JPH0532811A - Foamed resin molding - Google Patents

Foamed resin molding

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Publication number
JPH0532811A
JPH0532811A JP13672191A JP13672191A JPH0532811A JP H0532811 A JPH0532811 A JP H0532811A JP 13672191 A JP13672191 A JP 13672191A JP 13672191 A JP13672191 A JP 13672191A JP H0532811 A JPH0532811 A JP H0532811A
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aromatic
polymer
formula
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JPH0774285B2 (en
Inventor
Shunei Inoue
Minoru Kitanaka
Hirokazu Kobayashi
俊英 井上
實 北中
裕和 小林
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Toray Ind Inc
東レ株式会社
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Priority to JP3136721A priority Critical patent/JPH0774285B2/en
Publication of JPH0532811A publication Critical patent/JPH0532811A/en
Publication of JPH0774285B2 publication Critical patent/JPH0774285B2/en
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Abstract

PURPOSE:To obtain a foamed resin molding of improved isotropy by forming the molecule of the resin from aromatic dicarboxylic acid units, glycol units, aromatic diol units and hydroxybenzoic acid units in a specified molar ratio and form-molding the resin so that the cell fraction may fall within a specified range. CONSTITUTION:An aromatic condensation polymer which can develop optical anisotropy when melted is prepared by forming its molecule by combining units selected from among aromatic dicarboxylic acid units (A) of formula I (wherein R<1> is a bivalent aromatic ring residue), glycol units (B) of formula II (wherein R<2> is a bivalent aliphatic residue), aromatic diol units (C) of formula III (wherein R<3> is a bivalent residue having an aromatic ring) and hydroxybenzoic acid units (D) of formula IV in such amounts that units B are present in an amount of below 25mol% based on the total of units B, C and D. This polymer is mixed with a blowing agent, and the mixture is foam- molded to produce a foamed resin molding having a cell fraction of 5-50vol.% and improved in isotropy of the crystalline polymer.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は等方性にすぐれた機械的性質を有する発泡樹脂成形品に関するものである。 The present invention relates to relates to a foamed resin molded article having mechanical properties superior to isotropic.

【0002】 [0002]

【従来の技術】溶融時に異方性を示す芳香族系縮重合体(以下液晶性ポリマと呼ぶ。)は、その平行な分子の配列に起因してすぐれた機械的性質を有しており、主として繊維やフィルムなどの一軸配向品の分野において多くの用途に使用されている。 (Hereinafter referred to as liquid crystal polymer.) Aromatic based condensation polymer exhibited anisotropy in molten state has excellent mechanical properties due to the arrangement of the parallel molecular, It is used in many applications in the field of uniaxially oriented products mainly to fibers and films. しかしながら液晶性ポリマからなる三次元的広がりを持つ成形品は、その配向特性故に高度の異方性を有しており、とくに樹脂の流動方向に垂直な方向の機械的性質が極端に劣るという欠点がある。 However, a disadvantage in that a molded article having a three-dimensional expanse comprising a liquid crystalline polymer has the orientation characteristics because high anisotropy, particularly mechanical properties in the direction perpendicular to the flow direction of the resin is inferior in extreme there is.

【0003】 [0003]

【発明が解決しようとする課題】よって本発明は等方的に機械的性質の優れた液晶性ポリマ成形品を得ることを課題とする。 [SUMMARY OF THE INVENTION Thus the present invention it is an object to obtain isotropic liquid crystalline polymer molded article having excellent mechanical properties.

【0004】 [0004]

【課題を解決するための手段】本発明者らは、上記課題を解決すべく鋭意検討した結果、液晶性ポリマ成形品に発泡構造を付与せしめることにより、重合体分子鎖が発泡面に沿って高度に配向した構造をとり、三次元配向効果を発揮して等方的にすぐれた機械的性質が得られることを見出だし、本発明に到達した。 The present inventors have SUMMARY OF THE INVENTION As a result of extensive studies to solve the above problems, by allowed to impart foam structure in the liquid crystal polymer moldings, polymer molecular chains along the foam surface It takes highly oriented structure, false starts seen that mechanical properties isotropically superior to exhibit three-dimensional orientation effect is obtained, thereby achieving the present invention.

