JPH0576974B2 - - Google Patents
Info
- Publication number
- JPH0576974B2 JPH0576974B2 JP60271960A JP27196085A JPH0576974B2 JP H0576974 B2 JPH0576974 B2 JP H0576974B2 JP 60271960 A JP60271960 A JP 60271960A JP 27196085 A JP27196085 A JP 27196085A JP H0576974 B2 JPH0576974 B2 JP H0576974B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyester resin
- polyester
- polyethylene
- bottles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 24
- 229920001225 polyester resin Polymers 0.000 claims description 22
- 239000004645 polyester resin Substances 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KHMVSYUVMBMXKL-UHFFFAOYSA-N 2,3-dimethylterephthalic acid;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.CC1=C(C)C(C(O)=O)=CC=C1C(O)=O KHMVSYUVMBMXKL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019992 sake Nutrition 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Landscapes
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
（産業上の利用分野）
本発明は、透明性を損うことなく結晶化速度を
改善した、主としてボトル、フイルム等の成形用
として優れたポリエステル樹脂組成物ならびにそ
の製造方法に関するものである。
（従来の技術）
ポリエステル、特にポリエチレンテレフタレー
トは、繊維はもとより、ボトル、フイルム等の素
材として広く用いられている。
特にボトル用として、ポリエチレンテレフタレ
ートの使用量は近年急速に増大しており、しよう
油、ソース等の調味料、ウイスキー、日本酒、ビ
ール等のアルコール飲料、その他ジユース、炭酸
飲料、ミネラルウオーター等の食品容器として、
さらには液体洗剤、化粧品等の容器として使用し
て、
Γ軽くて破損しにくい。
Γ透明性に優れている。
Γ衛生性に優れている。
などの特徴を余すところなく生かしている。
しかしながら、従来のポリエステルボトルは70
℃以上の高い温度で調味料あるいは飲料を充填す
る際、ボトルの口頚部あるいは肩部のごとく延伸
配向されていない部分が変形して外観を損うた
め、高温での内容物の充填には適さない。
ポリエステルボトルのかかる欠点を改良して耐
熱性を付与し、高温充填可能なボトルを製造する
方法として、成形されたボトルまたはボトルの前
駆体であるポリエステルプレフオームの口頚部を
熱処理して結晶化する方法は、例えば特開昭55−
79237号公報、特開昭58−110221号公報等で従来
公知である。
（発明が解決しようとする問題点）
しかしながら、従来公知の技術に従つて耐熱ボ
トルを製造する際、延伸配向されない口頚部、肩
部を熱処理して結晶化させる方法にあつては、熱
処理が低温かつ短時間で完結するのが生産性の点
でも、製造された耐熱ボトルの外観の点でも好ま
しいが、通常、透明性に優れたボトル用の原料ポ
リエステルは同時に結晶化速度が遅いため、
Γ透明性を犠牲にして結晶化速度を改善する。
Γ耐熱ボトルの生産性を犠牲にして長時間熱処理
する。
Γ熱処理温度を高くし、熱処理時間を短縮するこ
とは加熱が不均一になり、ボトルの口頚部、肩
部の変形等外観を損うばかりか、口頚部の変形
は充填した内容物の洩れにつながる懸念すらあ
るため実施しにくい。
など何等かの問題点を包含する。
（問題点を解決するための手段）
本発明者等は、低温、短時間の熱処理によつて
耐熱ボトルの製造を可能にするべく、原料ポリエ
ステルについて鋭意検討の結果、本発明に到達し
たものである。すなわち、
(1) ポリエチレンテレフタレートまたは主として
エチレンテレフタレート成分からなるポリエス
テルに、ポリエチレン0.05〜500ppmを均一に
混合してなるポリエステル樹脂組成物。
(2) ポリエチレンテレフタレートまたは主として
エチレンテレフタレート成分からなるポリエス
テル樹脂組成物を製造するにあたり、重縮合反
応を開始する以前の工程でポリエチレンを投入
することを特徴とするポリエステル樹脂組成物
の製造方法。
であることを要旨としたものであつて、このよう
なポリエステル樹脂組成物を製造、調製すること
によつて、結晶化温度が低くなり、結晶化速度が
速くなるにもかかわらず、透明性が何等損われる
ことのない耐熱ボトル用の原料として理想的なポ
リエステル樹脂組成物を得ることができたもので
ある。
（作用）
本発明のポリエステル樹脂組成物を調製するに
あたり、均一に混合されていればいかなるポリエ
ステル製造工程で混合してもさしつかえなく、さ
らにはポリエステルペレツトを製造後、ポリエチ
レンを溶融混合してもよいが、ポリエステルの製
造工程、特に原料工程：テレフタル酸（テレフタ
ル酸ジメチル）またはエチレングリコール中に混
合しておく、スラリー調製工程：テレフタル酸と
エチレングリコールとを混合してスラリーを調製
する際、併せてポリエチレンを混合、エステル化
反応工程（テレフタル酸ジメチルを混合する場合
はエステル交換反応工程）、続いて行われる重縮
合反応工程の直前までの工程でポリエチレンを混
合する方法が、均一混合を可能にする点でも混合
コストの点でも有利である。
ポリエステル樹脂組成物を構成するポリエチレ
ンの量は0.05ppm未満では結晶化を促進する効果
が不十分であり、逆に500ppmを越えるとポリエ
ステルとの相溶性の悪さが表面化して白濁し、透
明性が損われるため0.05〜500ppm、好ましくは
0.5〜100ppmの範囲で混合する。
ポリエチレンを均一に混合したポリエステル樹
脂組成物は、必要な場合には、さらに固相重合を
行つた後ボトル、フイルム等の成形用途へ供す
る。
（実施例、発明の効果）
本発明のポリエステル樹脂組成物を評価するに
あたり、結晶化温度、結晶化速度などの熱的挙動
はパーキンエルマー社製DSC型を用いて20
℃／分で昇温して測定する。特に結晶化速度は結
晶化に起因する発熱ピークの高さ(B)を底辺の長さ
(A)で除した値で表す。
また、ポリエステル樹脂組成物の極限粘度は、
フエノール：テトラクロルエタンニ６：４（重量
比）混合溶媒中20℃で測定し、ポリエステル樹脂
組成物の透明性は、ポリエステル樹脂組成物を
130℃で10torrの減圧下５時間乾燥後、東洋機械
金属社製プラスター50型射出成形機を用いて、
280〜285℃で厚さ５ｍ／ｍ、4.5ｍ／ｍ、４ｍ／
ｍ、3.5ｍ／ｍ、３ｍ／ｍ、長さ10cm、巾６cmの
段付きプレートを成形し、スガ試験機社製HGM
−2D型直読ヘーズコンピユーターを用いて、ヘ
ーズ値（％）で評価する。
実施例１〜５、参考例１〜４
テレフタル酸166重量部、エチレングリコール
93重量部を混合してスラリーを調製し、直接エス
テル化反応槽へ供給して、加圧下250℃でエステ
ル化反応を行つてエチレンテレフタレート低重合
体を調製した。
続いて重縮合触媒として、ポリエステル樹脂組
成物に対して二酸化ゲルマニウム138ppm、燐酸
156ppmになる量でエチレングリコール溶液で加
え、表１に示す量でポリエチレン（三菱化成工業
社製NOVATEC−LF−161）を投入して重縮合
反応を行つて表−１に示すポリエステル樹脂組成
物を調製した。
実施例６および参考例５
