JP2017155070A - Cellulose ester composition - Google Patents
Cellulose ester composition Download PDFInfo
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- JP2017155070A JP2017155070A JP2016036710A JP2016036710A JP2017155070A JP 2017155070 A JP2017155070 A JP 2017155070A JP 2016036710 A JP2016036710 A JP 2016036710A JP 2016036710 A JP2016036710 A JP 2016036710A JP 2017155070 A JP2017155070 A JP 2017155070A
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229920002678 cellulose Polymers 0.000 title claims abstract description 22
- -1 water-soluble carbodiimide compound Chemical class 0.000 claims abstract description 29
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001278 adipic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- MXMSRLWLJCUTEQ-UHFFFAOYSA-N 6-o-benzyl 1-o-[2-(2-butoxyethoxy)ethyl] hexanedioate Chemical compound CCCCOCCOCCOC(=O)CCCCC(=O)OCC1=CC=CC=C1 MXMSRLWLJCUTEQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- SCABKEBYDRTODC-UHFFFAOYSA-N bis[2-(2-butoxyethoxy)ethyl] hexanedioate Chemical compound CCCCOCCOCCOC(=O)CCCCC(=O)OCCOCCOCCCC SCABKEBYDRTODC-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、流動性が良く、成形品からの異臭発生を抑制できるセルロースエステル組成物に関する。 The present invention relates to a cellulose ester composition having good fluidity and capable of suppressing the generation of a strange odor from a molded product.
セルロースエステルから得られる成形体は、射出成形法などにより成形したとき、原料に由来する脂肪酸（酢酸など）により臭気が問題になることがある。
特許文献１には、臭気の問題を解決する方法として、可塑化されたセルロースエステルおよびカルボジイミド化合物で構成されているセルロースエステル系樹脂組成物が記載されている。
前記組成物は、酢酸などの有機酸臭に由来する異臭を高いレベルで低減できることが記載されている（段落番号００１２）。
When a molded body obtained from cellulose ester is molded by an injection molding method or the like, odor may be a problem due to fatty acids (such as acetic acid) derived from raw materials.
Patent Document 1 describes a cellulose ester resin composition composed of a plasticized cellulose ester and a carbodiimide compound as a method for solving the problem of odor.
It is described that the composition can reduce a bad odor derived from an organic acid odor such as acetic acid at a high level (paragraph 0012).
本発明は、流動性が良く、成形品からの異臭発生を抑制できるセルロースエステル組成物を提供することを課題とする。 An object of the present invention is to provide a cellulose ester composition having good fluidity and capable of suppressing the generation of a strange odor from a molded product.
本発明は、（Ａ）セルロースエステル１００質量部に対して、
（Ｂ)可塑剤５〜４０質量部、
（Ｃ)水溶性のカルボジイミド化合物０．１〜５質量部を含有しており、
前記（Ｃ）成分の水溶性のカルボジイミド化合物が、２０℃の水に対する溶解度が０．３〜２００g／100mlのものであるセルロースエステル組成物を提供する。
The present invention relates to (A) 100 parts by mass of cellulose ester,
(B) 5-40 parts by mass of a plasticizer,
(C) contains 0.1 to 5 parts by mass of a water-soluble carbodiimide compound,
Provided is a cellulose ester composition in which the water-soluble carbodiimide compound of the component (C) has a solubility in water at 20 ° C. of 0.3 to 200 g / 100 ml.
本発明の組成物は、流動性が良く、成形品からの異臭発生を抑制できる。 The composition of the present invention has good fluidity and can suppress the generation of off-flavors from molded articles.
＜（Ａ）成分＞
本発明の組成物で用いる（Ａ）成分のセルロースエステルは公知のものであり、セルロースアセテート、セルロースプロピオネート、セルロースブチレート、セルロースアセテートプロピオネート、セルロースアセテートブチレートを挙げることができ、セルロースアセテート、セルロースアセテートプロピオネートおよびセルロースアセテートブチレートから選ばれるものが好ましく、セルロースアセテートがより好ましい。
その他、ポリカプロラクトングラフト化セルロースアセテート、アセチルメチルセルロース、アセチルエチルセルロース、アセチルプロピルセルロース、アセチルヒドロキシエチルセルロース、アセチルヒドロキシプロピルセルロースなども挙げることができる。
<(A) component>
The cellulose ester of component (A) used in the composition of the present invention is a known one, and examples thereof include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate. Those selected from acetate, cellulose acetate propionate and cellulose acetate butyrate are preferred, and cellulose acetate is more preferred.
