JPS5921897B2 - Processing of casein plastics - Google Patents
Processing of casein plasticsInfo
- Publication number
- JPS5921897B2 JPS5921897B2 JP8156375A JP8156375A JPS5921897B2 JP S5921897 B2 JPS5921897 B2 JP S5921897B2 JP 8156375 A JP8156375 A JP 8156375A JP 8156375 A JP8156375 A JP 8156375A JP S5921897 B2 JPS5921897 B2 JP S5921897B2
- Authority
- JP
- Japan
- Prior art keywords
- casein
- plastics
- casein plastics
- formaldehyde
- processing
- 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
Links
- 239000005018 casein Substances 0.000 title claims description 25
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 title claims description 25
- 235000021240 caseins Nutrition 0.000 title claims description 25
- 239000004033 plastic Substances 0.000 title claims description 20
- 229920003023 plastic Polymers 0.000 title claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 43
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 2
- 238000011282 treatment Methods 0.000 description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229940108461 rennet Drugs 0.000 description 2
- 108010058314 rennet Proteins 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- 206010000372 Accident at work Diseases 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
本発明はカゼインプラスチツクスの処理法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating casein plastics.
更に詳しく云えばカゼインをホルムアルデヒドで硬化し
て得たカゼインプラス’チックズを尿素類またはＰＫａ
４以上の有機もしくは無機酸のアンモニウム塩の水溶液
で処理することを特徴とするカゼインプラスチツクスか
らホルムアルヂヒドの湧出を防止する方法に関するもの
である。More specifically, casein plastics obtained by hardening casein with formaldehyde are used as ureas or PKa.
The present invention relates to a method for preventing formaldehyde from seeping out from casein plastics, which is characterized by treatment with an aqueous solution of ammonium salts of four or more organic or inorganic acids.
カゼインプラスチツクスはカゼインをホルムアルデヒド
で硬化して得られるプラスチックスであるが、カゼイン
プラスチツクス中には未反応の状態で存在するホルムア
ルデヒドは勿論、ホルムアルデヒドがカゼインと反応し
ても硬化に寄与しないメチロールとして存在しており、
熱、水分、不純物或いは加工中の諸要因によつて、再び
ホルムアルデヒドが湧出してくることがある。Casein plastics are plastics obtained by hardening casein with formaldehyde, but of course formaldehyde exists in an unreacted state in casein plastics, and even if formaldehyde reacts with casein, methylol does not contribute to hardening. exists,
Formaldehyde may come out again due to heat, moisture, impurities, or other factors during processing.
カゼインプラスチツクスの使用状況によつてはホルムア
ルデヒドによる公害、労働災害が危惧されるところ５
であり、この様な恐れのないカゼインプラスチツクスの
出現が望まれていたが、本問題解決の方法は今迄全く知
られていなかつた。本発明者らはかかる問題について鋭
意検討した結果本発明を完成した。１０本発明で用いら
れるカゼインプラスチツクスはカゼイン（特にレンネツ
トカゼイン）を必要に応じ、他の天然、人造高分子物、
有機、無機充填剤、可塑斉に酸化防止斉に防腐剤、安定
剤、染顔料などを添加した後ホルムアルデヒド単独又は
トリオ１５キサン、グリオキザールなど他の硬化剤をホ
ルムアルデヒドと併用して硬化したものである。Depending on how casein plastics are used, there are concerns about formaldehyde pollution and industrial accidents.5
Therefore, it has been hoped that casein plastics will emerge that are free from this fear, but until now no method has been known to solve this problem. The present inventors have completed the present invention as a result of intensive study on this problem. 10 The casein plastics used in the present invention contain casein (especially rennet casein) as necessary, and other natural or artificial polymers,
After adding organic or inorganic fillers, plasticizers, antioxidants, preservatives, stabilizers, dyes and pigments, etc., it is cured with formaldehyde alone or in combination with formaldehyde and other hardening agents such as trio-15xane and glyoxal. .