実施例４および参考例１と同様に、但し極限粘
度0.56の低重合度ポリエステル樹脂組成物（プレ
ポリマー）を調製し、続いてタンブラー型固相重
合装置を用いて減圧下、230℃で固相重合を行つ
て表−２に示すポリエステル樹脂組成物を調製し
た。
(Field of Industrial Application) The present invention relates to a polyester resin composition which has improved crystallization speed without impairing transparency and is excellent mainly for molding bottles, films, etc., and a method for producing the same. (Prior Art) Polyester, particularly polyethylene terephthalate, is widely used as a material for bottles, films, etc. as well as fibers. In particular, the amount of polyethylene terephthalate used for bottles has increased rapidly in recent years, and it has been used in containers for seasonings such as soybean oil and sauces, alcoholic beverages such as whiskey, sake, and beer, and food containers such as drinks, carbonated drinks, and mineral water. As,
Furthermore, it can be used as a container for liquid detergents, cosmetics, etc. It is lightweight and does not easily break. Γ Excellent transparency. Γ Excellent hygiene. It takes full advantage of these characteristics. However, traditional polyester bottles have a
When filling seasonings or beverages at temperatures as high as ℃ or higher, parts of the bottle that are not stretched or oriented, such as the neck or shoulder of the bottle, are deformed and the appearance is impaired, so it is not suitable for filling contents at high temperatures. do not have. As a method for improving these drawbacks of polyester bottles, imparting heat resistance, and manufacturing bottles that can be filled at high temperatures, the neck and neck of a molded bottle or a polyester preform, which is a precursor of the bottle, is heat-treated to crystallize it. The method is described, for example, in Japanese Patent Application Laid-open No. 1983-
This is conventionally known in JP-A No. 79237, Japanese Unexamined Patent Publication No. 110221-1980, and the like. (Problems to be Solved by the Invention) However, when manufacturing a heat-resistant bottle according to conventionally known technology, the neck and shoulder parts, which are not stretched and oriented, are heat-treated to crystallize, but the heat treatment is performed at a low temperature. It is preferable to complete the process in a short time both from the viewpoint of productivity and the appearance of the manufactured heat-resistant bottles. However, polyester, which is the raw material for bottles with excellent transparency, also has a slow crystallization rate, so Γ transparent improve crystallization rate at the expense of properties. Γ Heat treatment for a long time at the expense of productivity for heat-resistant bottles. Increasing the Γ heat treatment temperature and shortening the heat treatment time will not only result in uneven heating, which will damage the appearance of the bottle, such as deformation of the neck and shoulder of the bottle, but also deformation of the neck and neck, which may lead to leakage of the filled contents. It is difficult to implement because there are concerns that it may lead to this. It includes some problems such as. (Means for Solving the Problems) The present inventors have arrived at the present invention as a result of intensive studies on raw material polyester, in order to make it possible to manufacture heat-resistant bottles by heat treatment at low temperatures and in a short time. be. That is, (1) a polyester resin composition formed by uniformly mixing 0.05 to 500 ppm of polyethylene with polyethylene terephthalate or a polyester mainly consisting of an ethylene terephthalate component. (2) A method for