JP7401972B2 - Amino acid-based particles - Google Patents
Amino acid-based particles Download PDFInfo
- Publication number
- JP7401972B2 JP7401972B2 JP2019037472A JP2019037472A JP7401972B2 JP 7401972 B2 JP7401972 B2 JP 7401972B2 JP 2019037472 A JP2019037472 A JP 2019037472A JP 2019037472 A JP2019037472 A JP 2019037472A JP 7401972 B2 JP7401972 B2 JP 7401972B2
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- JP
- Japan
- Prior art keywords
- particles
- amino acid
- polyfunctional
- acid
- structural unit
- 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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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 5
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Landscapes
- Polyamides (AREA)
Description
本発明は、アミノ酸系粒子に関する。 The present invention relates to amino acid-based particles.
従来、石油原料より製造されたポリマー粒子は、樹脂フィルム用アンチブロッキング剤、静電荷像現像用トナー用添加剤、粉体塗料用添加剤、水分散体型塗料用添加剤、化粧品用充填剤および光拡散剤等の用途に用いられている。 Conventionally, polymer particles manufactured from petroleum raw materials have been used as anti-blocking agents for resin films, additives for toners for developing electrostatic images, additives for powder coatings, additives for water-dispersed coatings, fillers for cosmetics, and photonics. It is used for applications such as diffusing agents.
近年、プラスチック廃棄物による環境汚染が問題視されている。環境負荷低減の観点から、環境中において分解が進むプラスチックが注目を集めており（例えば、特許文献１参照）、様々な分野において、このような分解性プラスチック由来の粒子を使用することが進められている。 In recent years, environmental pollution caused by plastic waste has become a problem. From the perspective of reducing environmental impact, plastics that decompose in the environment are attracting attention (for example, see Patent Document 1), and the use of particles derived from such degradable plastics is being promoted in various fields. ing.
従来、土壌中での分解性を有する種々の粒子が提案されているが、耐溶剤性・耐水性に優れるとともに、土壌中での分解性に優れる粒子が依然として望まれている。このため、本発明は、耐溶剤性・耐水性および土壌中での分解性に優れる粒子を提供することを課題とする。 Conventionally, various particles that are degradable in soil have been proposed, but there is still a desire for particles that have excellent solvent resistance and water resistance as well as excellent degradability in soil. Therefore, an object of the present invention is to provide particles that are excellent in solvent resistance, water resistance, and degradability in soil.
本発明者らは上記課題を解決すべく検討を行った。その結果、以下の構成を有する粒子により上記課題を解決できることを見出し、本発明を完成するに至った。本発明は、例えば以下の［１］～［４］に関する。 The present inventors conducted studies to solve the above problems. As a result, it was discovered that the above problems could be solved by particles having the following configuration, and the present invention was completed. The present invention relates to, for example, the following [1] to [4].
［１］アミノ酸に由来する構造単位と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種に由来する構造単位とを有するアミノ酸系粒子であり、下記条件（ａ）を満たすアミノ酸系粒子：
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。
［２］下記条件（ｂ）、（ｃ）および（ｄ）から選ばれる少なくとも１つの条件をさらに満たす前記［１］に記載のアミノ酸系粒子：
（ｂ）前記粒子を２５℃、ｐＨ３の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｃ）前記粒子を２５℃、ｐＨ７の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｄ）前記粒子を２５℃、ｐＨ１４の水中に７２時間放置した後の
重量減少率が１０％以下である。
［３］前記アミノ酸が、アスパラギン酸およびグルタミン酸から選ばれる少なくとも１種である前記［１］または［２］に記載のアミノ酸系粒子。
［４］ポリアミノ酸に由来する構造単位と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種に由来する構造単位とを有するアミノ酸系粒子であり、下記条件（ａ）を満たすアミノ酸系粒子：
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。
[1] Amino acid-based particles having a structural unit derived from an amino acid and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, and which satisfy the following condition (a). :
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
[2] The amino acid-based particles according to [1] above, which further satisfy at least one condition selected from the following conditions (b), (c), and (d):
(b) The weight loss rate after the particles are left in water at 25° C. and pH 3 for 72 hours is 10% or less.
(c) The weight loss rate after the particles are left in water at 25° C. and pH 7 for 72 hours is 10% or less.
(d) The weight loss rate after the particles are left in water at 25° C. and pH 14 for 72 hours is 10% or less.
[3] The amino acid-based particles according to [1] or [2] above, wherein the amino acid is at least one selected from aspartic acid and glutamic acid.
[4] Amino acid-based particles having a structural unit derived from a polyamino acid and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, and which satisfy the following condition (a). particle:
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
本発明によれば、耐溶剤性・耐水性および土壌中での分解性に優れる粒子を提供することができる。 According to the present invention, it is possible to provide particles that are excellent in solvent resistance, water resistance, and degradability in soil.
本発明の第１のアミノ酸系粒子は、アミノ酸に由来する構造単位と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種に由来する構造単位とを有し、さらに下記条件（ａ）を満たす。
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。
The first amino acid-based particles of the present invention have a structural unit derived from an amino acid and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, and further under the following conditions (a). satisfy.
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
本発明の第２のアミノ酸系粒子は、ポリアミノ酸に由来する構造単位と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種に由来する構造単位とを有し、さらに下記条件（ａ）を満たす。
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。
The second amino acid-based particles of the present invention have a structural unit derived from a polyamino acid and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, and further under the following conditions (a). ) is satisfied.
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
前記条件（ａ）における重量減少率は、好ましくは８．０％以下であり、重量減少率は低い方が好ましいが、一実施態様において下限値は０．５％程度であっても実用上問題ない。 The weight loss rate under the above condition (a) is preferably 8.0% or less, and the lower the weight loss rate is, the more preferable it is, but in one embodiment, even if the lower limit is about 0.5%, there is no practical problem. do not have.
以下、本発明の第１のアミノ酸系粒子および第２のアミノ酸系粒子をまとめて「本発明の粒子」ともいう。
本発明の粒子は、通常、前記条件（ａ）を満たす架橋粒子である。
Hereinafter, the first amino acid-based particles and the second amino acid-based particles of the present invention are also collectively referred to as "particles of the present invention."
The particles of the present invention are usually crosslinked particles that satisfy the above condition (a).