更に本発明で用いられる処理剤には尿素類として尿素、
チオ尿素、Ｎ、Ｎ’−ジメチル尿素、ビウレアなど、又
ＰＫａ４以上の有機もしくは無機酸の２０アンモニウム
塩としては炭酸アンモニウム、重炭酸アンモニウム、カ
ルバミン酸アンモニウム、酢酸アンモニウム、プロピオ
ン酸アンモニウム、クエン酸アンモニウム、琥珀酸アン
モニウムなどがあげられる。５ 本発明の処理は一般に
上記処理剤の水溶液中に被処理カゼインプラスチツクス
を浸漬させることにより行なわれる。Furthermore, the processing agent used in the present invention includes urea,
Thiourea, N,N'-dimethylurea, biurea, etc., and 20 ammonium salts of organic or inorganic acids with a PKa of 4 or higher include ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium acetate, ammonium propionate, ammonium citrate, Examples include ammonium succinate. 5. The treatment of the present invention is generally carried out by immersing the casein plastics to be treated in an aqueous solution of the above treatment agent.
水溶液中の上記処理剤の濃度はカゼインプラスチツクス
中に残存するホルムアルデヒド量によつｎ て影響をう
けるが、通常１０％以下、０．０５％以上（％は重量％
、以下同じ）の濃度範囲、好ましくは５％以下０．１％
以上の濃度範囲が好ましい。The concentration of the above-mentioned treatment agent in the aqueous solution is affected by the amount of formaldehyde remaining in the casein plastics, but it is usually 10% or less and 0.05% or more (% is weight %).
, hereinafter the same) concentration range, preferably 5% or less 0.1%
The above concentration range is preferable.
１０％以上の濃度ではカゼインプラスチツクスが着色し
たり、はなはだしい場合には亀裂を生ずる３５等の好ま
しからざる影響を与える。Concentrations above 10% have undesirable effects such as coloring of the casein plastics and, in extreme cases, cracking.
又、０．０５％以下の濃度では必要な水溶液量が、いた
ずらに増加するのみならず、ホルマリン湧出防止効果の
点でも劣る他、長時間の処理を必要とする。５％以上１
０％以下の範囲では本処理後酸性染料を用いてカゼイン
プラスチツクスを染色する様な場合には色相の変化等を
防止する為水洗、中和等の特別な処理が不可欠となる場
合がある。Further, if the concentration is 0.05% or less, not only the amount of aqueous solution required increases unnecessarily, but also the effect of preventing formalin from seeping out is inferior, and a long treatment time is required. 5% or more1
In the range of 0% or less, when casein plastics are dyed using an acid dye after this treatment, special treatments such as washing with water and neutralization may be necessary to prevent changes in hue.
又０．０５％以上０．１７０以下では処理剤濃度がや＼
低いため長時間の処理が必要でカゼインプラスチツクス
の吸水が著しく寸法安定性を損ねる場合がある他乾燥に
も時間を要する様になる。勿論本発明における処理温度
及び時間は相関係するものである。Also, if it is 0.05% or more and 0.170 or less, the processing agent concentration will be too low.
Because of the low viscosity, a long treatment time is required, and the water absorption of the casein plastics may significantly impair the dimensional stability, and it also takes time to dry. Of course, the processing temperature and time in the present invention are interrelated.
処理温度が低いと処理時間は長くなり処理温度が高くな
るとその逆となる。実用上好ましい処理温度は５乃至６
０℃であり処理時間は１時間乃至４日である。本発明に
先立つてカゼインプラスチツクス中の残存ホルムアルデ
ヒドを減小させる為スチーム処理、乾燥、長時間の保存
による熟成などの他、ホルムアルデヒド及び処理剤の拡
散、浸透を助ける為の種々の加工を行なつておく事が望
ましい。When the processing temperature is low, the processing time becomes long, and vice versa when the processing temperature is high. Practically preferred treatment temperature is 5 to 6.
The temperature was 0° C. and the treatment time was 1 hour to 4 days. Prior to the present invention, in order to reduce residual formaldehyde in casein plastics, in addition to steam treatment, drying, and aging through long-term storage, various treatments were carried out to aid the diffusion and penetration of formaldehyde and processing agents. It is desirable to keep it.