【0005】すなわち本発明は分子構造が下記(A)〜 [0005] The present invention is the molecular structure below (A) ~
(D)から選ばれたユニットの組み合わせで表すことができ、かつ(B)のユニットが(B)、(C)および(D)のユニットの合計に対し25モル%未満であり、 Can be represented by a combination of units selected from (D), and (B) units of (B), is less than 25 mol% relative to the total of units (C) and (D),
溶融時に光学異方性を示す芳香族系縮重合体を発泡成形してなり、気泡分率が5〜50容量%である等方性が改良された発泡樹脂成形品を提供するものである。 Be foamed molding an aromatic condensation polymer which shows optical anisotropy in molten state, the bubble fraction in which isotropic 5 to 50% by volume to provide an improved resin foam product.

【0006】(A)一般式(I)で表わされる芳香族ジカルボン酸ユニット [0006] (A) an aromatic dicarboxylic acid unit represented by the general formula (I)

【0007】 [0007]

【化3】 [Formula 3]

【0008】(式中、R 1は少なくとも1個の芳香環を有する2価の残基を示す。) (B)一般式(II)で表わされるグリコールユニット −O−R 2 −O− (II) (式中、R 2は2価の脂肪族残基を示す。) (C)一般式(III )で表わされる芳香族ジオールユニット −O−R 3 −O− (III ) (式中、R 3は少なくとも1個の芳香環を有する2価の残基を示す。) (D)(IV)式で表わされるオキシ安息香酸ユニット [0008] (In the formula, R 1 represents a divalent residue having at least one aromatic ring.) (B) glycol represented by the general formula (II) units -O-R 2 -O- (II ) (wherein, R 2 is in divalent. showing the aliphatic residue) (C) the general formula (aromatic diol unit represented by III) -O-R 3 -O- ( III) ( wherein, R 3 represents a divalent residue having at least one aromatic ring.) (D) (IV) oxybenzoate units of the formula

【0009】 [0009]

【化4】 [Of 4]

【0010】従来の発泡樹脂成形品は、多孔質という形態的特徴および軽量性等の諸特性を有し、多くの用途に利用されているが、その機械的性質は成形品中で樹脂が占める体積分率にほぼ比例して低レベルのものであった。 [0010] Conventional foamed resin molded product has various characteristics such as morphological characteristics and lightweight as porous, have been utilized for many applications, the mechanical properties are occupied by the resin in the molded article It was those substantially proportional to a low level on the volume fraction. すなわち発泡樹脂成形品の機械的性質を表わす値をEとし、密度をρとした場合、E/ρはほぼ一定の値であり、ρが小さいことで軽量性の要求は満たされるが、 That is, a value representative of the mechanical properties of the resin foam product and E, when the density was [rho, E / [rho is a substantially constant value, but [rho lightweight requests are satisfied by a small,
Eもそれなりに小さな値となっていた。 E also has become a small value in its own way.

【0011】しかるに本発明は発泡樹脂成形品の製造における発泡工程での樹脂の流動に着目し、その流動に伴なう樹脂の配向強化によりE/ρ値を上昇させる可能性があることを知見し、樹脂として液晶性ポリマを用いる場合には特異的に発泡体のE/ρ値の上昇が達成されることを見出したものであり、いわゆる発泡技術と液晶性ポリマのすぐれた配向特性を有効に組合せた意味でまさに画期的といえる。 [0011] However the present invention is focused on the flow of the resin in the foaming process in the production of the resin foam product, finding that there is a possibility to increase the E / [rho value by the orientation strengthening accompanied resin to the flow and, which increases the E / [rho value of specific foam in the case of using a liquid crystalline polymer as a resin has been found to be achieved, enabling excellent orientation characteristics of the so-called foam technology and liquid crystal polymer it can be said that the truly revolutionary in the sense that the combination to. 本発明で使用する液晶性ポリマとは溶融状態で光学異方性を示し、いわゆるサーモトロピック液晶と呼ばれているものである。 The liquid crystalline polymer used in the present invention shows optical anisotropy in molten state is what is called a thermotropic liquid crystal. この光学異方性は溶融ポリマを例えば直交偏光子を備えた光学系において観察する際に偏光が透過して強い複屈折率を生ずることで確認することができる。 The optical anisotropy can be confirmed by polarized light to produce intense birefringence and transmitted when observed in an optical system having a melt polymer e.g. crossed polarizers.

