JPH05261802A - Manufacture of polyvinyl alcohol base resin made container - Google Patents
Manufacture of polyvinyl alcohol base resin made containerInfo
- Publication number
- JPH05261802A JPH05261802A JP9181192A JP9181192A JPH05261802A JP H05261802 A JPH05261802 A JP H05261802A JP 9181192 A JP9181192 A JP 9181192A JP 9181192 A JP9181192 A JP 9181192A JP H05261802 A JPH05261802 A JP H05261802A
- Authority
- JP
- Japan
- Prior art keywords
- container
- polyvinyl alcohol
- sheet
- mold
- molding
- 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
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフィルムまたはシート
（以下、シート状物とする）からの二次成形による容器
の成形が容易で、高い機械的強度を持つポリビニルアル
コール系樹脂製容器の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a polyvinyl alcohol-based resin container having a high mechanical strength, which is easy to form a container from a film or a sheet (hereinafter referred to as a sheet) by secondary molding. It is about.
【０００２】[0002]
【従来の技術】ポリビニルアルコール系樹脂からなるシ
ート状物は、１）ガスバリアー性に優れている、２）非
帯電性である、３）水蒸気透過性が大きい、４）透明性
に優れている、５）機械的強度が大きい、６）耐油性に
優れている、７）親水性である、８）生分解性を持つな
どの優れた特性を備えているため、衣料や食品などの包
装用または熱硬化性樹脂成形品の離型用のシート状物な
どとして広く利用されている。2. Description of the Related Art Sheets made of polyvinyl alcohol resin are 1) excellent in gas barrier property, 2) non-chargeable, 3) large in water vapor permeability, and 4) excellent in transparency. 5) High mechanical strength, 6) Excellent oil resistance, 7) Hydrophilic property, 8) Biodegradability, etc. Alternatively, it is widely used as a sheet-like product for releasing a thermosetting resin molded product from a mold.
【０００３】このシート状物の製造はポリビニルアルコ
ール系樹脂の融点が分解温度より高いため、ポリビニル
アルコール系樹脂に水を添加したものを、流延法または
溶融押出法によりシート状に成形した後、乾燥（調
湿）、場合によっては乾燥・熱処理を行った後、調湿
（＝シート状物に二次成形性を付与するために所定の水
分含有量になるように水を加える）して、製品中の水分
を20重量％以下にするという方法で行われている。Since the melting point of the polyvinyl alcohol-based resin is higher than the decomposition temperature in the production of this sheet-like material, a polyvinyl alcohol-based resin to which water is added is molded into a sheet by a casting method or a melt extrusion method, After drying (humidification) and, if necessary, drying and heat treatment, humidity conditioning (= adding water to a prescribed water content to give secondary formability to the sheet), This is done by keeping the water content in the product below 20% by weight.
【０００４】このようにして得られたシート状物の内、
水分の少ないものは機械的強度が大きいので、そのまま
加熱した場合には柔軟性を持たないため、塩化ビニル系
樹脂などの他の熱可塑性樹脂のように、真空成形、圧空
成形、真空圧空成形、プレス成形などの二次成形によっ
て容器とすることができなかった。また、水分の多いも
のは二次成形が可能であるが、この場合には得られる成
形品が柔らかくて容器としての機能を満足せず実用化に
は程遠いものであった。Of the sheet-like material thus obtained,
A material with low water content has high mechanical strength, so it does not have flexibility when heated as it is.Vacuum molding, pressure molding, vacuum pressure molding, like other thermoplastic resins such as vinyl chloride resin, The container could not be formed by secondary molding such as press molding. Further, although a product having a large amount of water can be subjected to secondary molding, in this case, the molded product obtained is soft and does not satisfy the function as a container, which is far from practical use.
