JPH07116342B2 - Cooling material - Google Patents
Cooling materialInfo
- Publication number
- JPH07116342B2 JPH07116342B2 JP880987A JP880987A JPH07116342B2 JP H07116342 B2 JPH07116342 B2 JP H07116342B2 JP 880987 A JP880987 A JP 880987A JP 880987 A JP880987 A JP 880987A JP H07116342 B2 JPH07116342 B2 JP H07116342B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- water
- polyvinyl chloride
- gel
- 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.)
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Links
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- Compositions Of Macromolecular Compounds (AREA)
- Thermotherapy And Cooling Therapy Devices (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は低温での柔軟性と弾力性に優れる保冷材に関す
る。TECHNICAL FIELD The present invention relates to a cold insulating material having excellent flexibility and elasticity at low temperatures.
（従来の技術およびその問題点） 市販の保冷材の多くはゼラチンやポリビニルアルコール
或いはポリエチレンオキサイドなどの水溶性高分子に水
を吸着せしめたゲルが用いられているが（特開昭56−36
538号公報および特開昭56−45977号公報）、このゲルは
低温では非常に固く固化するので低温柔軟性は無い。従
って、氷枕の代用として使用する場合には不便である。(Prior Art and its Problems) Most of the commercially available cold insulating materials use a gel in which water is adsorbed to a water-soluble polymer such as gelatin, polyvinyl alcohol or polyethylene oxide (JP-A-56-36).
No. 538 and JP-A-56-45977), this gel does not have low-temperature flexibility because it solidifies very hard at low temperature. Therefore, it is inconvenient when used as a substitute for an ice pillow.
特公昭47−18409号公報には未加硫弾性ブロック共重合
体とパラフィン系油からなる油性ゲルが開示されている
が、これらは柔軟ではあるが保冷性に劣る欠点を有す
る。JP-B-47-18409 discloses an oily gel composed of an unvulcanized elastic block copolymer and paraffin oil, but these have the drawback of being inferior in cold insulation although they are flexible.
特開昭60−79061号公報にはテレブロック共重合エラス
トマーと油成分からなる連続相に含水した吸水性架橋性
高分子粒子を分散したものが開示されており、特公昭60
−11738号公報には高沸点の油性物質と天然ゴム、合成
ゴム質とを含む均一系分散媒に水分散質を分散させた油
中水型エマルジョンを架橋剤の存在下で架橋してゲル化
したしたものが開示されている。これらはいずれも保冷
性に優れ、低温での柔軟性にすぐれるものの、工程が複
雑で高価になる。また、水の量が増すと機械的、熱的安
定性が損なわれ、水の分離がみられることがある。JP-A-60-79061 discloses a dispersion of water-absorptive crosslinkable polymer particles containing water in a continuous phase composed of a teleblock copolymer elastomer and an oil component.
No. 11738 discloses that a water-in-oil emulsion in which a water dispersoid is dispersed in a homogeneous dispersion medium containing an oily substance having a high boiling point, natural rubber, and synthetic rubber is crosslinked in the presence of a crosslinking agent to form a gel. What has been done is disclosed. All of these have excellent cold retention properties and excellent flexibility at low temperatures, but the process is complicated and expensive. Further, when the amount of water increases, mechanical and thermal stability may be impaired and water may be separated.
（発明の目的） 本発明は安価で保冷性に優れ、かつ低温での柔軟性に優
れる保冷材を提供する。(Object of the Invention) The present invention provides a cold insulating material which is inexpensive, has excellent cold insulating properties, and has excellent flexibility at low temperatures.
（発明の構成） 即ち、本発明はポリ塩化ビニル、可塑剤、含水吸水ゲル
または水溶性ポリマー水溶液および乳化剤を含有する保
冷材を提供する。(Structure of Invention) That is, the present invention provides a cold insulating material containing polyvinyl chloride, a plasticizer, a water-containing water-absorbing gel or an aqueous solution of a water-soluble polymer, and an emulsifier.
ポリ塩化ビニルは容易に入手できる安価な工業材料であ
る。ポリ塩化ビニルの平均重合度は通常900〜3000が好
適である。Polyvinyl chloride is a readily available and inexpensive industrial material. The average degree of polymerization of polyvinyl chloride is usually preferably 900 to 3000.