本発明の粒子は、下記条件（ｂ）、（ｃ）および（ｄ）から選ばれる少なくとも１つの条件をさらに満たすことが好ましく、下記条件（ｂ）、（ｃ）および（ｄ）の全てをさらに満たすことがより好ましい。
（ｂ）前記粒子を２５℃、ｐＨ３の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｃ）前記粒子を２５℃、ｐＨ７の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｄ）前記粒子を２５℃、ｐＨ１４の水中に７２時間放置した後の
重量減少率が１０％以下である。
The particles of the present invention preferably further satisfy at least one condition selected from the following conditions (b), (c), and (d), and further satisfy all of the following conditions (b), (c), and (d). It is more preferable to satisfy.
(b) The weight loss rate after the particles are left in water at 25° C. and pH 3 for 72 hours is 10% or less.
(c) The weight loss rate after the particles are left in water at 25° C. and pH 7 for 72 hours is 10% or less.
(d) The weight loss rate after the particles are left in water at 25° C. and pH 14 for 72 hours is 10% or less.
前記条件（ｂ）における重量減少率は、好ましくは８．５％以下であり、重量減少率は低い方が好ましいが、一実施態様において下限値は０．５％程度であっても実用上問題ない。 The weight loss rate under the above condition (b) is preferably 8.5% or less, and the lower the weight loss rate, the better, but in one embodiment, even if the lower limit is about 0.5%, there is no practical problem. do not have.
前記条件（ｃ）における重量減少率は、好ましくは９．０％以下であり、重量減少率は低い方が好ましいが、一実施態様において下限値は０．５％程度であっても実用上問題ない。 The weight loss rate under the above condition (c) is preferably 9.0% or less, and the lower the weight loss rate, the better, but in one embodiment, even if the lower limit is about 0.5%, there is no practical problem. do not have.
前記条件（ｄ）における重量減少率は、好ましくは６．０％以下であり、重量減少率は低い方が好ましいが、一実施態様において下限値は０．５％程度であっても実用上問題ない。 The weight loss rate under the above condition (d) is preferably 6.0% or less, and the lower the weight loss rate, the better, but in one embodiment, even if the lower limit is about 0.5%, there is no practical problem. do not have.
本発明の粒子は、条件（ａ）を満たし、好ましくは条件（ｂ）～（ｄ）から選ばれる少なくとも１つの条件をさらに満たすことから、塗料添加剤などの種々の用途において粒子形状を良好に維持することができる。 Since the particles of the present invention satisfy condition (a) and preferably further satisfy at least one condition selected from conditions (b) to (d), they can have a good particle shape in various uses such as paint additives. can be maintained.
本発明の第１のアミノ酸系粒子は、通常、アミノ酸と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種との反応物を含有し、例えば、アミノ酸と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種とを反応させることで得ることができる。 The first amino acid-based particles of the present invention usually contain a reaction product of an amino acid and at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, for example, an amino acid and a polyfunctional carbodiimide compound and a polyfunctional epoxy compound. It can be obtained by reacting with at least one selected from functional epoxy compounds.
本発明の第２のアミノ酸系粒子は、通常、ポリアミノ酸と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種との反応物を含有し、例えば、ポリアミノ酸と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種とを反応させることで得ることができる。 The second amino acid-based particles of the present invention usually contain a reaction product of a polyamino acid and at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound, for example, a polyamino acid and a polyfunctional carbodiimide compound. and at least one selected from polyfunctional epoxy compounds.
本発明の第１のアミノ酸系粒子および第２のアミノ酸系粒子において、アミノ酸とポリアミノ酸とを併用してもよい。以下、アミノ酸およびポリアミノ酸から選ばれる少なくとも１種を「成分（１）」ともいい、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種を「成分（２）」ともいう。 In the first amino acid-based particles and the second amino acid-based particles of the present invention, amino acids and polyamino acids may be used in combination. Hereinafter, at least one selected from amino acids and polyamino acids will also be referred to as "component (1)", and at least one selected from polyfunctional carbodiimide compounds and polyfunctional epoxy compounds will also be referred to as "component (2)".
本発明の粒子は、例えば、成分（１）と成分（２）とを水中で反応させ、水分を加熱蒸発させることにより、得ることができる。反応時の温度は、通常は６５℃以上、好ましくは７０～８０℃である。必要に応じて、水分蒸発後の粒子を粉砕してもよく、または乾燥造粒してもよい。 The particles of the present invention can be obtained, for example, by reacting component (1) and component (2) in water and heating and evaporating the water. The temperature during the reaction is usually 65°C or higher, preferably 70 to 80°C. If necessary, the particles after water evaporation may be pulverized or dried and granulated.
本発明の粒子における成分（１）に由来する構造単位および成分（２）に由来する構造単位の結合状態は定かではないが、以下のように推測される。
例えば成分（１）としてアミノ酸を用い、成分（２）として多官能カルボジイミド化合物を用いた場合、カルボキシ基とカルボジイミド基との反応性が高いため、アミノ酸におけるカルボキシ基と多官能カルボジイミド化合物におけるカルボジイミド基とが反応してＮ－アシルウレア構造を形成していると考えられる。
Although the bonding state of the structural unit derived from component (1) and the structural unit derived from component (2) in the particles of the present invention is not certain, it is assumed as follows.
For example, when an amino acid is used as component (1) and a polyfunctional carbodiimide compound is used as component (2), the carboxy group in the amino acid and the carbodiimide group in the polyfunctional carbodiimide compound have high reactivity. It is thought that these react to form an N-acylurea structure.
また、例えば成分（１）としてアミノ酸を用い、成分（２）として多官能エポキシ化合物を用いた場合、アミノ酸におけるカルボキシ基と多官能エポキシ化合物におけるエポキシ基とが開環反応して架橋構造を形成していると推測される。
ポリアミノ酸を用いた場合も同様の反応が進行すると推測される。
For example, when an amino acid is used as component (1) and a polyfunctional epoxy compound is used as component (2), the carboxyl group in the amino acid and the epoxy group in the polyfunctional epoxy compound undergo a ring-opening reaction to form a crosslinked structure. It is assumed that
It is assumed that a similar reaction proceeds when polyamino acids are used.
＜量比＞
本発明の第１のアミノ酸系粒子の製造において、成分（２）の使用量は、アミノ酸１００質量部に対して、通常は１０～１５００質量部、好ましくは１５～１３００質量部、より好ましくは５０～１１００質量部である。
<Quantity ratio>
In the production of the first amino acid-based particles of the present invention, the amount of component (2) used is usually 10 to 1500 parts by weight, preferably 15 to 1300 parts by weight, more preferably 50 parts by weight, based on 100 parts by weight of the amino acid. ~1100 parts by mass.