Other examples include polycaprolactone-grafted cellulose acetate, acetylmethylcellulose, acetylethylcellulose, acetylpropylcellulose, acetylhydroxyethylcellulose, acetylhydroxypropylcellulose, and the like.
（Ａ）成分のセルロースエステルは、平均置換度が２．７以下のセルロースアセテートが好ましい。
（Ａ）成分のセルロースエステルの重合度は、粘度平均重合度が１００〜１０００、好ましくは１００〜５００である。
The cellulose ester as the component (A) is preferably cellulose acetate having an average substitution degree of 2.7 or less.
(A) As for the polymerization degree of the cellulose ester of a component, a viscosity average polymerization degree is 100-1000, Preferably it is 100-500.
＜（Ｂ）成分＞
（Ｂ）成分の可塑剤は、セルロースアセテートの可塑剤として使用されている公知の可塑剤（例えば、特許第５７９８６４０号公報に記載の可塑剤）を使用することができるが、それらの中でもアジピン酸エステルが好ましい。
アジピン酸エステルとしては、アジピン酸ジブチル、アジピン酸ジオクチル、アジピン酸ブトキシエトキシエチル・ベンジル、アジピン酸ジブトキシエトキシエチルなどを挙げることができる。
またアジピン酸エステルとしては、特許第５７９８６４０号公報の特許請求の範囲に記載された式（I）、（II）、（III）、（IV）、（V）、（VI）で示されるアジピン酸エステルも使用することができる。
<(B) component>
As the plasticizer of the component (B), a known plasticizer used as a plasticizer for cellulose acetate (for example, a plasticizer described in Japanese Patent No. 5798640) can be used, and among them, adipic acid Esters are preferred.
Examples of adipic acid esters include dibutyl adipate, dioctyl adipate, butoxyethoxyethyl benzyl adipate, and dibutoxyethoxyethyl adipate.
Moreover, as adipic acid ester, the adipic acid shown by the formula (I), (II), (III), (IV), (V), (VI) described in the claim of patent 5798640 gazette Esters can also be used.
＜（Ｃ）成分＞
（Ｃ）成分の水溶性のカルボジイミド化合物は、分子内にカルボジイミド基［−Ｎ＝Ｃ＝Ｎ−］を少なくとも１つ有する水溶性の化合物であり、２０℃の水に対する溶解度（以下「溶解度」という）が０．３〜２００g／100mlのものである。
溶解度は０．３〜１００g／100mlが好ましく、０．３〜５０g／100mlがより好ましい。
水溶性のカルボジイミド化合物は、水溶性のモノカルボジイミド類であってもよく、水溶性のポリカルボジイミド類であってもよい。
<(C) component>
The water-soluble carbodiimide compound (C) is a water-soluble compound having at least one carbodiimide group [—N═C═N—] in the molecule, and is soluble in water at 20 ° C. (hereinafter referred to as “solubility”). ) Is from 0.3 to 200 g / 100 ml.
The solubility is preferably from 0.3 to 100 g / 100 ml, more preferably from 0.3 to 50 g / 100 ml.
The water-soluble carbodiimide compound may be a water-soluble monocarbodiimide or a water-soluble polycarbodiimide.
水溶性のモノカルボジイミド類は、分子内に１つのカルボジイミド基を有する化合物である。代表的なモノカルボジイミド化合物としては、脂肪族モノカルボジイミド類、脂環族モノカルボジイミド類、芳香族モノカルボジイミド類などが挙げられる。 Water-soluble monocarbodiimides are compounds having one carbodiimide group in the molecule. Representative monocarbodiimide compounds include aliphatic monocarbodiimides, alicyclic monocarbodiimides, aromatic monocarbodiimides, and the like.