【０００５】[0005]
【発明が解決しようとする課題】したがって、本発明の
目的はシート状物からの二次成形による容器の成形が容
易で、高い機械的強度を持つポリビニルアルコール系樹
脂製容器の製造方法を提供しようとするものである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a polyvinyl alcohol resin container having a high mechanical strength, which is easy to form a container from a sheet by secondary molding. It is what
【０００６】[0006]
【課題を解決するための手段】本発明によるポリビニル
アルコール系樹脂製容器の製造方法は、ポリビニルアル
コール系樹脂をシート状に成形した後、乾燥し、成形物
の水分を５〜20重量％に調湿し、40〜 150℃で予備加熱
し、50〜 170℃に保持した金型に入れ、二次成形により
容器を成形し、その金型内で後加熱し、しかる後に乾燥
することを特徴とするものである。Means for Solving the Problems A method for producing a polyvinyl alcohol resin container according to the present invention comprises molding a polyvinyl alcohol resin into a sheet and then drying it to adjust the water content of the molded product to 5 to 20% by weight. It is characterized in that it is moistened, preheated at 40 to 150 ° C, put in a mold kept at 50 to 170 ° C, molded into a container by secondary molding, post-heated in the mold, and then dried. To do.
【０００７】これを説明すると、本発明者らはポリビニ
ルアルコール系樹脂が含水時には柔軟性に富み、その状
態でシート状のものは、真空成形、圧空成形、真空圧空
成形、プレス成形などの従来公知の二次成形が可能であ
ること、これを後加熱し乾燥する（シート状物から容器
に成形したものを金型内で、または金型から取り出し
て、水分を除くようにする）と、容器としての機能を十
分満足できる機械的強度を有する成形品となることに着
目して研究を進めた結果、ポリビニルアルコール系樹脂
をシート状に成形した後、乾燥し、成形物の水分を５〜
20重量％に調湿し、40〜 150℃で予備加熱（シート状物
を加熱し軟化させることのみを目的とし、乾燥調湿は行
わない）し、50〜 170℃に保持した金型に入れ、二次成
形により容器を成形し、その金型内で後加熱し、しかる
後に乾燥させると、十分な機械的強度を持つ容器の得ら
れることを見出し、本発明を完成した。To explain this, the present inventors have found that polyvinyl alcohol-based resin is highly flexible when it contains water, and the sheet-like material in that state is conventionally known such as vacuum forming, pressure forming, vacuum pressure forming, and press forming. Secondary molding is possible, and it is heated and dried (a sheet-shaped material is molded into a mold or removed from the mold to remove water), and the container is As a result of advancing research focusing on the fact that a molded product having mechanical strength that can sufficiently satisfy the function as described above was formed, a polyvinyl alcohol-based resin was molded into a sheet and then dried, and the moisture content of the molded product was adjusted to 5 to 5.
Adjust the humidity to 20% by weight, preheat at 40 to 150 ° C (only for heating and softening the sheet material, do not perform dry humidity adjustment), and put it in the mold kept at 50 to 170 ° C. The inventors have found that a container having sufficient mechanical strength can be obtained by molding the container by secondary molding, post-heating in the mold, and then drying.
【０００８】本発明のポリビニルアルコール系樹脂製容
器の製造方法で用いられるポリビニルアルコール系樹脂
としては、ポリ酢酸ビニルなどのポリビニルエステルの
部分または完全ケン化物のほか、酢酸ビニルを主体と
し、これと他の共重合可能なモノマー、例えば不飽和カ
ルボン酸またはその部分または完全エステル・塩・無水
物・アミド・ニトリル、不飽和スルホン酸またはその
塩、炭素原子数２〜30のα−オレフィン、ビニルエーテ
ルなど、との共重合体をケン化した「共重合変性」ポリ
ビニルアルコールや、ポリビニルアルコールをアセター
ル化、ウレタン化、エーテル化、グラフト化またはリン
酸エステル化などした「後変性」ポリビニルアルコール
が挙げられる。The polyvinyl alcohol-based resin used in the method for producing a container made of a polyvinyl alcohol-based resin of the present invention includes partially or completely saponified polyvinyl ester such as polyvinyl acetate, and mainly vinyl acetate. A copolymerizable monomer of, for example, unsaturated carboxylic acid or its partial or complete ester / salt / anhydride / amide / nitrile, unsaturated sulfonic acid or its salt, α-olefin having 2 to 30 carbon atoms, vinyl ether, etc. Examples thereof include "copolymer-modified" polyvinyl alcohol obtained by saponifying a copolymer with and "post-modified" polyvinyl alcohol obtained by acetalizing, urethanizing, etherifying, grafting or phosphoricating polyvinyl alcohol.