本発明の第２のアミノ酸系粒子の製造において、成分（２）の使用量は、ポリアミノ酸１００質量部に対して、通常は１００～２０００質量部、好ましくは１００～１０００質量部、より好ましくは２００～１０００質量部である。 In the production of the second amino acid-based particles of the present invention, the amount of component (2) used is usually 100 to 2000 parts by mass, preferably 100 to 1000 parts by mass, and more preferably The amount is 200 to 1000 parts by mass.
本発明の第１および第２のアミノ酸系粒子の製造においてアミノ酸およびポリアミノ酸を併用する場合、成分（２）の使用量は、アミノ酸およびポリアミノ酸の合計１００質量部に対して、通常は１０～２０００質量部、好ましくは５０～１５００質量部、より好ましくは１００～１０００質量部、さらに好ましくは２００～１０００質量部である。
以下、各成分について説明する。
When amino acids and polyamino acids are used together in the production of the first and second amino acid-based particles of the present invention, the amount of component (2) used is usually 10 to 10 parts by mass, based on a total of 100 parts by mass of the amino acids and polyamino acids. The amount is 2000 parts by weight, preferably 50 to 1500 parts by weight, more preferably 100 to 1000 parts by weight, and even more preferably 200 to 1000 parts by weight.
Each component will be explained below.
＜アミノ酸＞
アミノ酸としては、例えば、α－アミノ酸が挙げられ、具体的には、アスパラギン酸、グルタミン酸等の負電荷をもつ側鎖を有するアミノ酸、特に側鎖にカルボキシ基を有するアミノ酸；アルギニン、リシン、ヒスチジン、オルニチン等の正電荷をもつ側鎖を有するアミノ酸；アスパラギン、グルタミン、セリン、トレオニン、チロシン等の電荷をもたず極性の側鎖を有するアミノ酸；アラニン、バリン、ロイシン、イソロイシン、プロリン、フェニルアラニン、メチオニン、トリプトファン、システイン、グリシン等の非極性側鎖を有するまたは側鎖を有さないアミノ酸が挙げられる。アミノ酸としては、その他、β－アラニン等のβ－アミノ酸、γ－アミノ酪酸等のγ－アミノ酸が挙げられる。アミノ酸は、後述するような金属塩、アンモニウム塩等の塩を形成していてもよい。
<Amino acids>
Examples of amino acids include α-amino acids, specifically amino acids having a negatively charged side chain such as aspartic acid and glutamic acid, especially amino acids having a carboxy group in the side chain; arginine, lysine, histidine, Amino acids with positively charged side chains such as ornithine; Amino acids with uncharged and polar side chains such as asparagine, glutamine, serine, threonine, and tyrosine; alanine, valine, leucine, isoleucine, proline, phenylalanine, methionine , tryptophan, cysteine, glycine, and other amino acids with or without a nonpolar side chain. Other amino acids include β-amino acids such as β-alanine, and γ-amino acids such as γ-aminobutyric acid. The amino acid may form a salt such as a metal salt or an ammonium salt as described below.
アミノ酸の中でも、多官能カルボジイミド化合物および多官能エポキシ化合物との反応性の観点から、側鎖にカルボキシ基またはアミノ基を有するアミノ酸がより好ましく、アスパラギン酸、グルタミン酸およびリシンから選ばれる少なくとも１種が特に好ましい。
アミノ酸は１種用いてもよく、２種以上を用いてもよい。
Among amino acids, from the viewpoint of reactivity with polyfunctional carbodiimide compounds and polyfunctional epoxy compounds, amino acids having a carboxyl group or an amino group in the side chain are more preferable, and at least one selected from aspartic acid, glutamic acid, and lysine is particularly preferable. preferable.
One type of amino acid may be used, or two or more types may be used.
＜ポリアミノ酸＞
ポリアミノ酸としては、例えば、アミノ酸が脱水縮合して得られたポリペプチド、およびその塩が挙げられる。前記アミノ酸としては、前述した具体例が挙げられる。
ポリアミノ酸としては、例えば、ポリアスパラギン酸、ポリグルタミン酸、ポリアルギニン、ポリリシン、ポリオルニチン、ポリセリン等の１種のアミノ酸が脱水縮合して得られたポリペプチド；２種以上のアミノ酸が脱水縮合して得られたポリペプチド；およびこれらのポリペプチドの塩が挙げられる。
<Polyamino acid>
Examples of polyamino acids include polypeptides obtained by dehydration condensation of amino acids and salts thereof. The above-mentioned amino acids include the specific examples mentioned above.
Examples of polyamino acids include polypeptides obtained by dehydration condensation of one type of amino acid such as polyaspartic acid, polyglutamic acid, polyarginine, polylysine, polyornithine, and polyserine; polypeptides obtained by dehydration condensation of two or more types of amino acids; and the resulting polypeptides; and salts of these polypeptides.
これらの中でも、土壌中での分解性と、多官能カルボジイミド化合物および多官能エポキシ化合物との反応性の観点から、側鎖にカルボキシ基を有するアミノ酸を少なくとも含むアミノ酸のポリペプチドおよびその塩が好ましく、アスパラギン酸およびグルタミン酸から選ばれる少なくとも１種を含むアミノ酸のポリペプチドおよびその塩がより好ましく、ポリアスパラギン酸、ポリグルタミン酸、およびこれらの塩が特に好ましい。 Among these, from the viewpoint of degradability in soil and reactivity with polyfunctional carbodiimide compounds and polyfunctional epoxy compounds, polypeptides of amino acids and salts thereof containing at least an amino acid having a carboxyl group in the side chain are preferred; Amino acid polypeptides containing at least one selected from aspartic acid and glutamic acid and salts thereof are more preferred, and polyaspartic acid, polyglutamic acid, and salts thereof are particularly preferred.
ポリペプチドの塩としては、例えば、金属塩、アンモニウム塩が挙げられる。金属塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩；カルシウム塩、マグネシウム塩、バリウム塩等のアルカリ土類金属塩；アルミニウム塩が挙げられる。
ポリアミノ酸は１種用いてもよく、２種以上を用いてもよい。
Examples of polypeptide salts include metal salts and ammonium salts. Examples of metal salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts, magnesium salts, and barium salts; and aluminum salts.