例えば装身凡ボタン等にあつては、切削、穴あけ、研磨
などの加工をほどこした後本発明の処理を実施すること
が好ましい。本発明による処理はカゼインプラスチツク
スの機械的強度、安定性等に特別な影響を与えない為か
かる実施の態様が採用されるものである。以下本発明に
ついて実施例を示すが、本発明はこれら実施例の態様に
限定されるものではない。For example, in the case of decorative buttons, etc., it is preferable to carry out the treatment of the present invention after processing such as cutting, drilling, polishing, etc. This mode of implementation is adopted because the treatment according to the present invention does not particularly affect the mechanical strength, stability, etc. of casein plastics. Examples of the present invention will be shown below, but the present invention is not limited to the embodiments of these Examples.
・実施例 １レンネツトカゼインで作つた骨白生地（白
色）をボタンの原型になる様直径２１１１１厚さ４．５
龍の輪切りサンプル１００部を５％ホルマリン水溶液１
０００部に浸漬し、室温で１４日間硬化させた。・Example 1 Bone white fabric (white) made from rennet casein was made into a button prototype with a diameter of 21111 and a thickness of 4.5
Add 100 parts of dragon slice sample to 1 part of 5% formalin aqueous solution.
000 parts and cured at room temperature for 14 days.
その間硬化液を時々攪拌した。硬化後水洗し直ちに尿素
１％液３００部に浸漬し、３０℃に４日間放置した。サ
ンプルを取出し水洗後４０±２℃の温風で７２時間乾燥
した。サンプルを１００メツシユ程度に粉砕し、厚生省
令３４号別表第一の試験法により溶出したホルムアルデ
ヒドを測定した所２７６０購であつた。未処理のサンプ
ルは１９３００ＰＦを示した。又粉砕しない丸ごとのサ
ンプルについては尿素処理品２５２ＰＦ未処理品２７１
０ＰＦであつた。尿素処理品は未処理の従来品と比較し
て色相、機械的強度、寸法安定性に何ら差は認められな
かつた。以下尿素に代えて各種薬剤による試験結果を第
１表に示す。実施例 ２
実施例１のサンプルを用いて酢酸アンモニウムについて
濃度、温度、時間を変えて実施例１と同じ方法で処理し
た。During this time, the hardening solution was stirred from time to time. After curing, it was washed with water, immediately immersed in 300 parts of 1% urea solution, and left at 30°C for 4 days. The sample was taken out, washed with water, and dried with warm air at 40±2°C for 72 hours. The sample was crushed into about 100 meshes, and the amount of formaldehyde eluted was measured using the test method listed in Appendix Table 1 of Ordinance No. 34 of the Ministry of Health and Welfare, and it was found to be 2,760 pieces. The untreated sample showed 19300PF. For whole samples that are not crushed, urea treated product 252PF untreated product 271
It was 0PF. No difference was observed between the urea-treated product and the untreated conventional product in terms of hue, mechanical strength, and dimensional stability. Table 1 below shows the test results using various drugs in place of urea. Example 2 The sample from Example 1 was treated with ammonium acetate in the same manner as in Example 1, but with different concentrations, temperatures, and times.
Claims (1)
上の有機又は無機酸のアンモニウム塩の０．０５〜１０
重量％の濃度範囲の水溶液で浸漬処理することを特徴と
するカゼインプラスチツクスからホルムアルデヒドの湧
出を防止する方法。1 Casein plastics are treated with ureas or ammonium salts of organic or inorganic acids with a PKa of 4 or more.
A method for preventing formaldehyde from seeping out from casein plastics, which comprises immersing the casein plastics in an aqueous solution having a concentration in the range of % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8156375A JPS5921897B2 (en) | 1975-07-01 | 1975-07-01 | Processing of casein plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8156375A JPS5921897B2 (en) | 1975-07-01 | 1975-07-01 | Processing of casein plastics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS525872A JPS525872A (en) | 1977-01-17 |
| JPS5921897B2 true JPS5921897B2 (en) | 1984-05-23 |
Family
ID=13749751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8156375A Expired JPS5921897B2 (en) | 1975-07-01 | 1975-07-01 | Processing of casein plastics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5921897B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518903A (en) * | 1978-07-26 | 1980-02-09 | Hitachi Ltd | Inspector for tubular body |
| SE438219B (en) * | 1981-09-29 | 1985-04-01 | Tekniska Roentgencentralen Ab | DEVICE FOR INSPECTION OF A REACTORER |
-
1975
- 1975-07-01 JP JP8156375A patent/JPS5921897B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS525872A (en) | 1977-01-17 |
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