producing a polyester resin composition, which comprises adding polyethylene in a step before starting a polycondensation reaction when producing a polyester resin composition consisting of polyethylene terephthalate or mainly an ethylene terephthalate component. By producing and preparing such a polyester resin composition, although the crystallization temperature is lowered and the crystallization speed is increased, the transparency is improved. It was possible to obtain a polyester resin composition that is ideal as a raw material for heat-resistant bottles that will not be damaged in any way. (Function) In preparing the polyester resin composition of the present invention, it may be mixed in any polyester production process as long as it is mixed uniformly, and even polyethylene may be melt-mixed after producing polyester pellets. However, the manufacturing process of polyester, especially the raw material process: mixing in terephthalic acid (dimethyl terephthalate) or ethylene glycol, and the slurry preparation process: when preparing a slurry by mixing terephthalic acid and ethylene glycol. This method enables uniform mixing by mixing polyethylene in the esterification reaction step (or transesterification reaction step if dimethyl terephthalate is mixed), and immediately before the subsequent polycondensation reaction step. It is advantageous both in terms of performance and mixing cost. If the amount of polyethylene constituting the polyester resin composition is less than 0.05 ppm, the effect of promoting crystallization will be insufficient, and if it exceeds 500 ppm, the poor compatibility with polyester will become apparent and the composition will become cloudy and lose its transparency. 0.05-500ppm, preferably
Mix in the range of 0.5-100ppm. The polyester resin composition in which polyethylene is uniformly mixed is further subjected to solid phase polymerization, if necessary, and then used for molding purposes such as bottles and films. (Examples, Effects of the Invention) In evaluating the polyester resin composition of the present invention, thermal behavior such as crystallization temperature and crystallization rate was measured using a PerkinElmer DSC model 20
Measure by increasing the temperature at a rate of °C/min. In particular, the crystallization rate is determined by the height (B) of the exothermic peak caused by crystallization, which is determined by the length of the base.
Expressed as the value divided by (A). In addition, the intrinsic viscosity of the polyester resin composition is
The transparency of the polyester resin composition was measured at 20°C in a 6:4 (weight ratio) mixed solvent of phenol:tetrachloroethane.
After drying at 130℃ for 5 hours under reduced pressure of 10torr, using a plaster 50 injection molding machine manufactured by Toyo Kikai Kinzoku Co., Ltd.
Thickness 5m/m, 4.5m/m, 4m/m at 280~285℃
A stepped plate with dimensions of 10 cm, 3.5 m/m, 3 m/m, length 10 cm, and width 6 cm was molded using HGM manufactured by Suga Test Instruments Co., Ltd.
- Evaluate by haze value (%) using a 2D direct reading haze computer. Examples 1 to 5, Reference Examples 1 to 4 166 parts by weight of terephthalic acid, ethylene glycol
A slurry was prepared by mixing 93 parts by weight, and the slurry was directly supplied to an esterification reaction tank, and an esterification reaction was carried out at 250° C. under pressure to prepare an ethylene terephthalate low polymer. Next, as a polycondensation catalyst, 138 ppm of germanium dioxide and phosphoric acid were added to the polyester resin composition.