【0012】本発明で用いる液晶ポリマは構成ユニットがエステル結合で結合された液晶ポリエステルであり、 [0012] The liquid crystal polymer used in the present invention is a liquid crystal polyester constituting units are bonded in an ester bond,
そのユニットは前記(I)〜(IV)の各ユニットから選ばれるものである。 Its units are those selected from the units of the (I) ~ (IV).

【0013】一般式(I)で表わされる芳香族ジカルボン酸ユニットとしてはテレフタル酸、イソフタル酸、 [0013] The aromatic dicarboxylic acids units represented by the general formula (I) terephthalic acid, isophthalic acid,
4,4´−ジフェニルジカルボン酸、4,4´−ジフェニルエーテルジカルボン酸、2,6−ナフタレンジカルボン酸、1,2−ビス(フェノキシ)エタン−4,4´ 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'
−ジカルボン酸、1,2−ビス(2−クロルフェノキシ)エタン−4,4´−ジカルボン酸などが好ましい例として挙げられる。 - dicarboxylic acids, such as 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid are preferred examples.

【0014】一般式(II)で表わされるグリコールユニットとしてはエチレングリコール、1,4−ブタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、1,4−シクロヘキサンジメタノールなどがその好ましい例として挙げられるが、中でもエチレングリコールがより好ましい。 [0014] mentioned general formula (II) of ethylene glycol as a glycol unit represented by, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and preferred examples thereof include 1,4-cyclohexane dimethanol It is, but among them ethylene glycol is more preferable.

【0015】一般式(III )で表わされる芳香族ジオールユニットとしては4,4´−ジヒドロキシビフェニル、3,3´,5,5´−テトラメチル−4,4´−ジヒドロキシビフェニル、ハイドロキノン、t−ブチルハイドロキノン、フェニルハイドロキノン、クロロハイドロキノン、メチルハイドロキノン、2,6−ジヒドロキシナフタレン、2,7−ジヒドロキシナフタレン、2, Examples of the aromatic diol unit represented by the general formula (III) 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t- butyl hydroquinone, phenyl hydroquinone, chloro hydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,
2−ビス(4−ヒドロキシフェニル)プロパンおよび4,4´−ジヒドロキシフェニルエーテルなどが好ましい例として挙げられる。 And 2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxyphenyl ether are preferred examples.

【0016】一般式(IV)で表わされるオキシ安息香酸ユニットとしてはp−オキシ安息香酸、m−オキシ安息香酸など挙げられるが、p−オキシ安息香酸ユニットが最も好ましい。 Examples of the hydroxybenzoic acid unit represented by the general formula (IV) p-oxybenzoate, m- oxybenzoate but the like, p- oxybenzoate units being most preferred.

【0017】本発明で使用し得る芳香族ポリエステルをさらに具体的に説明すれば例えば次ぎのものが挙げられる。 [0017] The present invention include the following example will be described aromatic polyesters more specifically which can be used in the like.