【０００９】これらのポリビニルアルコール系樹脂の重
合度は、通常機械的強度の観点から100〜3000のものが
好ましく、またそのケン化度は耐水性の観点から70〜 1
00モル％のものが好ましい。また、これらのポリビニル
アルコール系樹脂には、容器としての機能を損ねない範
囲で、必要に応じて、グリセリン、ジエチレングリコー
ルのごとき可塑剤、グリセリン脂肪酸エステルのごとき
界面活性剤、ステアリン酸、モノグリセリンのごとき滑
剤、でんぷん、タルク、炭酸カルシウムのごとき充填
剤、安定剤、発泡剤、酸化チタン、カーボンブラックな
どの各種の顔料または染料等の着色物質等を添加するこ
ともできる。The polymerization degree of these polyvinyl alcohol resins is preferably 100 to 3000 from the viewpoint of mechanical strength, and the saponification degree thereof is 70 to 1 from the viewpoint of water resistance.
A content of 00 mol% is preferable. In addition, these polyvinyl alcohol-based resins may, if necessary, contain glycerin, a plasticizer such as diethylene glycol, a surfactant such as glycerin fatty acid ester, a stearic acid, or a monoglycerin as long as the function as a container is not impaired. Lubricants, starch, talc, fillers such as calcium carbonate, stabilizers, foaming agents, various pigments such as titanium oxide and carbon black, and coloring substances such as dyes can also be added.
【００１０】本発明はこのようなポリビニルアルコール
系樹脂に水とさらに必要に応じて他の添加剤を加えたも
のを出発原料として、常法にしたがって流延法または溶
融押出法によりシート状に成形し、乾燥あるいは調湿し
て水分が５〜20重量％になるようにする。The present invention uses a polyvinyl alcohol resin as described above, to which water and, if necessary, other additives are added, as a starting material, and is cast into a sheet by a conventional casting method or melt extrusion method. Then, it is dried or adjusted to a moisture content of 5 to 20% by weight.
【００１１】ここで、シート状物の水分が５重量％未満
では二次成形により容器を形作ることができず、またこ
れが20重量％を超えると二次成形はできるものの金型内
で容器を後加熱して乾燥させるのに時間がかかり過ぎる
ため適切ではない。Here, if the water content of the sheet material is less than 5% by weight, the container cannot be formed by secondary molding, and if it exceeds 20% by weight, the secondary molding is possible, but the container is left in the mold. Not suitable because it takes too long to heat and dry.
【００１２】このシート状物から二次成形により容器を
製造するには、まず40〜 150℃でシート状物を予備加熱
する。これが40℃未満では二次成形で容器を形作ること
ができず、また 150℃を超えると水分が低い状態でもシ
ート状物に発泡現象が生じて外観のよい容器を製造する
ことができない。In order to manufacture a container from this sheet by secondary molding, the sheet is first preheated at 40 to 150 ° C. If it is less than 40 ° C, the container cannot be formed by secondary molding, and if it exceeds 150 ° C, a foaming phenomenon occurs in the sheet even if the water content is low, and a container with a good appearance cannot be manufactured.
【００１３】二次成形は50〜 170℃に保持した金型を用
いて真空成形、圧空成形、真空圧空成形またはプレス成
形等、従来公知の方法により行われる。このときの金型
温度が50℃未満では成形品を金型内で乾燥させるのに熱
量が不足して時間がかかり過ぎ、また 170℃を超えると
シート状物の水分が低くても発泡現象が起きて、外観の
よい容器を製造することができない。得られた成形品は
前述したように金型内にそのまま数秒〜５分程度放置す
ることによって後加熱し、機械的強度の優れた容器とす
ることができる。なお、容器を水溶性にしたいときは、
ケン化度の低いポリビニルアルコール系樹脂を選択し、
後述する熱処理を施さないのがよい。Secondary molding is carried out by a conventionally known method such as vacuum molding, pressure molding, vacuum pressure molding or press molding using a mold maintained at 50 to 170 ° C. If the mold temperature at this time is less than 50 ° C, it takes too much time to dry the molded product in the mold, and if it exceeds 170 ° C, the foaming phenomenon will occur even if the water content of the sheet is low. I can't get up and make good looking containers. As described above, the obtained molded product can be left in the mold as it is for several seconds to 5 minutes to be post-heated to form a container having excellent mechanical strength. If you want to make the container water-soluble,
Select a polyvinyl alcohol resin with a low saponification degree,
It is preferable not to perform the heat treatment described later.
