JP2000034307A5 - - Google Patents
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- JP2000034307A5 JP2000034307A5 JP1999114394A JP11439499A JP2000034307A5 JP 2000034307 A5 JP2000034307 A5 JP 2000034307A5 JP 1999114394 A JP1999114394 A JP 1999114394A JP 11439499 A JP11439499 A JP 11439499A JP 2000034307 A5 JP2000034307 A5 JP 2000034307A5
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- Prior art keywords
- unsaturated monomer
- salt
- polymerization
- monomer component
- water
- Prior art date
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- 239000000178 monomer Substances 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000000017 hydrogel Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000002250 absorbent Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003638 reducing agent Substances 0.000 description 3
- 230000003068 static Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000717 retained Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
Description
【特許請求の範囲】
【請求項１】 重合装置中で静置水溶液重合を行い、内部架橋剤と、重合により吸水性樹脂となる不飽和単量体成分または不飽和単量体成分の塩とから、架橋構造を有する含水ゲル状重合体を得る過程において、
前記重合装置中の含水ゲル状重合体がピーク温度を示した後、前記含水ゲル状重合体を前記ピーク温度より少なくとも１０℃低い温度で少なくとも３０分保持し、乾燥すること、
前記内部架橋剤は、２個以上の重合性不飽和基あるいは２個以上の反応性基を有すること、ならびに、
前記不飽和単量体成分は、アニオン性不飽和単量体、ノニオン性の親水基含有不飽和単量体、およびカチオン性不飽和単量体からなる群より選択される少なくとも１種であり、前記不飽和単量体成分の塩はアニオン性不飽和単量体の塩であること、
を特徴とする吸水性樹脂の製造方法。
【請求項２】 さらに、該含水ゲル状重合体に重合開始剤を添加することを特徴とする請求項１に記載の吸水性樹脂の製造方法。
【請求項３】 前記静置水溶液重合は、重合開始剤と還元剤とを併用したレドックス系により行われることを特徴とする請求項１または２に記載の吸水性樹脂の製造方法。
【請求項４】
前記含水ゲル重合体は、前記ピーク温度を示した後に、
前記重合装置から熟成用の装置に移されて前記保持されるか、または
前記重合装置から移されずに前記保持されることを特徴とする請求項１〜３のいずれかに記載の吸水性樹脂の製造方法。
【請求項５】 前記保持の後、含水ゲル状重合体を粉砕および乾燥することを特徴とする請求項１〜４のいずれかに記載の吸水性樹脂の製造方法。
【請求項６】 前記ピーク温度は８０℃以上であることを特徴とする請求項１〜５のいずれかに記載の吸水性樹脂の製造方法。
【請求項７】 前記保持の際の相対湿度は、５０％ＲＨ以上であることを特徴とする請求項１〜６のいずれかに記載の吸水性樹脂の製造方法。
【請求項８】 前記アニオン性不飽和単量体としてアクリル酸を含むか、または
前記アニオン性不飽和単量体の塩としてアクリル酸の塩を含み、
前記不飽和単量体成分または前記不飽和単量体成分の塩の含有量は１５〜４５重量％であり、
前記内部架橋剤の含有量は、前記不飽和単量体成分または前記不飽和単量体成分の塩に対して０．００５〜３モル％であることを特徴とする請求項１〜７のいずれかに記載の吸水性樹脂の製造方法。
【請求項９】 前記静置水溶液重合を開始する際の温度は０〜３０℃であり、
前記保持されている含水ゲル状重合体の比表面積は１０ｃｍ ２ ／ｇ以下であることを特徴とする請求項１〜８のいずれかに記載の吸水性樹脂の製造方法。
[Claims]
[Claim 1] A hydrogel polymer having a cross-linked structure is formed from an internal cross-linking agent and an unsaturated monomer component or a salt of an unsaturated monomer component that becomes a water-absorbing resin by polymerization by carrying out standing aqueous polymerization in a polymerization apparatus. In the process of obtaining
After the hydrogel polymer in the polymerization apparatus shows a peak temperature, the hydrogel polymer is held at a temperature at least 10 ° C lower than the peak temperature for at least 30 minutes, and dried,
The internal crosslinking agent has two or more polymerizable unsaturated groups or two or more reactive groups, and
The unsaturated monomer component is at least one selected from the group consisting of an anionic unsaturated monomer, a nonionic hydrophilic group-containing unsaturated monomer, and a cationic unsaturated monomer, The salt of the unsaturated monomer component is a salt of an anionic unsaturated monomer,
A method for producing a water-absorbent resin, comprising:
2. The method according to claim 1, further comprising adding a polymerization initiator to the hydrogel polymer.
[Claim 3] The method for producing a water-absorbent resin according to claim 1, wherein the static aqueous solution polymerization is performed by a redox system using a polymerization initiator and a reducing agent in combination.