【0018】(1)クロルハイドロキノン、メチルハイドロキノン、フェニルハイドロキノンなどの核置換ハイドロキノンとテレフタル酸などの対称性芳香族ジカルボン酸からなる全芳香族ポリエステル(例えば特開昭53 [0018] (1) chloro hydroquinone, methylhydroquinone, wholly aromatic polyester consisting of symmetrical aromatic dicarboxylic acids, such as nuclear-substituted hydroquinone and terephthalic acid, such as phenyl hydroquinone (for example, JP 53
−65421号公報、特公昭55−482号公報など) (2)ハイドロキノンとテレフタル酸などの対称性芳香族ジカルボン酸からなるポリエステルにp−ヒドロオキシ安息香酸を反応させ、縮重合してなる全芳香族コポリエステル(例えば特開昭50−43223号公報)これらの液晶性ポリマの中でも、ポリマを最適条件で紡糸した際の紡出糸の初期弾性率が200g/d以上のものが望ましく使用される。 -65421, JP-like JP-B-55-482) (2) hydroquinone and a polyester consisting of symmetrical aromatic dicarboxylic acids such as terephthalic acid by reacting p- hydroxycarbonate acid, wholly aromatic obtained by polycondensation among the copolyester (for example, JP 50-43223 JP) these liquid crystal polymer, spun yarn initial modulus of when spun in optimum condition polymer is more than 200 g / d is preferably used.

【0019】本発明の発泡樹脂成形品を構成する要件は、液晶性ポリマが発泡構造をとること、すなわち、成形品中に三次元的曲面を有することであり、その曲面の形態は、例えば、発泡による効果を大きくしようとすると必然的に泡構造が大きくなり、一方で成形品の不均一さが増大し、負荷時の応力分布が不均一になるという関係があり、目的とする機械特性により適宜最適化が必要であるが、一般には気泡径が小さく、均一なほど望ましい機械的性質を得ることができる。 The requirement that constitute the foamed resin molded article of the present invention, the liquid crystal polymer takes a foamed structure, i.e., is to have a three-dimensional curved surface in the molded article, the form of the curved surface is, for example, inevitably foam structure when trying to enlarge the effect of foaming is increased, whereas non-uniformity of the molded article is increased by, there is a relation that the stress distribution when load is uneven, the mechanical properties of interest it is necessary to appropriately optimize generally smaller cell diameter, it is possible to obtain a more uniform desired mechanical properties. また成形品の発泡率は、気泡分率が5〜50容量%、とくに10〜50容量%の範囲が好ましい。 The expansion ratio of the molded article, the bubble fraction of 5 to 50% by volume, in particular 10 to 50 volume% is preferred. 5容量%未満ではE/ρ値の上昇効果が小さく、50容量%を越えると形態保持性が損われ、機械的性質も全般に低下するため好ましくない。 If it is less than 5 volume% small increasing effect of E / [rho value, exceeds 50 volume%, the shape retention is compromised, undesirably lowers the mechanical properties in general.

【0020】本発明における発泡方法にはとくに制限はなく、発泡剤としては環式炭化水素、ハロゲン化炭化水素等の溶剤型発泡剤、炭酸カルシウム、炭酸ナトリウム等の炭酸塩、アゾ化合物、ニトロソ化合物、スルホニル化合物等の分解型発泡剤等の通常用いられているいかなる発泡剤も使用することができ液晶性重合体の種類、目的とする発泡構造により適宜選択することができる。 [0020] foaming process of the present invention is not particularly limited and cyclic hydrocarbons as blowing agents, solvent type foaming agents such as halogenated hydrocarbons, calcium carbonate, carbonates such as sodium carbonate, azo compounds, nitroso compounds , it can be appropriately selected liquid crystalline polymer type can also be used any blowing agents routinely used such decomposition type foaming agent such as sulfonyl compound, by foaming the desired structure. また目的とする発泡構造によっては液晶性重合体に架橋構造を導入することも可能であり、エポキシ化合物等の架橋剤を添加することもできる。 Also depending on the foam structure of interest is also possible to introduce a crosslinked structure in the liquid crystal polymer, it may be added a crosslinking agent for the epoxy compound.

【0021】成形方法についても、発泡構造を有する成形体が得られる方法であれば、いかなる方法をとることも可能であり、通常行われている押出成形、射出成形、 [0021] The molding method is also as long as the method molded body having a foam structure is obtained, it is also possible to adopt any method, extrusion is conventionally done, injection molding,
プレス成形、ブロー成形等が例示されるがこれに限定されるものではない。 Press molding, it does not but blow molding, and the like is not limited to this.