【００１４】得られる容器の耐水性を向上させるには、
ケン化度の高いポリビニルアルコール系樹脂を選択し、
成形後のシート状物を乾燥し、 100〜 200℃で数秒間〜
10分程度熱処理して結晶化させた後、前述した調湿・予
備加熱・金型装入・二次成形・後加熱・乾燥の各操作を
施すか、前述した方法によって得られた容器をさらにオ
ーブン、乾燥炉などで 100〜 200℃で数秒間〜10分程度
熱処理して結晶化するのが好ましい。なお、この際の熱
処理温度が 100℃未満では熱処理に時間がかかり過ぎ、
また 200℃を超えるとシート状物が変色する恐れがあ
る。To improve the water resistance of the resulting container,
Select a polyvinyl alcohol resin with a high degree of saponification,
Dry the molded sheet and keep it at 100-200 ℃ for several seconds.
After heat treatment for about 10 minutes to crystallize, perform each of the above-mentioned operations of humidity control, pre-heating, die charging, secondary molding, post-heating, and drying, or by further adding the container obtained by the method described above. It is preferable to heat-treat at 100 to 200 ° C. for several seconds to 10 minutes in an oven or a drying oven to crystallize. If the heat treatment temperature at this time is less than 100 ° C, the heat treatment will take too long,
Also, if the temperature exceeds 200 ° C, the sheet material may be discolored.
【００１５】上記のほか、容器に成形する前のシート状
物や成形後の容器の表面を、ウレタン系樹脂、アクリル
系樹脂、ポリ塩化ビニリデン樹脂、ポリ塩化ビニル樹脂
などでコーティングすることによっても耐水性を向上さ
せることができる。In addition to the above, water resistance can also be obtained by coating the sheet material before molding into a container or the surface of the container after molding with a urethane resin, an acrylic resin, a polyvinylidene chloride resin, a polyvinyl chloride resin or the like. It is possible to improve the sex.
【００１６】なお、本発明の方法における出発原料を、
上記流延法または溶融押出法によって得られたシート状
物の片面に他の熱可塑性樹脂からなるフィルムまたはシ
ートを積層したものとしたときは、片面からの乾燥で乾
燥効率が若干悪くなり易いものの、上記シート状物のみ
からなるものと同様の操作で、積層容器を製造すること
ができる。The starting materials used in the method of the present invention are
When a film or sheet made of another thermoplastic resin is laminated on one surface of the sheet-like material obtained by the casting method or the melt extrusion method, the drying efficiency tends to be slightly deteriorated due to drying from one surface. The laminated container can be manufactured by the same operation as that for forming only the above sheet-like material.
【００１７】[0017]
【作 用】ポリビニルアルコール系樹脂は水を含んでい
ると、水が可塑剤の役目を果たして柔軟性があり、真空
成形等の二次成形を容易に行うことができる。また、水
分を含まないものは硬質で機械的強度も大きく容器とし
ての特性に優れている。そこで、含水時に二次成形を行
い、そのまま金型の中で後加熱し乾燥させることで、容
器としての機械的強度を向上させることに成功した。[Operation] When the polyvinyl alcohol-based resin contains water, the water acts as a plasticizer and is flexible, and secondary molding such as vacuum molding can be easily performed. In addition, those that do not contain water are hard and have high mechanical strength, and are excellent in container characteristics. Therefore, we succeeded in improving the mechanical strength of the container by carrying out secondary molding while containing water and then post-heating and drying in the mold as it is.