[Claim 4]
After the hydrogel polymer shows the peak temperature,
Transferred from the polymerization device to an aging device and held or
The method for producing a water-absorbent resin according to any one of claims 1 to 3, wherein the resin is held without being transferred from the polymerization apparatus.
Claims5] After the holding, the hydrogel polymer is removed.GrindingAnd dryClaims 1 toFourThe method for producing a water-absorbent resin according to any one of the above.
Claims6] The peak temperature is 80 ° C. or higherClaim 1 characterized by the above-mentioned.5 ofThe method for producing a water-absorbent resin according to any one of the above.
[Claim 7] The method for producing a water absorbent resin according to any one of claims 1 to 6, wherein the relative humidity during the holding is 50% RH or more.
[Claim 8] Including acrylic acid as the anionic unsaturated monomer, or
Including a salt of acrylic acid as a salt of the anionic unsaturated monomer,
The content of the unsaturated monomer component or the salt of the unsaturated monomer component is 15 to 45% by weight,
The content of the internal crosslinking agent is 0.005 to 3 mol% with respect to the unsaturated monomer component or the salt of the unsaturated monomer component. A method for producing a water-absorbent resin according to any one of the above.
[Claim 9] The temperature at which the standing aqueous solution polymerization is started is 0 to 30 ° C.,
The specific surface area of the retained hydrogel polymer is 10 cm. 2 / G or less, The method for producing a water-absorbent resin according to any one of claims 1 to 8, wherein
【０００９】
【課題を解決するための手段】
本願発明者等は、上記目的を達成すべく鋭意検討した結果、重合装置中で静置水溶液重合を行い、内部架橋剤と、重合により吸水性樹脂となる不飽和単量体成分または不飽和単量体成分の塩とから、架橋構造を有する含水ゲル状重合体を得る過程において、前記重合装置中の含水ゲル状重合体がピーク温度を示した後、前記含水ゲル状重合体を前記ピーク温度より少なくとも１０℃低い温度で少なくとも３０分保持し、乾燥すること、前記内部架橋剤は、２個以上の重合性不飽和基あるいは２個以上の反応性基を有すること、ならびに、前記不飽和単量体成分は、アニオン性不飽和単量体、ノニオン性の親水基含有不飽和単量体、およびカチオン性不飽和単量体からなる群より選択される少なくとも１種であり、前記不飽和単量体成分の塩はアニオン性不飽和単量体の塩であること、により、吸収倍率が高く、水可溶成分量および残存モノマー量が従来よりも低減されている吸水性樹脂を安定して得ることができることを見出した。
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, carried out static aqueous solution polymerization in a polymerization apparatus, and with an internal crosslinking agent, an unsaturated monomer component or an unsaturated monomer which becomes a water absorbent resin by polymerization. In the process of obtaining a hydrogel polymer having a cross-linked structure from a salt of a monomer component, after the hydrogel polymer in the polymerization apparatus exhibits a peak temperature, the hydrogel polymer is subjected to the peak temperature. Holding at a temperature at least 10 ° C. lower for at least 30 minutes and drying; the internal crosslinking agent having two or more polymerizable unsaturated groups or two or more reactive groups; The monomer component is at least one selected from the group consisting of an anionic unsaturated monomer, a nonionic hydrophilic group-containing unsaturated monomer, and a cationic unsaturated monomer. The salt of the monomer component is It is a salt of anion unsaturated monomers, by, found that it is possible to absorption capacity is high, the water-soluble content and residual monomer content can be a water-absorbent resin which is reduced than the conventional stable Was.
さらに、該含水ゲル状重合体に重合開始剤を添加することが好ましい。Further, it is preferable to add a polymerization initiator to the hydrogel polymer.