本発明に使用する可塑剤はポリ塩化ビニル用のものであ
ればいかなるものを用いてもよい。使用し得る可塑剤の
例としてはジ２−エチルヘキシルフタレート（DOP）、
ジブチルフタレート（DBP）、ジ２−エチルヘキシルア
ジペート（DOA）、ジ２−エチルヘキシルセバケート（D
OS）、ジ２−エチルヘキシルアゼレート（DOZ）、ジイ
ソデシルアジペート（DIDA）、ジブチルセバケート（DB
S）エポキシ化大豆油、塩素化パラフィン、ポリエステ
ル可塑剤等が挙げられる。可塑剤の使用量はポリ塩化ビ
ニル10重量部に対して30〜500重量部、好ましくは75〜2
00重量部である。500重量部を越えるとゲル強度が悪く
なる等の欠点を有する。70重量部より少ないと取り出し
時の温度を高くしないと流れが悪くなる等の欠点を有す
る。As the plasticizer used in the present invention, any plasticizer may be used as long as it is for polyvinyl chloride. Examples of plasticizers that can be used are di2-ethylhexyl phthalate (DOP),
Dibutyl phthalate (DBP), di2-ethylhexyl adipate (DOA), di2-ethylhexyl sebacate (D
OS), di2-ethylhexyl azelate (DOZ), diisodecyl adipate (DIDA), dibutyl sebacate (DB)
S) Epoxidized soybean oil, chlorinated paraffin, polyester plasticizer and the like. The amount of plasticizer used is 30 to 500 parts by weight, preferably 75 to 2 parts by weight based on 10 parts by weight of polyvinyl chloride.
00 parts by weight. If it exceeds 500 parts by weight, there is a drawback that the gel strength becomes poor. If the amount is less than 70 parts by weight, the flow will be deteriorated unless the temperature at the time of taking out is raised.
吸水ゲルは吸水性の高分子重合体であり、例えばアクリ
ル酸ソーダ重合体、ビニルアルコール−アクリル酸共重
合体、またはイソプレン−無水マレイン酸共重合体等が
挙げられる。吸水ゲルの代わりに水溶性ポリマーを用い
てもよい。水溶性ポリマーの例としてはカルボキシメチ
ルセルローズ（CMC）、メチルセルローズ（MC）、ポリ
ビニルアルコール（PVA）、アルギン酸ソーダ、デンプ
ン、寒天、プルラン等が挙げられる。吸水ゲルまたは水
溶性ポリマーは水溶液の形で保冷材中に添加される。吸
水ゲルは水100重量部に対し、0.1〜5.5重量部、好まし
くは0.2〜2.0重量部添加する。水溶性ポリマーは水100
重量部に対し0.1〜5.5重量部、好ましくは2.0〜3.1重量
部添加する。ポリ塩化ビニル10重量部に対する含水吸水
ゲルまたは水溶性ポリマー水溶液の量は50〜200重量
部、好ましくは80〜150重量部である。200重量部を越え
ると冷凍時の硬さが増す等の欠点を有し、50重量部より
小さいと保冷熱量が小さくなる等の欠点を有する。The water-absorbent gel is a water-absorbing polymer, and examples thereof include sodium acrylate polymer, vinyl alcohol-acrylic acid copolymer, isoprene-maleic anhydride copolymer, and the like. A water-soluble polymer may be used instead of the water-absorbing gel. Examples of water-soluble polymers include carboxymethyl cellulose (CMC), methyl cellulose (MC), polyvinyl alcohol (PVA), sodium alginate, starch, agar, pullulan and the like. The water-absorbing gel or the water-soluble polymer is added to the cold insulator in the form of an aqueous solution. The water-absorbing gel is added in an amount of 0.1 to 5.5 parts by weight, preferably 0.2 to 2.0 parts by weight, based on 100 parts by weight of water. Water-soluble polymer is water 100
0.1 to 5.5 parts by weight, preferably 2.0 to 3.1 parts by weight, is added to parts by weight. The amount of the water-containing water-absorbing gel or the aqueous solution of the water-soluble polymer is 50 to 200 parts by weight, preferably 80 to 150 parts by weight, based on 10 parts by weight of polyvinyl chloride. If it exceeds 200 parts by weight, the hardness during freezing will increase, and if it is less than 50 parts by weight, the cold storage heat amount will decrease.