【００１８】[0018]
【実施例】以下、本発明の具体的態様を実施例、比較例
および参考例により説明する。 実施例１〜４、比較例１〜３：表１に示す重合度および
ケン化度のポリビニルアルコール樹脂 100重量部に対し
100重量部の水を添加してペレット化した後、40φ押出
機を用いて 400mm幅のＴダイより溶融押出して表１に示
すシート状物を得た。次に、これを用いて表１に示す条
件で真空成形を行い、直径96φ、高さ30mmの円筒状の容
器を作製した。なお、この際の後加熱温度は金型温度と
同じとし、後加熱時間は１分とした。得られた容器の側
壁部よりダンベル状の試料片を打ち抜いて、JIS K-6734
に基づいて引張強度を測定し、その値が 400kg/cm2以上
のものを○、 400kg/cm2未満のものを×として、表１に
併記した。EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples, Comparative Examples and Reference Examples. Examples 1 to 4, Comparative Examples 1 to 3: Based on 100 parts by weight of the polyvinyl alcohol resin having the degree of polymerization and the degree of saponification shown in Table 1.
After 100 parts by weight of water was added to form pellets, they were melt extruded from a T-die having a width of 400 mm using a 40φ extruder to obtain sheet-like materials shown in Table 1. Next, using this, vacuum forming was performed under the conditions shown in Table 1 to produce a cylindrical container having a diameter of 96φ and a height of 30 mm. The post-heating temperature at this time was the same as the mold temperature, and the post-heating time was 1 minute. A dumbbell-shaped sample piece was punched out from the side wall of the obtained container to JIS K-6734.
The tensile strength was measured on the basis of that value ○ those 400 kg / cm 2 or more, as × a of less than 400 kg / cm 2, are also shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】参考例１〜３：実施例２と全く同じ条件で
真空成形して作製した円筒状容器（参考例１）、実施例
２で得られたシート状物に 190℃で３分の熱処理を施
し、水分を８重量％に調湿した後、実施例２と同様に真
空成形して作製した円筒状容器（参考例２）および実施
例２と全く同じ条件で真空成形して作製した円筒状容器
に、 190℃で５分の熱処理を施した容器（参考例３）を
準備し、それぞれの容器を23℃の水に24時間浸漬した
後、重量を測定し、重量の増加率が10％未満（機械的強
度の低下が見られないとされる目安）のものを○、10％
以上のものを×として耐水性の目安とし、その結果を表
２に示した。Reference Examples 1 to 3: A cylindrical container (Reference Example 1) produced by vacuum forming under exactly the same conditions as in Example 2, and the sheet-like material obtained in Example 2 heat treated at 190 ° C. for 3 minutes. And the moisture was adjusted to 8% by weight, and then a cylindrical container (Reference Example 2) produced by vacuum forming in the same manner as in Example 2 and a cylinder produced by vacuum forming under exactly the same conditions as in Example 2 A container (reference example 3) that had been subjected to a heat treatment at 190 ° C for 5 minutes was prepared, and each container was immersed in water at 23 ° C for 24 hours, and then the weight was measured. %, ○ (10%)
The above was designated as x to be a measure of water resistance, and the results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【発明の効果】本発明によれば、ポリビニルアルコール
系樹脂を主成分とするシート状物から二次成形により容
易に容器を製造することができるので、例えば １）従来のフィルムに比べて厚いものが用いられるた
め、ハイバリアー容器の製造が可能になる、 ２）非帯電性の（とくに充填剤を加えないときは透明
な）容器ができるため、電子部品など静電気を嫌うもの
の包装容器として最適である、 ３）でんぷんなどの水溶性成分の添加により、水中や土
中で分解可能な容器となるため、環境問題に対応できる
ものとなる、 ４）ケン化度の低いポリビニルアルコール系樹脂を使用
し、熱処理を施さないものは、水または熱水に可溶なた
め容器の減容化ができゴミ問題に対応できる、などポリ
ビニルアルコール系樹脂の特性を生かした用途展開が図
れる。EFFECTS OF THE INVENTION According to the present invention, a container can be easily manufactured from a sheet-like material containing a polyvinyl alcohol resin as a main component by secondary molding. Therefore, for example, 1) a thicker film than a conventional film is used. It is possible to manufacture high-barrier containers because it is used. 2) Since it is possible to make non-chargeable (especially transparent when no filler is added) containers, it is ideal as a packaging container for those who dislike static electricity such as electronic parts. Yes, 3) Addition of water-soluble components such as starch makes it a container that can be decomposed in water or soil, which makes it possible to deal with environmental problems. 4) Uses polyvinyl alcohol resin with a low degree of saponification. , Those that are not heat-treated are soluble in water or hot water, so the volume of the container can be reduced and the problem of dust can be addressed. Can be achieved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 22:00 4Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B29L 22:00 4F
Claims (3)
成形した後、乾燥し、成形物の水分を５〜20重量％に調
湿し、40〜 150℃で予備加熱し、50〜 170℃に保持した
金型に入れ、二次成形により容器を成形し、その金型内
で後加熱し、しかる後に乾燥することを特徴とするポリ
ビニルアルコール系樹脂製容器の製造方法。1. A polyvinyl alcohol resin is molded into a sheet and then dried, the moisture content of the molded product is adjusted to 5 to 20% by weight, preheated at 40 to 150 ° C., and maintained at 50 to 170 ° C. The method for producing a polyvinyl alcohol-based resin container is characterized in that the container is molded by secondary molding, the container is post-heated in the mold, and then dried.