また、前記静置水溶液重合は重合開始剤と還元剤とを併用したレドックス系により、行われることが好ましい、Further, the static aqueous solution polymerization is preferably performed by a redox system using a polymerization initiator and a reducing agent in combination,
また、前記含水ゲル重合体は、前記ピーク温度を示した後に、前記重合装置から熟成用の装置に移されて前記保持されるか、または前記重合装置から移されずに前記保持されることが好ましい。 In addition, the water-containing gel polymer may be transferred from the polymerization apparatus to a ripening apparatus after the peak temperature is indicated and held, or may be held without being transferred from the polymerization apparatus. preferable.
また、前記保持の後、含水ゲル状重合体を粉砕および乾燥することが好ましい。After the holding, the hydrogel polymer is preferably ground and dried.
また、前記ピーク温度は８０℃以上であることが好ましい。Further, the peak temperature is preferably 80 ° C. or higher.
また、前記保持の際の相対湿度は、５０％ＲＨ以上であることが好ましい。Further, the relative humidity during the holding is preferably 50% RH or more.
また、前記アニオン性不飽和単量体としてアクリル酸を含むか、または前記アニオン性不飽和単量体の塩としてアクリル酸の塩を含むことが好ましく、Further, it is preferable that acrylic acid is contained as the anionic unsaturated monomer, or a salt of acrylic acid is contained as a salt of the anionic unsaturated monomer,
また、前記不飽和単量体成分または前記不飽和単量体成分の塩の含有量は１５〜４５重量％であることが好ましく、 Further, the content of the unsaturated monomer component or the salt of the unsaturated monomer component is preferably from 15 to 45% by weight,
また、前記内部架橋剤の含有量は、前記不飽和単量体成分または前記不飽和単量体成分の塩に対して０．００５〜３モル％であることが好ましい。 In addition, the content of the internal crosslinking agent is preferably 0.005 to 3 mol% with respect to the unsaturated monomer component or the salt of the unsaturated monomer component.
また、前記静置水溶液重合を開始する際の温度は０〜３０℃であることが好ましく、 Further, the temperature at the time of starting the standing aqueous solution polymerization is preferably 0 to 30 ° C.,
前記保持されている含水ゲル状重合体の比表面積は１０ｃｍ The specific surface area of the retained hydrogel polymer is 10 cm.
２2
／ｇ以下であることが好ましい。/ G or less.
また、前記において、重合開始剤に過硫酸塩、アゾ系反応開始剤、酸化剤および還元剤、を用いることを特徴とする方法を採用する。In the above, a method characterized by using a persulfate, an azo-based reaction initiator, an oxidizing agent and a reducing agent as the polymerization initiator is adopted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11439499A JP4198266B2 (en) | 1998-05-14 | 1999-04-22 | Method for producing water absorbent resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13175998 | 1998-05-14 | ||
| JP10-131759 | 1998-05-14 | ||
| JP11439499A JP4198266B2 (en) | 1998-05-14 | 1999-04-22 | Method for producing water absorbent resin |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000034307A JP2000034307A (en) | 2000-02-02 |
| JP2000034307A5 true JP2000034307A5 (en) | 2006-06-29 |
| JP4198266B2 JP4198266B2 (en) | 2008-12-17 |
Family
ID=26453145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11439499A Expired - Lifetime JP4198266B2 (en) | 1998-05-14 | 1999-04-22 | Method for producing water absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4198266B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE284903T1 (en) * | 2000-12-29 | 2005-01-15 | Dow Global Technologies Inc | WATER ABSORBING RESIN PARTICLES MADE OF CROSS-LINKED POLYMERS CONTAINING CARBOXYL GROUPS WITH LOW MONOMER CONTENT |
| US7214753B2 (en) | 2004-03-24 | 2007-05-08 | Nippon Shokubai Co., Ltd. | N-vinyl amide polymer and production method thereof |
| JP4878116B2 (en) * | 2004-11-18 | 2012-02-15 | 旭化成ケミカルズ株式会社 | Water absorbent resin production method |
| JP5042674B2 (en) * | 2006-03-29 | 2012-10-03 | 株式会社日本触媒 | Method for producing polyacrylic acid (salt) water-absorbing resin |
| DE102010043113A1 (en) * | 2010-10-29 | 2012-05-03 | Evonik Stockhausen Gmbh | Process for the preparation of improved absorbent polymers by cryogenic milling |
| JP7105586B2 (en) * | 2017-03-24 | 2022-07-25 | 住友精化株式会社 | Method for manufacturing water absorbent resin |
-
1999
- 1999-04-22 JP JP11439499A patent/JP4198266B2/en not_active Expired - Lifetime
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