乳化剤は通常使用されるいかなるものを用いてもよい
が、凝集または沈澱を防止するためにノニオン界面活性
剤が好適である。そのようなものの例としてはグリセリ
ンモノオレエート、ソルビタンモノオレエート、ポリエ
チレングリコールオレイルエーテル等が挙げられる。ポ
リ塩化ビニル10重量部に対する乳化剤の使用量は１〜25
重量部、好ましくは７〜17重量部である。25重量部を越
えると冷凍時の硬さが増す等の欠点を有し、１重量部よ
り小さいと水分が分離しやすくなる等の欠点を有する。As the emulsifier, any emulsifier usually used may be used, but a nonionic surfactant is preferable in order to prevent aggregation or precipitation. Examples of such substances include glycerin monooleate, sorbitan monooleate, polyethylene glycol oleyl ether and the like. The amount of emulsifier used is 10 to 25 parts by weight of polyvinyl chloride.
Parts by weight, preferably 7 to 17 parts by weight. If it exceeds 25 parts by weight, the hardness during freezing increases, and if it is less than 1 part by weight, water easily separates.
本発明の保冷材にはフィラーあるいはガラス粉末を混入
してもよい。フィラーの例としては炭酸カルシウム、酸
化アルミニウム、オクチル酸アルミニウム、粉末マイ
カ、発泡ポリエチレン、発泡ポリスチレン、タルク、コ
ルク等が挙げられる。ガラス粉末の例としては硼酸塩ガ
ラス、珪酸塩ガラス、リン酸塩ガラス等が挙げられる。
水溶性ポリマーとの反応性の観点から硼酸塩ガラスまた
は硼酸塩ガラスと他の酸化物ガラスとの混合物が好まし
い。硼酸塩ガラスは通常B2O3を主成分として含有する
が、ガラス化を妨げない限り他の成分、例えばAl2O3、K
2O、Na2O、CaO、MgO等を含んでもよい。酸化物ガラスは
通常ガラスを常法により溶融、冷却後、粉砕して用い
る。ガラス粉末の粒度は特に制限がないが、10〜250
μ、好ましくは50〜150μが好ましい。A filler or glass powder may be mixed in the cold insulating material of the present invention. Examples of the filler include calcium carbonate, aluminum oxide, aluminum octylate, powdered mica, expanded polyethylene, expanded polystyrene, talc, cork and the like. Examples of the glass powder include borate glass, silicate glass, phosphate glass and the like.
From the viewpoint of reactivity with the water-soluble polymer, borate glass or a mixture of borate glass and another oxide glass is preferable. Borate glass usually contains B 2 O 3 as a main component, but other components such as Al 2 O 3 and K may be used as long as they do not prevent vitrification.
2 O, Na 2 O, CaO, MgO, etc. may be contained. The oxide glass is usually used by melting glass by a conventional method, cooling it, and then crushing it. The particle size of the glass powder is not particularly limited, but 10 to 250
μ, preferably 50 to 150 μ.
本発明の保冷材は通常ポリ塩化ビニルと可塑剤を140〜1
70℃で均一に混合し、次いで含水吸水ゲルまたは水溶性
ポリマー水溶液を配合して乳化剤の存在下に両者を十分
に混合することにより得られる。通常撹拌は70〜100℃
で１〜２時間混合したのち、ホモミキサーで十分に混合
する。この混合に際し、必要に応じて顔料等の着色剤、
防腐剤、紫外線吸収剤、酸化防止剤等の他の添加剤を混
入してもよい。The cold insulating material of the present invention usually contains polyvinyl chloride and a plasticizer in an amount of 140 to 1
It can be obtained by uniformly mixing at 70 ° C., then adding a water-containing water-absorbing gel or an aqueous solution of a water-soluble polymer and thoroughly mixing both in the presence of an emulsifier. Normal stirring is 70-100 ° C
After mixing for 1-2 hours, thoroughly mix with a homomixer. Upon this mixing, if necessary, a coloring agent such as a pigment,
You may mix other additives, such as a preservative, an ultraviolet absorber, and an antioxidant.