One type of polyamino acid may be used, or two or more types may be used.
＜多官能カルボジイミド化合物＞
多官能カルボジイミド化合物は、１分子中に２個以上のカルボジイミド基（－Ｎ＝Ｃ＝Ｎ－；「ＮＣＮ基」とも記載する）を有する。多官能カルボジイミド化合物は、好ましくは下記式（Ｅ１）に示す繰り返し単位を有する。
－Ｎ＝Ｃ＝Ｎ－Ｒ1－ …（Ｅ１）
式（Ｅ１）中、Ｒ1は２価の有機基である。
カルボジイミド基はカルボキシ基およびアミノ基等の官能基と反応し、特にカルボキシ基と反応性が高いため、多官能カルボジイミド化合物はアミノ酸および／またはポリアミノ酸と反応して架橋構造を形成すると考えられる。
<Polyfunctional carbodiimide compound>
A polyfunctional carbodiimide compound has two or more carbodiimide groups (-N=C=N-; also referred to as "NCN group") in one molecule. The polyfunctional carbodiimide compound preferably has a repeating unit represented by the following formula (E1).
-N=C=N-R 1 -...(E1)
In formula (E1), R 1 is a divalent organic group.
Carbodiimide groups react with functional groups such as carboxy groups and amino groups, and are particularly highly reactive with carboxy groups, so it is thought that polyfunctional carbodiimide compounds react with amino acids and/or polyamino acids to form crosslinked structures.
カルボジイミド基の反応は、例えば、赤外吸収分光法（ＩＲ）により確認することができる。ＩＲでは、例えば２１００ｃｍ-1付近のピ－クを観察し、このピークの消失により、カルボジイミド基が反応したことがわかる。 The reaction of the carbodiimide group can be confirmed, for example, by infrared absorption spectroscopy (IR). In IR, for example, a peak near 2100 cm -1 is observed, and the disappearance of this peak indicates that the carbodiimide group has reacted.
多官能カルボジイミド化合物におけるＮＣＮ当量は、好ましくは２００～８００、より好ましくは２５０～６００である。ＮＣＮ当量とは、ＮＣＮ基１モル当たりの化学式量を表す。 The NCN equivalent in the polyfunctional carbodiimide compound is preferably 200 to 800, more preferably 250 to 600. NCN equivalent represents the chemical formula weight per mole of NCN group.
多官能カルボジイミド化合物は、例えば、ポリイソシアネートの脱炭酸縮合反応物である。ポリイソシアネートとしては、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネート等の有機ジイソシアネートが挙げられる。具体的には、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート、；シクロヘキサン－１，３－ジイソシアネート、シクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、メチルシクロヘキサンジイソシアネート等の脂環族ジイソシアネート；１，５－ナフタレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルジメチルメタンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、２，６－ジイソプロピルフェニルイソシアネート、１，３，５－トリイソプロピルベンゼン－２，４－ジイソシアネート等の芳香族ジイソシアネートが挙げられる。 The polyfunctional carbodiimide compound is, for example, a decarboxylation condensation reaction product of polyisocyanate. Examples of the polyisocyanate include organic diisocyanates such as aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Specifically, aliphatic diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-2 , 4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate and other alicyclic diisocyanates; 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate , 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1 , 3,5-triisopropylbenzene-2,4-diisocyanate and the like.
ポリイソシアネートの中でも、得られる粒子の土壌中での分解性の観点から、脂肪族ジイソシアネートおよび脂環族ジイソシアネートから選ばれる少なくとも１種が好ましい。
ポリイソシアネートは１種用いてもよく、２種以上を用いてもよい。
Among the polyisocyanates, at least one selected from aliphatic diisocyanates and alicyclic diisocyanates is preferred from the viewpoint of degradability of the resulting particles in soil.
One type of polyisocyanate may be used, or two or more types may be used.
多官能カルボジイミド化合物におけるポリイソシアネートの重合度は、２～２０が好ましく、５～２０がより好ましい。多官能カルボジイミド化合物の製造において、ポリイソシアネートの脱炭酸縮合反応を冷却等により途中で停止させることで、重合度を制御することができる。 The degree of polymerization of the polyisocyanate in the polyfunctional carbodiimide compound is preferably from 2 to 20, more preferably from 5 to 20. In the production of a polyfunctional carbodiimide compound, the degree of polymerization can be controlled by stopping the decarboxylation condensation reaction of polyisocyanate midway through cooling or the like.
多官能カルボジイミド化合物としては、公知の種々の方法で製造したものを使用することができるが、基本的には、従来の多官能カルボジイミド化合物の製造方法［例えば、米国特許第２９４１９５６号明細書、特公昭４７－３３２７９号公報、Ｊ．０ｒｇ．Ｃｈｅｍ．２８，２０６９－２０７５（１９６３）、Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗ ｌ９８１，Ｖｏｌ．８１Ｎｏ．４、ｐ６１９－６２１］により、製造されたものを用いることができる。 As the polyfunctional carbodiimide compound, those produced by various known methods can be used, but basically, conventional methods for producing polyfunctional carbodiimide compounds [for example, U.S. Pat. No. 2,941,956, Publication No. 47-33279, J. 0rg. Chem. 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81 No. 4, p619-621] can be used.
多官能カルボジイミド化合物は、例えば、ポリイソシアネートを、カルボジイミド化触媒の存在下で、無溶媒または不活性溶媒中、脱炭酸縮合反応させることにより合成することができる。ポリイソシアネートの反応温度は、例えば７０℃以上、一実施態様では７０～２００℃である。 A polyfunctional carbodiimide compound can be synthesized, for example, by subjecting a polyisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidation catalyst, without a solvent or in an inert solvent. The reaction temperature of the polyisocyanate is, for example, 70°C or higher, and in one embodiment 70 to 200°C.