【0022】なお成形時には液晶性ポリマに対し、発泡剤とともに、強化剤、充てん剤、核剤、顔料、酸化防止剤、安定剤、可塑剤、滑剤、離型剤などの添加剤を添加して、成形品に所望の特性を付与することができる。 [0022] Note to the liquid crystal polymer during molding, with foaming agents, reinforcing agents, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, added lubricants, additives such as release agents , it is possible to impart desired properties to the molded article.

【0023】かくしてなる本発明の発泡樹脂成形品は等方的にすぐれた機械的性質を有しており、種々の用途に有用である。 [0023] Thus comprised foamed resin molded article of the present invention have mechanical properties isotropically excellent useful for a variety of applications.

【0024】以下に実施例を挙げて本発明をさらに説明する。 [0024] The invention is further illustrated by the following examples. なお実施例中の曲げ弾性率はASTM D−79 Note flexural modulus in Examples ASTM D-79
0に準じて測定した。 0 was measured in accordance with.

【0025】実施例1 攪拌器、留出管を有する反応容器にフェニルハイドロキノンジアセテート650重量部、テレフタル酸381重量部、およびp−アセトキシ安息香酸73重量部を入れ、150〜300℃、窒素雰囲気下、常圧で2時間、 [0025] Example 1 stirrer, 650 parts by weight of phenyl hydroquinone diacetate in a reaction vessel having a distillation pipe, 381 parts by weight of terephthalic acid, and p- acetoxy benzoic acid 73 parts by weight was placed, 150 to 300 ° C., a nitrogen atmosphere below, under normal pressure for 2 hours,
300〜350℃、減圧下で約2時間加熱反応させたところ、ほぼ理論量の酢酸が留出し、淡緑色のポリマが得られた。 300 to 350 ° C., was allowed to approximately 2 hours while heating the reaction at reduced pressure, approximately theoretical amount of acetic acid is distilled off, pale green polymer was obtained.

【0026】 [0026]

【化5】 [Of 5]

【0027】このポリマの融点は325℃であり、溶融状態では良好な光学異方性を示した。 The melting point of this polymer is 325 ° C., showed good optical anisotropy in a molten state. 上記で得た液晶性ポリエステル100重量部に発泡剤として炭酸カリウムを表1の割合で添加し、65mmφの押出機に供して340℃で溶融混合後ガット状に押出し、ペレタイズした。 Potassium carbonate as a foaming agent in the liquid crystalline polyester to 100 parts by weight obtained above was added in an amount shown in Table 1 was extruded, pelletized in the melt after mixing gut-form by subjecting to extruder 65mmφ to 340 ° C..

【0028】各ペレットを340℃に設定した5オンスのスクリューインライン型射出成形機に供し、金型温度60℃の条件で厚み3mm×80mm×80mmの角板を成形した。 [0028] subjected to a screw in-line type injection molding machine 5 oz set to 340 ° C. Each pellet was molded square plate having a thickness of 3 mm × 80 mm × 80 mm under the conditions of mold temperature 60 ° C.. この角板を流動方向および垂直方向に各々巾12mmに切削して得た試験片の曲げ弾性率を測定した。 The square plate was measured flexural modulus of the flow direction and the vertical direction to each obtained by cutting the width 12mm specimen. この結果および試験片の密度(ρ)、気泡倍率およびE/ρの評価結果を併せて表1に示す。 The density of this result and the test piece ([rho), shown in Table 1 together evaluation results of the bubble magnification and E / [rho.

【0029】 [0029]

【表1】 [Table 1]

【0030】表1から明らかなように本発明の発泡樹脂成形品(No. 1〜3)は未発泡品(No. 4)、気泡分率が5容量%未満の成形品に比し、曲げ弾性率の等方性が極めて改良されている。 The foamed resin molded article as is apparent the invention from Table 1 (No. 1 to 3) is unfoamed articles (No. 4), the bubble fraction than in the molded article of less than 5 volume%, the bending isotropic elastic modulus is extremely improved. また気泡分率が50容量%を越えると曲げ弾性率の低下が著しい。 The bubble fraction is a significant reduction in the flexural modulus exceeds 50 volume%.