（発明の効果） 得られた保冷材は−10〜20℃の低温に於いても充分な柔
軟性と弾力性を保ち且つ油水の分離がない。また70℃〜
100℃の加熱に対しても充分安定である。(Effect of the invention) The obtained cold insulating material maintains sufficient flexibility and elasticity even at a low temperature of -10 to 20 ° C and does not separate oil and water. Also 70 ℃ ~
It is sufficiently stable even when heated to 100 ° C.
（実施例） 本発明を実施例により更に詳細に説明する。(Examples) The present invention will be described in more detail with reference to Examples.
実施例１ ポリ塩化ビニル（住友化学製スミリットSX−11F）10重
量部、ジ２−エチルヘキシルフタレート70重量部、ジ２
−エチルヘキシルアジペート40重量部をよく撹拌し乍ら
150℃に昇温し、30分間その温度で撹拌を続けた。これ
にグリセリンモノオレエート10重量部を加え充分に撹拌
して均一になったら100℃迄冷却した。次いでカルボキ
シメチルセルローズ４重量部を水100重量部に溶解させ
た溶液を90℃に昇温しておき、これに前述のポリ塩化ビ
ニルの可塑剤溶液を加えて撹拌し白色のゲルを得た。Example 1 Polyvinyl chloride (Summit SX-11F manufactured by Sumitomo Chemical Co., Ltd.) 10 parts by weight, di2-ethylhexyl phthalate 70 parts by weight, di 2
-Agitate 40 parts by weight of ethylhexyl adipate well.
The temperature was raised to 150 ° C. and stirring was continued at that temperature for 30 minutes. To this, 10 parts by weight of glycerin monooleate was added, and the mixture was sufficiently stirred and cooled to 100 ° C. when uniform. Then, a solution prepared by dissolving 4 parts by weight of carboxymethyl cellulose in 100 parts by weight of water was heated to 90 ° C., and the above-mentioned polyvinyl chloride plasticizer solution was added thereto and stirred to obtain a white gel.
このものは−20℃に一夜放置後も指先で押して充分変形
しうる柔軟性と指先で押した変形が元に戻る弾力性を失
わなかった。Even after being left at -20 ° C overnight, this product did not lose the flexibility that could be sufficiently deformed by pushing with a fingertip and the elasticity that the deformation pushed by a fingertip returns to its original state.
実施例２ ポリ塩化ビニル10重量部、ジブチルフタレート40重量
部、ジ２−エチルヘキシルフタレート40重量部、ジ２−
エチルヘキシルアジペート40重量部を用いて実施例１と
同様の操作をし、グリセリンモノオレエート12重量部を
加え、撹拌後100℃に冷却した。ポリビニルアルコール
３重量部、ホウ酸ガラス粉末0.3重量部を水100重量部に
加え、加熱撹拌して90℃に昇温し、これに前記ポリ塩化
ビニルの可塑剤溶液を加えて撹拌して白色のゲルを得
た。Example 2 10 parts by weight of polyvinyl chloride, 40 parts by weight of dibutyl phthalate, 40 parts by weight of di2-ethylhexyl phthalate, di2-
The same operation as in Example 1 was performed using 40 parts by weight of ethylhexyl adipate, 12 parts by weight of glycerin monooleate was added, and the mixture was stirred and cooled to 100 ° C. Add 3 parts by weight of polyvinyl alcohol and 0.3 parts by weight of boric acid glass powder to 100 parts by weight of water, heat and stir to raise the temperature to 90 ° C., add the plasticizer solution of polyvinyl chloride to this and stir to give a white color. A gel was obtained.
このものも−20℃に一夜放置后、柔軟性、弾力性を失わ
なかった。This product also did not lose its flexibility and elasticity after being left overnight at -20 ° C.
実施例３ ポリ塩化ビニル10量部、ジ２−エチルヘキシルフタレー
ト89重量部、ジ２−エチルヘキシルセバケート33重量部
とソルビタンモノオレエート11重量部及びポリビニルア
ルコール3.3重量部、ホウ酸ガラス粉末0.3重量部を用い
て実施例１と同様の操作によってゲルを得た。Example 3 10 parts by weight of polyvinyl chloride, 89 parts by weight of di2-ethylhexyl phthalate, 33 parts by weight of di2-ethylhexyl sebacate, 11 parts by weight of sorbitan monooleate and 3.3 parts by weight of polyvinyl alcohol, 0.3 part by weight of boric acid glass powder. A gel was obtained by the same procedure as in Example 1 using.