カルボジイミド化触媒は、イソシアネ－ト基のカルボジイミド化反応を促進する触媒であり、例えば、有機リン系化合物、有機金属化合物が挙げられ、具体的には、１－フェニル－２－ホスホレン－１－オキシド、３－メチル－１－フェニル－２－ホスホレン-1-オキシド、１－エチル－２－ホスホレン－１－オキシド、３－メチル－２－ホスホレン－１－オキシド、１－エチル－２－ホスホレン－１－スルフィド、１，３－ジメチル－２－ホスホレン－１－スルフィド等のホスホレン化合物；ペンタカルボニル鉄、ノナカルボニル鉄、ヘキサカルボニルタンブステン等の金属カルボニル錯体；鉄、アルミニウム、クロム、ジルコニウム等のアセチルアセトナイト錯体；トリメチルホスフェート、トリエチルホスフェート、トリフェニルホスフェート等の燐酸エステルが挙げられる。 The carbodiimidization catalyst is a catalyst that promotes the carbodiimidation reaction of isocyanate groups, and examples thereof include organic phosphorus compounds and organometallic compounds, and specifically, 1-phenyl-2-phosphorene-1-oxide. , 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1 - Phosphorene compounds such as sulfide and 1,3-dimethyl-2-phosphorene-1-sulfide; Metal carbonyl complexes such as pentacarbonyl iron, nonacarbonyl iron, and hexacarbonyl tambusten; Acetylaceto of iron, aluminum, chromium, zirconium, etc. Night complex; phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, etc. are mentioned.
カルボジイミド化触媒は１種用いてもよく、２種以上を用いてもよい。
カルボジイミド化触媒の使用量は、ポリイソシアネート１００質量部に対して、通常は３０質量部以下、好ましくは０．０１～１０質量部である。
One type of carbodiimidation catalyst may be used, or two or more types may be used.
The amount of the carbodiimidization catalyst used is usually 30 parts by weight or less, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the polyisocyanate.
不活性溶媒としては、例えば、１，１－ジクロロエタン、テトラクロロエチレン、ｐ－クロロベンゼン等のハロゲン化炭化水素溶媒；ベンゼン、トルエン、エチルベンゼン等の芳香族炭化水素溶媒；テトラヒドロフラン、ジオキサン、ジエチレングリコールジメチルエーテル等のエーテル溶媒；２－メチルシクロヘキサノン、シクロヘキサノン、シクロヘプタノン、２，４－ジメチル－３－ヘプタノン等のケトン溶媒；２－メトキシエチルアセテート、ジエチレングリコールモノメチルエーテルアセテート等のアセテート溶媒が挙げられる。 Examples of inert solvents include halogenated hydrocarbon solvents such as 1,1-dichloroethane, tetrachloroethylene, and p-chlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene, and ethylbenzene; and ether solvents such as tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether. Ketone solvents such as 2-methylcyclohexanone, cyclohexanone, cycloheptanone and 2,4-dimethyl-3-heptanone; Acetate solvents such as 2-methoxyethyl acetate and diethylene glycol monomethyl ether acetate.
多官能カルボジイミド化合物は、末端にイソシアネート基を有する多官能カルボジイミド化合物であっても、前記末端イソシアネート基を変性して得られる変性多官能カルボジイミド化合物であってもよい。 The polyfunctional carbodiimide compound may be a polyfunctional carbodiimide compound having an isocyanate group at its terminal, or a modified polyfunctional carbodiimide compound obtained by modifying the terminal isocyanate group.
例えば、多官能カルボジイミド化合物の末端イソシアネート基と反応する化合物（以下「末端封止剤」ともいう）を用いて、多官能カルボジイミド化合物中に残存する末端イソシアネート基の一部または全てを封止することができる。 For example, using a compound that reacts with the terminal isocyanate groups of the polyfunctional carbodiimide compound (hereinafter also referred to as "terminal capping agent"), part or all of the terminal isocyanate groups remaining in the polyfunctional carbodiimide compound may be capped. I can do it.
末端封止剤としては、例えば、ブチルイソシアネート、シクロヘキシルイソシアネート、フェニルイソシアネート、トリルイソシアネート、ジメチルフェニルイソシアネート、ナフチルイソシアネート等のモノイソシアネート化合物；イソシアネート基と反応し得る活性水素化合物が挙げられる。 Examples of the terminal capping agent include monoisocyanate compounds such as butyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, dimethylphenylisocyanate, and naphthylisocyanate; active hydrogen compounds that can react with isocyanate groups.
イソシアネート基と反応し得る活性水素化合物としては、例えば、メタノール、エタノール、フェノール、シクロヘキサノール、Ｎ－メチルエタノールアミン、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコールモノメチルエーテル等の水酸基含有化合物；ブチルアミン、シクロヘキシルアミン、ジエチルアミン、ジシクロヘキシルアミン等のアミノ基含有化合物；コハク酸、安息香酸、シクロヘキサン酸等のカルボキシ基含有化合物；無水酢酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等の酸無水物；エチルメルカプタン、アリルメルカプタン、チオフェノール等のチオール基含有化合物が挙げられる。 Examples of active hydrogen compounds that can react with isocyanate groups include hydroxyl group-containing compounds such as methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, and polypropylene glycol monomethyl ether; butylamine, cyclohexylamine, and diethylamine. , amino group-containing compounds such as dicyclohexylamine; carboxy group-containing compounds such as succinic acid, benzoic acid, and cyclohexanoic acid; acid anhydrides such as acetic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride; ethyl mercaptan, allyl Examples include thiol group-containing compounds such as mercaptan and thiophenol.
本発明では、多官能カルボジイミド化合物が水等の溶媒に分散または溶解しているエマルションまたは溶液を用いることもできる。
多官能カルボジイミド化合物としては、市販品を用いることができる。前記市販品としては、日清紡ケミカル社製の「カルボジライト」の商標名にて入手できるＶ－０２、Ｖ－０４、Ｖ－０６、Ｅ－０１、Ｅ－０２、Ｅ－０５等の水性タイプ（水溶液または水分散体）；Ｖ－０１、Ｖ－０３、Ｖ－０５、Ｖ－０７、Ｖ－０９等の油性タイプが挙げられる。
多官能カルボジイミド化合物は１種用いてもよく、２種以上を用いてもよい。
In the present invention, an emulsion or solution in which a polyfunctional carbodiimide compound is dispersed or dissolved in a solvent such as water can also be used.
As the polyfunctional carbodiimide compound, commercially available products can be used. The commercially available products include aqueous types (aqueous solutions) such as V-02, V-04, V-06, E-01, E-02, and E-05 available under the trade name "Carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. or aqueous dispersion); examples include oil-based types such as V-01, V-03, V-05, V-07, and V-09.
One type of polyfunctional carbodiimide compound may be used, or two or more types may be used.