Ethylene glycol solution was added in an amount of 156 ppm, and polyethylene (NOVATEC-LF-161 manufactured by Mitsubishi Chemical Industries, Ltd.) was added in the amount shown in Table 1 to perform a polycondensation reaction to produce the polyester resin composition shown in Table 1. Prepared. Example 6 and Reference Example 5 In the same manner as Example 4 and Reference Example 1, however, a low degree of polymerization polyester resin composition (prepolymer) with an intrinsic viscosity of 0.56 was prepared, and then the pressure was reduced using a tumbler type solid phase polymerization apparatus. Solid phase polymerization was carried out at 230°C to prepare polyester resin compositions shown in Table 2.
【表】
表−１において、Tccはポリエステル樹脂組成
物の昇温時の結晶化温度を、Ｂ／Ａを結晶化速度
の代表特性として、さらにTmは融点を各々示
す。[Table] In Table 1, Tcc indicates the crystallization temperature of the polyester resin composition during heating, B/A indicates the representative characteristic of crystallization rate, and Tm indicates the melting point.
【表】
温して測定した値である。
続いて、表−２に示す各ポリエステル樹脂組成
物を用いて、日精ASB社製ASB−50射出成形機
を用いて、口頚部38ｍ／ｍφ、内容量1.5（目
付55ｇ）のボトルを成形した後、口頚部のみを
140℃で10秒間加熱して結晶化処理した後、70〜
90℃の温水を充填したところ、10本あたりの欠点
数は表−３のごとく得られた。[Table] Values measured after heating.
Next, using each polyester resin composition shown in Table 2, a bottle with a mouth and neck part of 38 m/mφ and a content capacity of 1.5 (basis weight 55 g) was molded using an ASB-50 injection molding machine manufactured by Nissei ASB. , mouth and neck only
After crystallization treatment by heating at 140℃ for 10 seconds, 70~
When filled with 90°C hot water, the number of defects per 10 bottles was as shown in Table 3.
【表】
参考例５のポリエステル樹脂組成物を用いたボ
トルを無欠点とするためには140℃で35秒間の結
晶化処理を必要とした。
実施例にみるように、本発明のものは結晶化温
度が低くなり、結晶化速度が速くなるにもかかわ
らず透明性が少しも損われることがないことを示
している。[Table] In order to make the bottle using the polyester resin composition of Reference Example 5 defect-free, it was necessary to undergo a crystallization treatment at 140° C. for 35 seconds. As shown in the examples, the crystallization temperature of the present invention is lower and the crystallization rate is faster, but the transparency is not impaired at all.
Claims (1)
エチレンテレフタレート成分からなるポリエステ
ルに、ポリエチレン0.05〜500ppmを均一に混合
してなるポリエステル樹脂組成物。 ２ ポリエチレンテレフタレートまたは主として
エチレンテレフタレート成分からなるポリエステ
ル樹脂組成物を製造するにあたり、重縮合反応を
開始する以前の工程でポリエチレンを投入するこ
とを特徴とするポリエステル樹脂組成物の製造方
法。[Scope of Claims] 1. A polyester resin composition obtained by uniformly mixing 0.05 to 500 ppm of polyethylene with polyethylene terephthalate or a polyester mainly consisting of an ethylene terephthalate component. 2. A method for producing a polyester resin composition, which comprises adding polyethylene in a step before starting a polycondensation reaction when producing a polyester resin composition consisting of polyethylene terephthalate or mainly an ethylene terephthalate component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27196085A JPS62131055A (en) | 1985-12-03 | 1985-12-03 | Polyester resin composition and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27196085A JPS62131055A (en) | 1985-12-03 | 1985-12-03 | Polyester resin composition and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62131055A JPS62131055A (en) | 1987-06-13 |
| JPH0576974B2 true JPH0576974B2 (en) | 1993-10-25 |
Family
ID=17507205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27196085A Granted JPS62131055A (en) | 1985-12-03 | 1985-12-03 | Polyester resin composition and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62131055A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023476A1 (en) * | 1999-09-27 | 2001-04-05 | Eastman Chemical Company | Polyester-wax compositions and methods of making the same |
| JP5203615B2 (en) * | 2006-11-29 | 2013-06-05 | 日本エステル株式会社 | Polyester resin and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6214578A (en) * | 1985-07-11 | 1987-01-23 | Nec Corp | Code converting system for facsimile signal |
-
1985
- 1985-12-03 JP JP27196085A patent/JPS62131055A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6214578A (en) * | 1985-07-11 | 1987-01-23 | Nec Corp | Code converting system for facsimile signal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62131055A (en) | 1987-06-13 |
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