1 (en) | 2011-10-04 | 2018-03-28 | VOCO GmbH | Compounds for infiltrating and/or sealing of dental hard substance and method |
| DE102012001979A1 (en) | 2012-02-02 | 2013-08-08 | Voco Gmbh | A curable composition comprising plasticizer having a polyalicyclic structural element for use in the manufacture of dental materials |
| DE102012001978A1 (en) | 2012-02-02 | 2013-08-08 | Voco Gmbh | Dental composite materials containing tricyclic plasticizers |
| DE102013008176A1 (en) | 2012-10-05 | 2014-04-10 | Voco Gmbh | Kit and method for the indirect chairside production of composite inlays |
| DE102018114690A1 (en) | 2018-06-19 | 2019-12-19 | Voco Gmbh | Thermally effective dental composite composition |
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1994
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| JPH07206740A (en) | 1995-08-08 |
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