＜多官能エポキシ化合物＞
多官能エポキシ化合物は、１分子中に２個以上のエポキシ基を有し、好ましくは、１分子中に２～８個、より好ましくは２～６個のエポキシ基を有する。
多官能エポキシ化合物としては、例えば、脂肪族多官能エポキシ化合物、脂環式多官能エポキシ化合物、芳香族多官能エポキシ化合物が挙げられ、土壌中での分解性の観点から、脂肪族多官能エポキシ化合物および脂環式多官能エポキシ化合物が好ましい。
<Polyfunctional epoxy compound>
The polyfunctional epoxy compound has two or more epoxy groups in one molecule, preferably 2 to 8, more preferably 2 to 6 epoxy groups in one molecule.
Examples of polyfunctional epoxy compounds include aliphatic polyfunctional epoxy compounds, alicyclic polyfunctional epoxy compounds, and aromatic polyfunctional epoxy compounds.From the viewpoint of degradability in soil, aliphatic polyfunctional epoxy compounds and alicyclic polyfunctional epoxy compounds are preferred.
脂肪族多官能エポキシ化合物および脂環式多官能エポキシ化合物としては、例えば、グリシジルエーテル系エポキシ化合物、グリシジルアミン系エポキシ化合物、グリシジルエステル系エポキシ化合物が挙げられ、具体的には、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノエチル）シクロヘキサンが挙げられる。芳香族多官能エポキシ化合物としては、例えば、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）ベンゼン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）トルエンが挙げられる。
多官能エポキシ化合物は１種用いてもよく、２種以上を用いてもよい。
Examples of aliphatic polyfunctional epoxy compounds and alicyclic polyfunctional epoxy compounds include glycidyl ether-based epoxy compounds, glycidylamine-based epoxy compounds, and glycidyl ester-based epoxy compounds. Specifically, ethylene glycol diglycidyl ether , polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycidyl ether Glycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidyl) (aminoethyl) cyclohexane. Examples of the aromatic polyfunctional epoxy compound include 1,3-bis(N,N-diglycidylaminomethyl)benzene and 1,3-bis(N,N-diglycidylaminomethyl)toluene.
One type of polyfunctional epoxy compound may be used, or two or more types may be used.
＜他の成分＞
本発明の粒子は、前述した成分（１）と成分（２）との反応物の他、条件（ａ）（好ましくは条件（ａ）～（ｄ））を満たす限り、従来公知の生分解性ポリマーをさらに含有することができる。前記生分解性ポリマーとしては、例えば、天然物系生分解性ポリマー、微生物合成系生分解性ポリマー、化学合成系生分解性ポリマーが挙げられる。
<Other ingredients>
In addition to the reaction product of component (1) and component (2) described above, the particles of the present invention can be any of the conventionally known biodegradable particles as long as they satisfy condition (a) (preferably conditions (a) to (d)). It may further contain a polymer. Examples of the biodegradable polymer include natural product-based biodegradable polymers, microbially synthesized biodegradable polymers, and chemically synthesized biodegradable polymers.
天然物系生分解性ポリマーとしては、例えば、キトサン、デンプン、セルロースおよびその誘導体等の多糖類が挙げられる。微生物合成系生分解性ポリマーとしては、例えば、ポリヒドロキシブチレートおよびその誘導体が挙げられる。化学合成系生分解性ポリマーとしては、例えば、ポリ乳酸、ポリカプロラクトン、ポリグリコール酸等の脂肪族ポリエステル系樹脂、脂肪族ポリエステルアミド共重合体等のポリアミド系樹脂、ポリビニルアルコール、エチレン－ビニルアルコール共重合体等のビニルアルコール系樹脂が挙げられる。 Examples of natural biodegradable polymers include polysaccharides such as chitosan, starch, cellulose, and derivatives thereof. Examples of microbially synthesized biodegradable polymers include polyhydroxybutyrate and derivatives thereof. Chemically synthesized biodegradable polymers include, for example, aliphatic polyester resins such as polylactic acid, polycaprolactone, and polyglycolic acid, polyamide resins such as aliphatic polyesteramide copolymers, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers. Examples include vinyl alcohol resins such as polymers.
前記生分解性ポリマーは１種用いてもよく、２種以上を用いてもよい。
本発明の粒子は、土壌中での分解性を抑制しない範囲で、非生分解性ポリマーをさらに含有することができる。非生分解性ポリマーとしては、例えば、ポリオレフィン系樹脂、ポリスチレン系樹脂、（メタ）アクリル系樹脂が挙げられる。
One type of the biodegradable polymer may be used, or two or more types may be used.
The particles of the present invention may further contain a non-biodegradable polymer within a range that does not inhibit degradability in soil. Examples of non-biodegradable polymers include polyolefin resins, polystyrene resins, and (meth)acrylic resins.
前記非生分解性ポリマーは１種用いてもよく、２種以上を用いてもよい。
本発明の粒子は、添加剤をさらに含有することができる。添加剤としては、例えば、フィラー、可塑剤、軟化剤、滑剤、熱安定剤、酸化防止剤、紫外線吸収剤、増粘剤、着色剤、分散剤、難燃剤、帯電防止剤が挙げられる。
One type of the non-biodegradable polymer may be used, or two or more types may be used.
The particles of the invention can further contain additives. Examples of additives include fillers, plasticizers, softeners, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, thickeners, colorants, dispersants, flame retardants, and antistatic agents.
前記添加剤は１種用いてもよく、２種以上を用いてもよい。
本発明の粒子は、以上説明したように他の成分を含有することができるが、本発明の粒子において、成分（１）に由来する構造単位と成分（２）に由来する構造単位との合計含有量（あるいは、成分（１）と成分（２）との反応物の含有量）は、９０質量％以上であることが好ましく、より好ましくは９５質量％以上、さらに好ましくは９８質量％以上である。本発明の粒子では、成分（１）に由来する構造単位において、アミノ酸に由来する構造単位とポリアミノ酸に由来する構造単位とのいずれかが含まれなくともよい。
One type of the additive may be used, or two or more types may be used.
The particles of the present invention can contain other components as explained above, but in the particles of the present invention, the total of the structural units derived from component (1) and the structural units derived from component (2) The content (or the content of the reactant between component (1) and component (2)) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more. be. In the particles of the present invention, the structural unit derived from component (1) does not need to contain either a structural unit derived from an amino acid or a structural unit derived from a polyamino acid.