した後、調湿することを特徴とする請求項１記載のポリ
ビニルアルコール系樹脂製容器の製造方法。2. The method for producing a polyvinyl alcohol-based resin container according to claim 1, wherein the molded and dried sheet material is subjected to heat treatment and then subjected to humidity control.
処理を施すことを特徴とする請求項１記載のポリビニル
アルコール系樹脂製容器の製造方法。3. The method for producing a polyvinyl alcohol-based resin container according to claim 1, wherein the container obtained by the method according to claim 1 is heat-treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9181192A JPH05261802A (en) | 1992-03-17 | 1992-03-17 | Manufacture of polyvinyl alcohol base resin made container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9181192A JPH05261802A (en) | 1992-03-17 | 1992-03-17 | Manufacture of polyvinyl alcohol base resin made container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05261802A true JPH05261802A (en) | 1993-10-12 |
Family
ID=14037017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9181192A Pending JPH05261802A (en) | 1992-03-17 | 1992-03-17 | Manufacture of polyvinyl alcohol base resin made container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05261802A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996029189A3 (en) * | 1995-03-22 | 1996-11-07 | Harding Product Supply Ltd | Vacuum formed three-dimensional surface article |
| US5904962A (en) * | 1996-07-12 | 1999-05-18 | Hallmark Cards, Incorporated | Raised mounting system for artistic work |
| US6444148B2 (en) | 1996-05-08 | 2002-09-03 | Glenn T. Harding | Process and making molds for thermoforming a three-dimensional relief reproduction |
| JP2002293961A (en) * | 2001-03-30 | 2002-10-09 | Unitika Ltd | Bag for clothes |
| GB2405828A (en) * | 2003-09-12 | 2005-03-16 | Reckitt Benckiser Nv | Improvements in or relating to containers using a thermoforming process |
| WO2014154710A1 (en) * | 2013-03-28 | 2014-10-02 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for producing an object made of a hardened polymer material |
-
1992
- 1992-03-17 JP JP9181192A patent/JPH05261802A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996029189A3 (en) * | 1995-03-22 | 1996-11-07 | Harding Product Supply Ltd | Vacuum formed three-dimensional surface article |
| US5667747A (en) * | 1995-03-22 | 1997-09-16 | Harding Product Supply Ltd. | Vacuum formed three-dimensional surface article |
| US6444148B2 (en) | 1996-05-08 | 2002-09-03 | Glenn T. Harding | Process and making molds for thermoforming a three-dimensional relief reproduction |
| US5904962A (en) * | 1996-07-12 | 1999-05-18 | Hallmark Cards, Incorporated | Raised mounting system for artistic work |
| JP2002293961A (en) * | 2001-03-30 | 2002-10-09 | Unitika Ltd | Bag for clothes |
| GB2405828A (en) * | 2003-09-12 | 2005-03-16 | Reckitt Benckiser Nv | Improvements in or relating to containers using a thermoforming process |
| WO2014154710A1 (en) * | 2013-03-28 | 2014-10-02 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for producing an object made of a hardened polymer material |
| FR3003788A1 (en) * | 2013-03-28 | 2014-10-03 | Commissariat Energie Atomique | METHOD FOR MANUFACTURING AN OBJECT OF A CURED POLYMERIC MATERIAL |
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