このものも実施例１と同様−20℃に一夜放置後も柔軟
性、弾力性を失わなかった。Similar to Example 1, this product did not lose its flexibility and elasticity even after being left overnight at -20 ° C.
実施例４ ポリ塩化ビニル10重量部、ジ２−エチルヘキシルフタレ
ート100重量部、ジ２−エチルヘキシルアジペート37.5
重量部とグリセリンモノオレエート15重量部を用いて実
施例１と同様の操作で溶液とし、これに炭酸カルシウム
12.5重量部を加えて充分均一溶液になるよう撹拌し、こ
れをカルボキシメチルセルローズ５重量部と水125重量
部の溶液に実施例１と同様の方法で加えてゲルを得た。Example 4 Polyvinyl chloride 10 parts by weight, di2-ethylhexyl phthalate 100 parts by weight, di2-ethylhexyl adipate 37.5
A solution was prepared by the same procedure as in Example 1 using 15 parts by weight of glycerin monooleate and 1 part by weight of calcium carbonate.
12.5 parts by weight was added and stirred to form a sufficiently homogeneous solution, which was added to a solution of 5 parts by weight of carboxymethyl cellulose and 125 parts by weight of water in the same manner as in Example 1 to obtain a gel.
このゲルも−20℃に一夜放置後も柔軟性、弾力性を保有
していた。This gel retained its flexibility and elasticity even after being left overnight at -20 ° C.
実施例５ ポリ塩化ビニル10重量部にジ２−エチルヘキシルフタレ
ート58重量部およびジ２−エチルヘキシルアジペート33
重量部を加え、150℃に加温し、充分に溶解した。後に
グリセリンモノオレエート８重量部を加えた。別にイソ
プレン−無水マレイン酸共重合体（クラレイソプレンケ
ミカル製KIゲル−201、Ｋ−F2）1.7重量部に83重量部の
水を含水させたものを用意しておき、95℃で上記ポリ塩
化ビニル溶液中に徐々に投入し乍ら撹拌した。Example 5 10 parts by weight of polyvinyl chloride, 58 parts by weight of di2-ethylhexyl phthalate and 33 parts of di2-ethylhexyl adipate 33
Part by weight was added, and the mixture was heated to 150 ° C. and sufficiently dissolved. Afterwards 8 parts by weight of glycerin monooleate were added. Separately, 1.7 parts by weight of isoprene-maleic anhydride copolymer (KI gel-201, K-F2 manufactured by Kuraray Isoprene Chemical) and 83 parts by weight of water were prepared, and the polyvinyl chloride was prepared at 95 ° C. The mixture was gradually added to the solution and stirred.
充分撹拌後取り出したゲルは−20℃に一夜放置後も充分
な柔軟性と弾力性のある保冷材であった。The gel taken out after sufficient stirring was a cold insulating material having sufficient flexibility and elasticity even after being left overnight at -20 ° C.
実施例６ ポリ塩化ビニル10重量部にジ２−エチルヘキシルフタレ
ート80重量部およびジ２−エチルヘキシルアジペート30
重量部を加え、150℃に加温し充分に溶解した後にグリ
セリンモノオレエート10重量部を加えた。別にビニルア
ルコール−アクリル酸共重合体（住友化学製スミカゲル
SP−520）２重量部に100重量部の水を含水させたものを
用意しておき、これに95℃で上記ポリ塩化ビニルの可塑
剤溶液を撹拌しながら徐々に添加した。Example 6 10 parts by weight of polyvinyl chloride, 80 parts by weight of di2-ethylhexyl phthalate and 30 parts of di2-ethylhexyl adipate
10 parts by weight of glycerin monooleate was added after adding 1 part by weight and heating to 150 ° C. to sufficiently dissolve it. Separately, vinyl alcohol-acrylic acid copolymer (Sumitomo Chemical's Sumika gel
2 parts by weight of SP-520) containing 100 parts by weight of water was prepared, and the plasticizer solution of polyvinyl chloride was gradually added thereto at 95 ° C. with stirring.