＜形状および用途＞
本発明の粒子の形状は、粒子状であれば特に限定されず、例えば、球状、楕円体状、多角体状、角柱状、円柱状、棒状、不定形状が挙げられる。
本発明の粒子の平均粒子径は、特に制限されず、用途に応じて選択することができる。前記平均粒子径は、例えば、０．２～３０００μｍ、０．３～１０００μｍ、または０．３～５００μｍである。前記平均粒子径は、例えば走査型電子顕微鏡（ＳＥＭ）画像から任意に１００個選択した粒子の長径の数平均値である。
<Shape and usage>
The shape of the particles of the present invention is not particularly limited as long as they are particulate, and examples thereof include spherical, ellipsoidal, polygonal, prismatic, cylindrical, rod-like, and irregular shapes.
The average particle diameter of the particles of the present invention is not particularly limited and can be selected depending on the intended use. The average particle diameter is, for example, 0.2 to 3000 μm, 0.3 to 1000 μm, or 0.3 to 500 μm. The average particle diameter is the number average value of the long diameters of 100 particles arbitrarily selected from, for example, a scanning electron microscope (SEM) image.
本発明の粒子は、耐溶剤性、好ましくはさらに耐水性に優れるともに、自然界の土壌中での分解性に優れている。土壌中での分解性は、土壌中に存在する微生物により分解される生分解性を本発明の粒子が有するためであると推測される。このため、本発明の粒子は、例えば、農薬、医薬、化粧品、塗料（例えば、粉体塗料、水分散体型塗料、船底用塗料）、コーティング剤、接着剤、インキ、トナー等への添加剤として、またはアンチブロッキング剤、充填剤、光拡散剤として有用である。 The particles of the present invention have excellent solvent resistance, preferably water resistance, and are also excellent in degradability in soil in the natural world. It is presumed that the degradability in soil is due to the fact that the particles of the present invention have biodegradability to be decomposed by microorganisms present in soil. Therefore, the particles of the present invention can be used as additives for, for example, agricultural chemicals, medicines, cosmetics, paints (e.g., powder paints, water-dispersed paints, ship bottom paints), coating agents, adhesives, inks, toners, etc. , or as an anti-blocking agent, filler, or light diffusing agent.
また、本発明の粒子を用いて、種々の成形体を製造することができる。本発明の粒子を用いた成形方法としては、例えば、押出成形、射出成形、ブロー成形、カレンダー成形が挙げられる。 Moreover, various molded bodies can be manufactured using the particles of the present invention. Examples of molding methods using the particles of the present invention include extrusion molding, injection molding, blow molding, and calender molding.
以下、本発明を実施例に基づいて更に具体的に説明するが、本発明はこれら実施例に限定されない。以下の説明において、特に言及しないかぎり、「質量部」は「部」と表す。
［実施例１］
攪拌機、温度計、水分定量受器を取り付けた冷却管および窒素導入管を備えた反応装置に、アスパラギン酸１０部、カルボジライト（登録商標）Ｅ－０５（日清紡ケミカル社製、多官能カルボジイミド化合物）９０部および蒸留水１５０部を仕込み、得られた混合物を撹拌しながら昇温し、７５℃に達した時点から１時間反応させた。その後、オイルバスで水の沸点以上の温度で前記混合物を加熱し、反応装置に窒素を導入しながら、水を全て蒸発させ水分定量受器で回収し、アスパラギン酸と多官能カルボジイミド化合物との反応物である粒子１を得た。得られた粒子１を１００℃の棚段乾燥機で乾燥させた。
Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. In the following description, "parts by mass" is expressed as "parts" unless otherwise specified.
[Example 1]
10 parts of aspartic acid and 90 parts of Carbodilite (registered trademark) E-05 (manufactured by Nisshinbo Chemical Co., Ltd., a polyfunctional carbodiimide compound) were added to a reaction apparatus equipped with a cooling tube equipped with a stirrer, a thermometer, and a water content receiver, and a nitrogen introduction tube. 150 parts of distilled water were charged, and the resulting mixture was heated while stirring, and from the time it reached 75°C, it was reacted for 1 hour. Thereafter, the mixture is heated in an oil bath at a temperature higher than the boiling point of water, and while nitrogen is introduced into the reaction apparatus, all the water is evaporated and collected in a water quantitative receiver, and the reaction between aspartic acid and the polyfunctional carbodiimide compound is carried out. Particle 1, which is a product, was obtained. The obtained particles 1 were dried in a tray dryer at 100°C.
［実施例２～６、比較例１］
原料成分を表１に記載したとおりに変更したこと以外は実施例１と同様に行った。
[Examples 2 to 6, Comparative Example 1]
The same procedure as in Example 1 was carried out except that the raw material components were changed as shown in Table 1.
［比較例２］
攪拌機、温度計、冷却管および窒素導入管を備えた反応装置に、メチルメタクリレート（ＭＭＡ）９５部、エチレングリコールジメタクリレート（ＥＧＤＭＡ）５部、過酸化ベンゾイル１部および蒸留水２００部を仕込み、得られた混合物を３０分撹拌して乳化液を得た。その後、反応装置に窒素を導入しながら昇温し、７５℃に達した時点から１．５時間反応させ、さらに、９５℃まで昇温し、２時間攪拌を行った。その後、ろ過、乾燥を行い、架橋ＰＭＭＡ粒子を得た。
[Comparative example 2]
95 parts of methyl methacrylate (MMA), 5 parts of ethylene glycol dimethacrylate (EGDMA), 1 part of benzoyl peroxide, and 200 parts of distilled water were charged into a reaction apparatus equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube. The resulting mixture was stirred for 30 minutes to obtain an emulsion. Thereafter, the temperature was raised while introducing nitrogen into the reaction apparatus, and when the temperature reached 75°C, the reaction was carried out for 1.5 hours, and the temperature was further raised to 95°C, and stirring was performed for 2 hours. Thereafter, filtration and drying were performed to obtain crosslinked PMMA particles.