【0031】 [0031]

【発明の効果】本発明の発泡樹脂成形体は液晶性ポリマの等方性が著しく改善されており、エンジニアリングプラスチックとして種々の用途に供することができる。 Foamed resin molded article of the present invention, according to the present invention has been significantly improved isotropic liquid crystal polymer, can be subjected to various applications as engineering plastics.

Claims (1)

  1. 【特許請求の範囲】 【請求項1】 分子構造が下記(A)〜(D)から選ばれたユニットの組み合わせで表すことができ、かつ(B)のユニットが(B)、(C)および(D)のユニットの合計に対し25モル%未満であり、溶融時に光学異方性を示す芳香族系縮重合体を発泡成形してなり、気泡分率が5〜50容量%である等方性が改良された発泡樹脂成形品。 Claims 1. A molecular structure can be represented by a combination of units selected from the following (A) ~ (D), and the unit of (B) (B), (C) and less than 25 mol% relative to the total of units (D), it was foam molding an aromatic condensation polymer which shows optical anisotropy in molten state, the bubble fraction of 5 to 50 volume percent isotropic sex improved resin foam product. (A)一般式(I)で表わされる芳香族ジカルボン酸ユニット【化1】 (A) an aromatic dicarboxylic acid unit embedded image represented by the general formula (I) (式中、R 1は少なくとも1個の芳香環を有する2価の残基を示す。) (B)一般式(II)で表わされるグリコールユニット−O−R 2 −O− (II) (式中、R 2は2価の脂肪族残基を示す。) (C)一般式(III )で表わされる芳香族ジオールユニット−O−R 3 −O− (III ) (式中、R 3は少なくとも1個の芳香環を有する2価の残基を示す。) (D)(IV)式で表わされるオキシ安息香酸ユニット【化2】 (In the formula, R 1 represents a divalent residue having at least one aromatic ring.) (B) glycol units -O-R 2 -O- represented by the general formula (II) (II) (wherein among, R 2 is in divalent. showing the aliphatic residue) (C) the general formula (aromatic diol unit represented by III) -O-R 3 -O- ( III) ( wherein, R 3 is at least a divalent residue having one aromatic ring.) (D) (IV) oxybenzoate units embedded image of the formula
JP3136721A 1991-06-07 1991-06-07 The resin foam product Expired - Lifetime JPH0774285B2 (en)

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JP3136721A JPH0774285B2 (en) 1991-06-07 1991-06-07 The resin foam product

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JP3136721A JPH0774285B2 (en) 1991-06-07 1991-06-07 The resin foam product

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JPH0532811A true JPH0532811A (en) 1993-02-09
JPH0774285B2 JPH0774285B2 (en) 1995-08-09

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5673249A (en) * 1994-10-27 1997-09-30 Kabushiki Kaisha Toshiba Phase change type optical recording apparatus and optical recording method using an overwrite system
US5673248A (en) * 1994-10-27 1997-09-30 Kabushiki Kaisha Toshiba Phase change type optical recording apparatus and optical recording method using an overwrite system
US5732062A (en) * 1995-10-16 1998-03-24 Ricoh Company, Ltd. Information recording apparatus, method and computer program product
US8210786B2 (en) 2006-12-06 2012-07-03 Piolax Inc. Fastening device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS518395A (en) * 1974-06-07 1976-01-23 Eastman Kodak Co Kohoriesuterunoseizoho

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS518395A (en) * 1974-06-07 1976-01-23 Eastman Kodak Co Kohoriesuterunoseizoho

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5673249A (en) * 1994-10-27 1997-09-30 Kabushiki Kaisha Toshiba Phase change type optical recording apparatus and optical recording method using an overwrite system
US5673248A (en) * 1994-10-27 1997-09-30 Kabushiki Kaisha Toshiba Phase change type optical recording apparatus and optical recording method using an overwrite system
US5732062A (en) * 1995-10-16 1998-03-24 Ricoh Company, Ltd. Information recording apparatus, method and computer program product
US8210786B2 (en) 2006-12-06 2012-07-03 Piolax Inc. Fastening device

Also Published As

Publication number Publication date
JPH0774285B2 (en) 1995-08-09

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