水溶性のポリカルボジイミド類は、分子内に少なくとも２つのカルボジイミド基を有する化合物である。代表的なポリカルボジイミド化合物としては、脂肪族ポリカルボジイミド類、脂環族ポリカルボジイミド類、芳香族ポリカルボジイミド類などが挙げられる。 Water-soluble polycarbodiimides are compounds having at least two carbodiimide groups in the molecule. Typical polycarbodiimide compounds include aliphatic polycarbodiimides, alicyclic polycarbodiimides, aromatic polycarbodiimides, and the like.
水溶性のカルボジイミド化合物は、好ましくは水溶性のポリカルボジイミド類であり、より好ましくは水溶性の脂肪族ポリカルボジイミド類、水溶性の脂環族ポリカルボジイミド類および水溶性の芳香族ポリカルボジイミド類から選択された少なくとも１種である。 The water-soluble carbodiimide compound is preferably a water-soluble polycarbodiimide, more preferably selected from water-soluble aliphatic polycarbodiimides, water-soluble alicyclic polycarbodiimides and water-soluble aromatic polycarbodiimides. At least one selected.
（Ａ）成分と（Ｂ）成分の含有割合は、（Ａ）成分１００質量部に対して（Ｂ）成分は５〜４０質量部であり、好ましくは８〜３０質量部、より好ましくは１０〜２０質量部である。 The content ratio of the component (A) and the component (B) is 5 to 40 parts by mass, preferably 8 to 30 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the component (A). 20 parts by mass.
（Ａ）成分と（Ｃ）成分の含有割合は、（Ａ）成分１００質量部に対して（Ｃ）成分は０．１〜５質量部であり、好ましくは０．３〜３質量部、より好ましくは０．５〜１．５質量部である。 The content ratio of the component (A) and the component (C) is 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, with respect to 100 parts by mass of the component (A). Preferably it is 0.5-1.5 mass parts.
本発明の組成物が（Ａ）、（Ｂ）および（Ｃ）成分からなる組成物であるときのＭＦＲは、（Ａ）および（Ｂ）成分からなる組成物であるときのＭＦＲと比べると、同等以上の数値を示しており、（Ｃ）成分の含有量を調整することによりＭＦＲの増加程度（ΔＭＦＲ）を１〜２０ｇ／10minの範囲にすることができる。 The MFR when the composition of the present invention is a composition composed of the components (A), (B) and (C) is compared with the MFR when the composition is composed of the components (A) and (B). A numerical value equal to or higher than that is shown. By adjusting the content of component (C), the degree of increase in MFR (ΔMFR) can be set in the range of 1 to 20 g / 10 min.
本発明の組成物は、さらに充填剤を含有することができる。
充填剤としては、繊維状充填剤、非繊維状充填剤（粉粒状または板状充填剤など）が含まれ、例えば、特開２００５−１９４３０２号公報の段落番号００２５〜００３２に記載のものを挙げることができる。
充填剤の含有割合は、（Ａ）成分のセルロースエステル１００質量部に対して、５〜５０質量部が好ましく、より好ましくは５〜４０質量部、さらに好ましくは５〜３０質量部である。
The composition of the present invention may further contain a filler.
Examples of the filler include fibrous fillers and non-fibrous fillers (powder or plate-like fillers), and examples include those described in paragraph numbers 0025 to 0032 of JP-A-2005-194302. be able to.
As for the content rate of a filler, 5-50 mass parts is preferable with respect to 100 mass parts of cellulose ester of (A) component, More preferably, it is 5-40 mass parts, More preferably, it is 5-30 mass parts.
本発明の組成物は、特開２００５−１９４３０２号公報の段落番号００３５〜００４２に記載のエポキシ化合物、段落番号００４３〜００５２に記載の有機酸、チオエーテル、亜リン酸エステル化合物などの安定化剤を含有することができる。 The composition of the present invention comprises a stabilizer such as an epoxy compound described in paragraph Nos. 0035 to 0042 of JP-A No. 2005-194302, an organic acid, a thioether, a phosphite compound described in paragraph Nos. Can be contained.
本発明の組成物は、用途に応じて、慣用の添加剤、例えば、他の安定化剤（例えば、酸化防止剤、紫外線吸収剤、熱安定剤、耐光安定剤など）、着色剤（染料、顔料など）、難燃剤、帯電防止剤、滑剤、アンチブロッキング剤、分散剤、流動化剤、ドリッピング防止剤、抗菌剤などを含んでいてもよい。 Depending on the application, the composition of the present invention may contain conventional additives such as other stabilizers (for example, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc.), colorants (dyes, Pigments, etc.), flame retardants, antistatic agents, lubricants, anti-blocking agents, dispersants, fluidizing agents, anti-dripping agents, antibacterial agents and the like.
本発明の組成物は、例えば、各成分をタンブラーミキサー、ヘンシェルミキサー、リボンミキサー、ニーダーなどの混合機を用いて乾式または湿式で混合して調製してもよい。
さらに、前記混合機で予備混合した後、一軸または二軸押出機などの押出機で混練してペレットに調製する方法、加熱ロールやバンバリーミキサーなどの混練機で溶融混練して調製する方法を適用することができる。
The composition of the present invention may be prepared by, for example, mixing each component dry or wet using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, or a kneader.
Furthermore, after premixing with the mixer, a method of kneading into a pellet by an extruder such as a single-screw or twin-screw extruder, and a method of melting and kneading with a kneader such as a heating roll or a Banbury mixer are applied. can do.
本発明の組成物は、射出成形、押出成形、真空成形、異型成形、発泡成形、インジェクションプレス、プレス成形、ブロー成形、ガス注入成形などによって各種成形品に成形することができる。 The composition of the present invention can be molded into various molded articles by injection molding, extrusion molding, vacuum molding, profile molding, foam molding, injection press, press molding, blow molding, gas injection molding and the like.
実施例および比較例
ヘンシェルミキサーを用いて、ミキサー内の摩擦熱で７０℃以上となるように各組成物を攪拌混合した後、二軸押出機（シリンダー温度：２００℃、ダイス温度：２２０℃）に供給し、押し出してペレット化した。
得られたペレットを、射出成形機に供給して、シリンダー温度２３０℃、金型温度８０℃、成形サイクル３０秒（射出１５秒、冷却時間１５秒）の条件で試験片を射出成形して、各評価試験に使用した。
Examples and Comparative Examples Using a Henschel mixer, each composition was stirred and mixed so that the frictional heat in the mixer was 70 ° C or higher, and then a twin screw extruder (cylinder temperature: 200 ° C, die temperature: 220 ° C). And extruded to pelletize.
The obtained pellets were supplied to an injection molding machine, and a test piece was injection molded under the conditions of a cylinder temperature of 230 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds (injection 15 seconds, cooling time 15 seconds), Used for each evaluation test.
（ＭＦＲ）
ＩＳＯ１１３３に基づいて、温度２６０℃および荷重５ｋｇで測定した。ＭＦＲが大きいほど、流動性が良いことを示している。
（ΔＭＦＲ）
カルボジイミド化合物を含有していない比較例５に対するＭＦＲの差を示した。
(MFR)
Based on ISO 1133, measurement was performed at a temperature of 260 ° C. and a load of 5 kg. It shows that fluidity is so good that MFR is large.
(ΔMFR)
The difference of MFR with respect to the comparative example 5 which does not contain a carbodiimide compound was shown.
（官能試験）
射出成形直後の試験片をポリエチレン袋に入れて密閉し、室温（２０〜２５℃）で２時間放置した。そして、この放置したポリエチレン袋を開放した直後のポリエチレン袋内の臭気について、５名の試験員の臭覚で以下の基準で官評価を行った。
○：５名全員が無臭であるか、４名が無臭であると感じた。
△：５名全員が、かすかに酢酸臭があると感じた。
×：５名全員が、はっきりと酢酸臭があると感じた。
(Sensory test)
The test piece immediately after injection molding was put in a polyethylene bag, sealed, and left at room temperature (20 to 25 ° C.) for 2 hours. Then, the odor in the polyethylene bag immediately after the left polyethylene bag was opened was subjected to government evaluation based on the following criteria based on the sense of smell of five examiners.
○: All 5 people felt odorless or 4 felt odorless.
(Triangle | delta): All five persons felt that there was a faint acetic acid smell.
X: All five people felt that there was a clear acetic acid odor.
（Ａ）成分
セルロースアセテート：Ｌ−４０（（株）ダイセル製）
（Ｂ）成分（可塑剤）
アジピン酸エステル：ＤＡＩＦＡＴＴＹ−１０１（大八化学工業（株）製）
（Ｃ）成分（水溶性のカルボジイミド化合物）
Ｖ−０４Ｋ：水溶性芳香族ポリカルボジイミド（日清紡ケミカル（株）製）溶解度０．３〜５ｇ／１００ｍｌ，５％重量減少温度３０２℃
（Ｃ’）成分（（Ｃ）成分の比較化合物）
ＨＭＶ−１５ＣＡ：脂環族ポリカルボジイミド（日清紡ケミカル（株）製），溶解度（２０℃の水に不溶），５％重量減少温度３５０℃
ＤＩＣ：モノカルボジイミド（川口化学工業（株）製）溶解度（２０℃の水に難溶；０．０１g／100ml以下），５％重量減少温度４０℃
安定剤
ＳＵ１６８：亜リン酸エステル化合物（イルガフォス（ＩＲＧＡＦＯＳ）１６８、ＢＡＳＦジャパン（株）製）
２０２１Ｐ：エポキシ化合物（セロキサイド２０２１Ｐ、（株）ダイセル製）
ＣＡ３２Ｍ：クエン酸（一水和物）（クエン酸（結晶）３２Ｍ、昭和化工（株）製）
(A) Component Cellulose acetate: L-40 (manufactured by Daicel Corporation)
(B) component (plasticizer)
Adipic acid ester: DAIFATTY-101 (manufactured by Daihachi Chemical Industry Co., Ltd.)
Component (C) (water-soluble carbodiimide compound)
V-04K: Water-soluble aromatic polycarbodiimide (manufactured by Nisshinbo Chemical Co., Ltd.) Solubility 0.3-5 g / 100 ml, 5% weight loss temperature 302 ° C.
Component (C ′) (Comparative compound of component (C))
HMV-15CA: alicyclic polycarbodiimide (manufactured by Nisshinbo Chemical Co., Ltd.), solubility (insoluble in water at 20 ° C), 5% weight loss temperature 350 ° C
DIC: Monocarbodiimide (manufactured by Kawaguchi Chemical Industry Co., Ltd.) Solubility (Slightly soluble in water at 20 ° C; 0.01 g / 100 ml or less), 5% weight loss temperature 40 ° C
Stabilizer SU168: Phosphite compound (IRGAFOS 168, manufactured by BASF Japan Ltd.)
2021P: Epoxy compound (Celoxide 2021P, manufactured by Daicel Corporation)
CA32M: Citric acid (monohydrate) (citric acid (crystal) 32M, manufactured by Showa Kako Co., Ltd.)
実施例１、２から明らかなとおり、（Ｃ）成分の水溶性のカルボジイミド化合物を使用することで、組成物のＭＦＲが良く、また成形品からの酢酸臭もほとんどなかった。
カルボジイミド化合物を含有していない比較例４は、組成物のＭＦＲが良いが、成形品からの酢酸臭があった。
水溶性のカルボジイミド化合物ではない（Ｃ’）成分を使用した比較例１〜２は、成形品からの酢酸臭は無かったが、組成物のＭＦＲが小さくなった。
モノカルボジイミドを使用した比較例３は、５％重量減少温度が低く、押出成形時に揮発してしまい、生産性が不可であった。
なお、実施例で使用したＨＭＶ−１５ＣＡは、水不溶性の脂環族ポリカルボジイミドであり、特許文献１の実施例で使用している「カルボジイミド化合物（１）：ポリ（４，４'−ジシクロヘキシルメタンカルボジイミド）（重合度１０）」と同じか、類似するものと考えられる。
また、実施例で使用したＤＩＣは、モノカルボジイミドであり、特許文献１の実施例で使用している「カルボジイミド化合物（２）：１，３−ジイソプロピルカルボジイミド（川口化学工業（株）製）」と同じか、類似するものと考えられる。
よって、特許文献１の発明の実施例では、本発明の効果が得られないことが明らかであるから、引用文献１の発明には、事実上、本発明が開示されていないものである。
As is clear from Examples 1 and 2, by using the water-soluble carbodiimide compound of component (C), the MFR of the composition was good and there was almost no acetic acid odor from the molded product.
Although the comparative example 4 which does not contain a carbodiimide compound had good MFR of a composition, there was an acetic acid odor from a molded article.
In Comparative Examples 1 and 2 using the component (C ′) which is not a water-soluble carbodiimide compound, there was no acetic acid odor from the molded product, but the MFR of the composition was small.
Comparative Example 3 using monocarbodiimide had a low 5% weight loss temperature and volatilized at the time of extrusion molding, and productivity was not possible.
In addition, HMV-15CA used in the examples is a water-insoluble alicyclic polycarbodiimide, and “carbodiimide compound (1): poly (4,4′-dicyclohexylmethane) used in the examples of Patent Document 1. Carbodiimide) (degree of polymerization 10) "is considered the same or similar.
The DIC used in the examples is monocarbodiimide, and “carbodiimide compound (2): 1,3-diisopropylcarbodiimide (manufactured by Kawaguchi Chemical Industry Co., Ltd.)” used in the examples of Patent Document 1. It is considered the same or similar.
Therefore, since it is clear that the effect of the present invention cannot be obtained in the example of the invention of Patent Document 1, the invention of Cited Document 1 does not effectively disclose the present invention.
本発明の組成物は、例えば、ＯＡ・家電機器分野、電気・電子分野、通信機器分野、サニタリー分野、自動車などの輸送車両分野、家具・建材などの住宅関連分野、雑貨分野などの各パーツ、ハウジングなどに使用することができる。
The composition of the present invention includes, for example, each part in the OA / home appliance field, the electrical / electronic field, the communication field, the sanitary field, the transportation vehicle field such as an automobile, the housing-related field such as furniture and building materials, the miscellaneous field, It can be used for a housing or the like.
Claims (5)
（Ｂ)可塑剤５〜４０質量部、
（Ｃ)水溶性のカルボジイミド化合物０．１〜５質量部を含有しており、
前記（Ｃ）成分の水溶性のカルボジイミド化合物が、２０℃の水に対する溶解度が０．３〜２００g／100mlのものであるセルロースエステル組成物。 (A) For 100 parts by mass of cellulose ester,
(B) 5-40 parts by mass of a plasticizer,
(C) contains 0.1 to 5 parts by mass of a water-soluble carbodiimide compound,
A cellulose ester composition in which the water-soluble carbodiimide compound of the component (C) has a solubility in water at 20 ° C. of 0.3 to 200 g / 100 ml.
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| JP2005162875A (en) * | 2003-12-02 | 2005-06-23 | Sony Corp | Resin composition, molded product, electrical product, and method for producing the resin composition |
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| JP2006183009A (en) * | 2004-12-28 | 2006-07-13 | Daicel Chem Ind Ltd | Cellulose ester-based resin composition and molded article made thereof |
| JP2007161943A (en) * | 2005-12-16 | 2007-06-28 | Daicel Chem Ind Ltd | Cellulose ester-based resin composition |
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Patent Citations (6)
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| US3252817A (en) * | 1961-12-22 | 1966-05-24 | Bayer Ag | Stabilization of synthetic plastics based on cellulose esters |
| JP2004035811A (en) * | 2002-07-05 | 2004-02-05 | Miyoshi Oil & Fat Co Ltd | Aqueous biodegradable resin dispersion |
| JP2005162875A (en) * | 2003-12-02 | 2005-06-23 | Sony Corp | Resin composition, molded product, electrical product, and method for producing the resin composition |
| JP2006111765A (en) * | 2004-10-15 | 2006-04-27 | Kansai Paint Co Ltd | Anionic electrodeposition coating |
| JP2006183009A (en) * | 2004-12-28 | 2006-07-13 | Daicel Chem Ind Ltd | Cellulose ester-based resin composition and molded article made thereof |
| JP2007161943A (en) * | 2005-12-16 | 2007-06-28 | Daicel Chem Ind Ltd | Cellulose ester-based resin composition |
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