実施例で用いた製品を以下に記載する。
・アクアデュウ（登録商標）ＳＰＡ－３０Ｂ：ポリアスパラギン酸ナトリウム、
味の素社製
・カルボジライト（登録商標）Ｅ－０５：水分散性多官能カルボジイミドエマルション、固形分４０質量％、ＮＣＮ当量：３１０（ＮＣＮ基１モル当たりの化学式量）、日清紡ケミカル社製（表１中の配合量は固形分量である）
・Ｔｅｔｒａｄ－Ｃ：１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、三菱ガス化学社製
・Ｔｅｔｒａｄ－Ｘ：１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）ベンゼン、三菱ガス化学社製
The products used in the examples are described below.
・Aquadew (registered trademark) SPA-30B: Sodium polyaspartate,
Carbodilite (registered trademark) E-05, manufactured by Ajinomoto Co., Ltd.: water-dispersible polyfunctional carbodiimide emulsion, solid content 40% by mass, NCN equivalent: 310 (chemical formula amount per mole of NCN group), manufactured by Nisshinbo Chemical Co., Ltd. (in Table 1) The blended amount is the solid content)
・Tetrad-C: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical ・Tetrad-X: 1,3-bis(N,N-diglycidylaminomethyl)benzene, Mitsubishi Manufactured by Gas Kagaku Co., Ltd.
［重量減少率］
実施例および比較例で得られた粒子を、
２５℃のメチルエチルケトン（ＭＥＫ）中、
２５℃、ｐＨ３の水中、
２５℃、ｐＨ７の水中、
２５℃、ｐＨ１４の水中
に７２時間放置した後、前記粒子を取り出し、８０℃で７時間乾燥させた。
得られた前記粒子の重量減少率を、下記式から算出した。
重量減少率（％）＝｛１－［ＭＥＫまたは水中で前記放置し、前記乾燥後の粒子の重量］／［前記放置前の粒子の重量］｝×１００
[Weight reduction rate]
The particles obtained in the examples and comparative examples were
in methyl ethyl ketone (MEK) at 25°C.
In water at 25°C and pH 3.
In water at 25°C and pH 7.
After standing in water at 25°C and pH 14 for 72 hours, the particles were taken out and dried at 80°C for 7 hours.
The weight reduction rate of the obtained particles was calculated from the following formula.
Weight reduction rate (%) = {1-[Weight of particles after drying after being left in MEK or water]/[Weight of particles before being left]}×100
［土壌埋没試験］
実施例および比較例で得られた粒子を１０μｍナイロンメッシュに包み、土に埋めた。９０日後、土から前記粒子が包まれたナイロンメッシュを取り出し、目視にて粒子の存在有無を確認した。
〇：目視にて粒子の存在が確認できなかった
×：目視にて粒子の存在が確認できた
[Soil burial test]
The particles obtained in Examples and Comparative Examples were wrapped in 10 μm nylon mesh and buried in soil. After 90 days, the nylon mesh in which the particles were wrapped was removed from the soil, and the presence or absence of particles was visually confirmed.
〇: The presence of particles could not be visually confirmed. ×: The presence of particles could be confirmed visually.
表１中の原料成分は固形分量である。
表１より、アミノ酸またはポリアミノ酸に由来する構造単位と、多官能カルボジイミド化合物および多官能エポキシ化合物から選ばれる少なくとも１種に由来する構造単位とを有する粒子は、耐溶剤性・耐水性に優れ、かつ土壌中での分解性にも優れることがわかる（実施例１～６）。一方、架橋構造を有しないポリアスパラギン酸粒子は土壌中での分解は確認されるものの、メチルエチルケトンおよび水中での重量減少率試験において粒子が溶解する結果となった（比較例１）。また、（メタ）アクリル系粒子は耐溶剤性・耐水性には優れるものの、土壌中での分解は確認されなかった（比較例２）。
The raw material components in Table 1 are solid content amounts.
From Table 1, particles having a structural unit derived from an amino acid or a polyamino acid and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound have excellent solvent resistance and water resistance, It can also be seen that the decomposition properties in soil are excellent (Examples 1 to 6). On the other hand, although decomposition of polyaspartic acid particles without a crosslinked structure in soil was confirmed, the particles were dissolved in a weight loss rate test in methyl ethyl ketone and water (Comparative Example 1). Further, although (meth)acrylic particles have excellent solvent resistance and water resistance, decomposition in soil was not confirmed (Comparative Example 2).
Claims (4)
下記条件（ａ）を満たすアミノ酸系粒子：
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。 Amino acid-based particles having a structural unit derived from at least one selected from aspartic acid and glutamic acid , and a structural unit derived from at least one selected from a polyfunctional carbodiimide compound and a polyfunctional epoxy compound,
Amino acid-based particles that satisfy the following condition (a):
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
（ｂ）前記粒子を２５℃、ｐＨ３の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｃ）前記粒子を２５℃、ｐＨ７の水中に７２時間放置した後の
重量減少率が１０％以下である。
（ｄ）前記粒子を２５℃、ｐＨ１４の水中に７２時間放置した後の
重量減少率が１０％以下である。 The amino acid-based particles according to claim 1, further satisfying at least one condition selected from the following conditions (b), (c), and (d):
(b) The weight loss rate after the particles are left in water at 25° C. and pH 3 for 72 hours is 10% or less.
(c) The weight loss rate after the particles are left in water at 25° C. and pH 7 for 72 hours is 10% or less.
(d) The weight loss rate after the particles are left in water at 25° C. and pH 14 for 72 hours is 10% or less.
下記条件（ａ）を満たすアミノ酸系粒子：
（ａ）前記粒子を２５℃のメチルエチルケトン中に７２時間放置した後の
重量減少率が１０％以下である。 Amino acid-based particles having a structural unit derived from sodium polyaspartate and a structural unit derived from a polyfunctional carbodiimide compound,
Amino acid-based particles that satisfy the following condition (a):
(a) The weight loss rate after the particles are left in methyl ethyl ketone at 25° C. for 72 hours is 10% or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001131283A (en) | 1999-11-05 | 2001-05-15 | Mitsui Chemicals Inc | Crosslinked polyamino acid-containing particle having crosslinked surface |
| JP2001278974A (en) | 2000-03-31 | 2001-10-10 | Mitsui Chemicals Inc | Crosslinked polymer and production method of the same |
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| JP2001131283A (en) | 1999-11-05 | 2001-05-15 | Mitsui Chemicals Inc | Crosslinked polyamino acid-containing particle having crosslinked surface |
| JP2001278974A (en) | 2000-03-31 | 2001-10-10 | Mitsui Chemicals Inc | Crosslinked polymer and production method of the same |
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