充分撹拌後取り出したゲルは−20℃に一夜放置後も充分
な柔軟性と弾力性のある保冷材であった。The gel taken out after sufficient stirring was a cold insulating material having sufficient flexibility and elasticity even after being left overnight at -20 ° C.
比較例１ 特公昭60−11738号公報の実施例１に基づいて作成し
た。Comparative Example 1 It was prepared based on Example 1 of JP-B-60-11738.
比較例２ カルボキシメチルセルロース30部と水500部を70℃でよ
く撹拌して含水ゲルを得た。Comparative Example 2 30 parts of carboxymethyl cellulose and 500 parts of water were well stirred at 70 ° C. to obtain a hydrogel.
試験例 上記実施例中、実施例２、４および５と比較例１および
２について保冷時、冷凍時の柔軟性、形状記憶および油
水分散について試験した。結果を表−１に示す。Test Example In the above Examples, Examples 2, 4 and 5 and Comparative Examples 1 and 2 were tested for flexibility during cold storage and during freezing, shape memory and oil-water dispersion. The results are shown in Table-1.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭55−102653（ＪＰ，Ａ) 特開 昭60−79061（ＪＰ，Ａ) 特開 昭59−82939（ＪＰ，Ａ) 特開 昭56−18917（ＪＰ，Ａ) 特公 昭46−19601（ＪＰ，Ｂ１) 特公 昭46−19602（ＪＰ，Ｂ１) 特公 昭52−48895（ＪＰ，Ｂ２) 特公 昭61−54074（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-55-102653 (JP, A) JP-A-60-79061 (JP, A) JP-A-59-82939 (JP, A) JP-A-56- 18917 (JP, A) JP 46-19601 (JP, B1) JP 46-19602 (JP, B1) JP 52-48895 (JP, B2) JP 61-54074 (JP, B2)
Claims (2)
たは水溶性ポリマー水溶液および乳化剤を含有する保冷
材。1. A cold insulating material containing polyvinyl chloride, a plasticizer, a water-containing water-absorbing gel or an aqueous solution of a water-soluble polymer, and an emulsifier.
〜500重量部、含水吸水ゲルまたは水溶性ポリマー水溶
液50〜200重量部および乳化剤１〜25重量部含有する第
１項記載の保冷材。2. A plasticizer 30 per 10 parts by weight of polyvinyl chloride.
The cold-insulating material according to claim 1, which comprises -500 parts by weight, 50-200 parts by weight of a water-containing water-absorbing gel or an aqueous solution of a water-soluble polymer, and 1-25 parts by weight of an emulsifier.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP880987A JPH07116342B2 (en) | 1987-01-17 | 1987-01-17 | Cooling material |
| PCT/JP1988/000031 WO1988005458A1 (en) | 1987-01-17 | 1988-01-16 | Low-temperature insulating material |
| DE88900849T DE3884683T2 (en) | 1987-01-17 | 1988-01-16 | MATERIAL INSULATING AT LOW TEMPERATURE. |
| US07/254,660 US5077336A (en) | 1987-01-17 | 1988-01-16 | Low-temperature insulating material |
| EP88900849A EP0298131B1 (en) | 1987-01-17 | 1988-01-16 | Low-temperature insulating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP880987A JPH07116342B2 (en) | 1987-01-17 | 1987-01-17 | Cooling material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63178156A JPS63178156A (en) | 1988-07-22 |
| JPH07116342B2 true JPH07116342B2 (en) | 1995-12-13 |
Family
ID=11703161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP880987A Expired - Fee Related JPH07116342B2 (en) | 1987-01-17 | 1987-01-17 | Cooling material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07116342B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5248895B2 (en) | 2008-03-31 | 2013-07-31 | 株式会社小松製作所 | Traveling work vehicle |
| JP6154074B2 (en) | 2013-08-21 | 2017-06-28 | ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ | Method for crushing polycrystalline silicon fragments and polycrystalline silicon rods |
-
1987
- 1987-01-17 JP JP880987A patent/JPH07116342B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5248895B2 (en) | 2008-03-31 | 2013-07-31 | 株式会社小松製作所 | Traveling work vehicle |
| JP6154074B2 (en) | 2013-08-21 | 2017-06-28 | ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ | Method for crushing polycrystalline silicon fragments and polycrystalline silicon rods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63178156A (en) | 1988-07-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |