JP2017066178A - Resin composition, foam, microorganism carrier and foam production process - Google Patents
Resin composition, foam, microorganism carrier and foam production process Download PDFInfo
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- JP2017066178A JP2017066178A JP2015189412A JP2015189412A JP2017066178A JP 2017066178 A JP2017066178 A JP 2017066178A JP 2015189412 A JP2015189412 A JP 2015189412A JP 2015189412 A JP2015189412 A JP 2015189412A JP 2017066178 A JP2017066178 A JP 2017066178A
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- 239000006260 foam Substances 0.000 title claims abstract description 68
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 244000005700 microbiome Species 0.000 title abstract description 18
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract description 28
- 238000005187 foaming Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 238000010097 foam moulding Methods 0.000 claims abstract description 13
- 238000004898 kneading Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 40
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 20
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 20
- 230000000813 microbial effect Effects 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 210000000497 foam cell Anatomy 0.000 abstract description 6
- 229920005672 polyolefin resin Polymers 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000013494 PH determination Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、発泡成形に好適な樹脂組成物、前記樹脂組成物を用いて成形された発泡体、前記発泡体からなる微生物担体、および発泡体の製造方法に関する。 The present invention relates to a resin composition suitable for foam molding, a foam molded using the resin composition, a microbial carrier comprising the foam, and a method for producing the foam.
従来、発泡成形の一つである押出発泡成形により微生物担体用発泡体を製造する方法として、オレフィン系樹脂、親水化剤としてのセルロース系粉末、発泡剤としての重曹を含む混練物を押出発泡する発泡体の製造方法がある(特許文献1)。 Conventionally, as a method for producing a foam for a microorganism carrier by extrusion foam molding, which is one of foam molding, a kneaded product containing an olefin resin, a cellulose powder as a hydrophilizing agent, and baking soda as a foaming agent is extruded and foamed. There exists a manufacturing method of a foam (patent document 1).
従来の押出発泡成形では、発泡剤として重曹を用いているため、押出発泡時に重曹から生成されたNa2CO3が発泡体に含まれることになり、製造した発泡体を微生物担体として汚水等の処理水に投入すると、発泡体に含まれているNa2CO3が水中に溶出して処理水のpHが上昇するようになる。しかし、一般的に、水棲微生物の生育環境としてはpH6〜8が最適なため、発泡体の使用によってpHが上昇した処理水に対して何らかの中和処理が必要になる問題がある。 In conventional extrusion foam molding, baking soda is used as a foaming agent, so Na 2 CO 3 generated from baking soda during extrusion foaming is contained in the foam, and the produced foam is used as a microorganism carrier for sewage and the like. When it is introduced into the treated water, Na 2 CO 3 contained in the foam is eluted into the water and the pH of the treated water is increased. However, in general, pH 6 to 8 is optimal as a growth environment for varicella microorganisms, and thus there is a problem that some neutralization treatment is required for treated water whose pH has been increased by the use of foam.
なお、前記pH制御のためにクエン酸等の低分子多価酸を添加して押出発泡成形すると、過剰発泡してセルが不均一になり、良好な発泡体が得られなくなる。また、得られる発泡体は水に対する沈降性が低下し、微生物担体として使用する場合には処理効率が悪くなる問題がある。 In addition, when low molecular polyvalent acid such as citric acid is added for the pH control and extrusion foam molding is performed, excessive foaming occurs and cells become non-uniform, and a good foam cannot be obtained. Further, the obtained foam has a problem that the settling property with respect to water is lowered, and the treatment efficiency is deteriorated when used as a microorganism carrier.
本発明は前記の点に鑑みなされたものであって、水に投入した場合にpHの上昇を抑えることができ、微生物担体のようにpHの制御が必要な用途に好適な発泡体の製造に用いられる樹脂組成物、前記樹脂組成物を用いて成形された発泡体、前記発泡体からなる微生物担体および発泡体の製造方法の提供を目的とする。 The present invention has been made in view of the above points, and can suppress an increase in pH when introduced into water, and can be used to produce a foam suitable for applications that require pH control, such as microbial carriers. It aims at providing the resin composition used, the foam shape | molded using the said resin composition, the microorganisms carrier which consists of the said foam body, and the manufacturing method of a foam body.
請求項1の発明は、発泡成形に用いられる熱可塑性樹脂、無機粉末、発泡剤、発泡助剤を含む原料を溶融混練した樹脂組成物であって、前記発泡剤は重曹であり、前記発泡助剤はポリ(メタ)アクリル酸(部分中和物)であることを特徴とする樹脂組成物に係る。 The invention of claim 1 is a resin composition obtained by melt-kneading a raw material containing a thermoplastic resin, an inorganic powder, a foaming agent, and a foaming aid used for foam molding, wherein the foaming agent is baking soda, and the foaming aid. The agent is a poly (meth) acrylic acid (partially neutralized product).
請求項2の発明は、請求項1において、前記重曹およびポリ(メタ)アクリル酸(部分中和物)の量が前記熱可塑性樹脂と無機粉末の合計100重量部に対して重曹が1〜5重量部、かつポリ(メタ)アクリル酸(部分中和物)が2〜25重量部であることを特徴とする。 The invention of claim 2 is the invention according to claim 1, wherein the amount of the baking soda and poly (meth) acrylic acid (partially neutralized product) is 1 to 5 with respect to a total of 100 parts by weight of the thermoplastic resin and the inorganic powder. It is characterized by 2 to 25 parts by weight of poly (meth) acrylic acid (partially neutralized product).
請求項3の発明は、請求項1または2に記載した樹脂組成物を用いて作成された発泡体に係る。 Invention of Claim 3 concerns on the foam created using the resin composition described in Claim 1 or 2.
請求項4の発明は、請求項1または2に記載した樹脂組成物を用いて作成された発泡体からなる微生物担体に係る。 The invention of claim 4 relates to a microbial carrier comprising a foam produced using the resin composition according to claim 1 or 2.
請求項5の発明は、熱可塑性樹脂、無機粉末、発泡剤、発泡助剤を含む原料を溶融混練して発泡成形する発泡体の製造方法において、前記発泡剤に重曹を使用し、前記発泡助剤にポリ(メタ)アクリル酸(部分中和物)を使用することを特徴とする。 According to a fifth aspect of the present invention, there is provided a foam manufacturing method in which a raw material containing a thermoplastic resin, an inorganic powder, a foaming agent, and a foaming aid is melt-kneaded and foam-molded. Poly (meth) acrylic acid (partially neutralized product) is used as the agent.
請求項6の発明は、請求項5において、重曹と前記ポリ(メタ)アクリル酸(部分中和物)の量が前記熱可塑性樹脂と無機粉末の合計100重量部に対して重曹が1〜5重量部、ポリ(メタ)アクリル酸(部分中和物)が2〜25重量部であることを特徴とする。 The invention according to claim 6 is the invention according to claim 5, wherein the amount of baking soda and the poly (meth) acrylic acid (partially neutralized product) is 1 to 5 with respect to a total of 100 parts by weight of the thermoplastic resin and the inorganic powder. It is characterized by 2 to 25 parts by weight of poly (meth) acrylic acid (partially neutralized product).
請求項7の発明は、請求項5または6において、前記発泡体が微生物担体用の発泡体であることを特徴とする。 The invention of claim 7 is characterized in that, in claim 5 or 6, the foam is a foam for a microorganism carrier.
本発明によれば、発泡助剤にポリ(メタ)アクリル酸(部分中和物)を使用するため、発泡剤を入手が容易かつ安価な重曹としても、水中へ投入した場合にpHの上昇を抑えることのできる発泡体を製造することができ、微生物担体のようにpHの制御が必要な用途に好適な発泡体を安価に製造することができる。 According to the present invention, since poly (meth) acrylic acid (partially neutralized product) is used as a foaming aid, even when baking soda, which is easily available and inexpensive, is added to water, the pH is increased. The foam which can be suppressed can be manufactured and the foam suitable for the use which needs control of pH like a microorganisms carrier can be manufactured at low cost.
以下に本発明の樹脂組成物、発泡体、微生物担体および発泡体の製造方法について説明する。
本発明の樹脂組成物は、押出発泡成形や発泡射出成形等の発泡成形に好適なものであり、熱可塑性樹脂、無機粉末、発泡剤、発泡助剤を含む原料を溶融混練した樹脂組成物である。
The resin composition, foam, microbial carrier and foam production method of the present invention are described below.
The resin composition of the present invention is suitable for foam molding such as extrusion foam molding and foam injection molding, and is a resin composition obtained by melting and kneading raw materials including a thermoplastic resin, an inorganic powder, a foaming agent, and a foaming aid. is there.
熱可塑性樹脂は、特に限定されないが、ポリオレフィン系樹脂が好適である。ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、ポリメタクリル酸メチル等を挙げることができ、それらを単独で使用または二種以上の混合物を使用することができる。なお、ポリエチレンは、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)の何れでもよい。 The thermoplastic resin is not particularly limited, but a polyolefin resin is preferable. Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polymethyl methacrylate, and the like. These can be used alone or in a mixture of two or more. The polyethylene may be any of high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
無機粉末は、発泡体の比重調整、発泡時の気泡調整、他の材料の使用量低減のために使用される。無機粉末としては、炭酸カルシウム、硫酸バリウム、亜リン酸カルシウム、ゼオライト、シリカ、タルク、酸化チタン、チタン酸カルシウム、水酸化アルミニウム等を挙げることができ、それらを単独または組み合わせて使用することができる。無機粉末の量は、熱可塑性樹脂:無機粉末=30:70〜80:20(重量比)が好ましい。 The inorganic powder is used for adjusting the specific gravity of the foam, adjusting the bubbles during foaming, and reducing the amount of other materials used. Examples of the inorganic powder include calcium carbonate, barium sulfate, calcium phosphite, zeolite, silica, talc, titanium oxide, calcium titanate, aluminum hydroxide, and the like, and these can be used alone or in combination. The amount of the inorganic powder is preferably thermoplastic resin: inorganic powder = 30: 70 to 80:20 (weight ratio).
発泡剤は、重曹(重炭酸ナトリウム)が使用される。重曹は、分解温度が低く、かつ安価なため、発泡剤として好適なものである。重曹の量は、熱可塑性樹脂と無機粉末の合計100重量部に対して1〜5重量部が好ましい。 As the foaming agent, sodium bicarbonate (sodium bicarbonate) is used. Baking soda is suitable as a foaming agent because it has a low decomposition temperature and is inexpensive. The amount of baking soda is preferably 1 to 5 parts by weight based on 100 parts by weight of the total of the thermoplastic resin and the inorganic powder.
発泡助剤は、発泡を良好に行わせるために添加される。発泡助剤としては、ポリ(メタ)アクリル酸(部分中和物)が必須である。ポリ(メタ)アクリル酸部分中和物は、非架橋型、架橋型の何れでもよく、また部分中和物であってもよい。ポリ(メタ)アクリル酸(部分中和物)の量は、熱可塑性樹脂と無機粉末の合計100重量部に対し、重曹が1〜5重量部。これに対し、ポリ(メタ)アクリル酸(部分中和物)が2〜25重量部が好ましい。ポリ(メタ)アクリル酸(部分中和物)の量が少ないと発泡セルが不均一になり、かつ、水中へ投入した時にpH10以上になり、逆に多いと水中へ投入した時に増粘され、共に微生物担持体として好ましくない。また、ポリ(メタ)アクリル酸(部分中和物)と共に他の発泡助剤を併用してもよい。ポリ(メタ)アクリル酸(部分中和物)と併用可能な発泡助剤として、例えば脂肪酸グリセリンを挙げることができる。 The foaming auxiliary agent is added in order to perform foaming well. As the foaming aid, poly (meth) acrylic acid (partially neutralized product) is essential. The partially neutralized poly (meth) acrylic acid may be either a non-crosslinked type or a crosslinked type, or may be a partially neutralized product. The amount of poly (meth) acrylic acid (partially neutralized product) is 1 to 5 parts by weight of baking soda with respect to 100 parts by weight of the total of the thermoplastic resin and the inorganic powder. On the other hand, the poly (meth) acrylic acid (partially neutralized product) is preferably 2 to 25 parts by weight. When the amount of poly (meth) acrylic acid (partially neutralized product) is small, the foamed cells become non-uniform, and when it is poured into water, the pH becomes 10 or more. Both are not preferred as a microorganism carrier. Further, other foaming aids may be used in combination with poly (meth) acrylic acid (partially neutralized product). Examples of the foaming aid that can be used in combination with poly (meth) acrylic acid (partially neutralized product) include fatty acid glycerin.
その他適宜添加される添加剤として多孔性鉱物が挙げられる。
多孔性鉱物は、吸水物質として添加され、パーライト、ゼオライト、バイコールガラス等が挙げられる。多孔性鉱物の量は、熱可塑性樹脂と無機粉末の合計100重量部に対して0〜50重量部が好ましい。
In addition, a porous mineral is mentioned as an additive added suitably.
The porous mineral is added as a water-absorbing substance, and examples thereof include pearlite, zeolite, and vycor glass. The amount of the porous mineral is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the total of the thermoplastic resin and the inorganic powder.
発泡体の製造方法は、前記樹脂組成物で説明した熱可塑性樹脂、無機粉末、発泡剤、発泡助剤、その他適宜添加される添加剤を含む原料を溶融混練して発泡成形することにより発泡体を製造する。発泡成形は、押出発泡成形に限らず、発泡射出成形等を用いることもできる。以下、押出発泡成形の例について説明する。
発泡体の製造は、前記熱可塑性樹脂、無機粉末、発泡剤、発泡助剤及び適宜の添加剤を前記の量で押出機に投入し、押出機内で溶融混練してストランド上に押出して発泡させることにより発泡体を形成し、その発泡体を水中冷却槽を通して冷却硬化させペレタイザーで切断してペレット状の発泡体とすることにより行う。
The foam is produced by melt-kneading and foam-molding the raw material containing the thermoplastic resin, inorganic powder, foaming agent, foaming aid, and other additives that are added as appropriate, as described in the resin composition. Manufacturing. Foam molding is not limited to extrusion foam molding, and foam injection molding or the like can also be used. Hereinafter, an example of extrusion foaming will be described.
In the production of the foam, the thermoplastic resin, inorganic powder, foaming agent, foaming aid and appropriate additives are introduced into the extruder in the above amounts, melt-kneaded in the extruder, extruded onto the strand, and foamed. This is performed by forming a foam, cooling and curing the foam through an underwater cooling tank, and cutting with a pelletizer to form a pellet-like foam.
前記ペレットの断面形状は、円形、楕円形、三角形・四角形・十字形、等にすることができる。この場合、断面形状を円形以外の上記形状とすることにより、ペレット状発泡体の表面積が増大し、発泡体を微生物担体とする場合、微生物の付着効率が高まる効果があり、微生物担体の処理効率が向上する。 The cross-sectional shape of the pellet can be circular, elliptical, triangular, quadrangular, cruciform, or the like. In this case, by setting the cross-sectional shape to the above-mentioned shape other than circular, the surface area of the pellet-shaped foam increases, and when the foam is used as a microbial carrier, there is an effect of increasing the adhesion efficiency of microorganisms, and the processing efficiency of the microbial carrier Will improve.
前記押出機は単軸、二軸、三軸以上の多軸のいずれでもよい。二軸、多軸は混練効果が高く、より好ましい。押出条件の例として押出機の温度を150〜200℃、吐出量を20kg/hとする例を挙げる。また、ペレット状に切断して得られる発泡体の寸法は、発泡体の用途に応じて適宜の寸法とされるが、微生物担体用としては、直径1〜5mm、長さ1〜10mm程度が好ましい。 The extruder may be uniaxial, biaxial, or triaxial or multiaxial. Biaxial and multiaxial are more preferable because of high kneading effect. As an example of extrusion conditions, an example in which the temperature of the extruder is 150 to 200 ° C. and the discharge rate is 20 kg / h is given. In addition, the dimensions of the foam obtained by cutting into pellets are appropriate dimensions according to the use of the foam, but for microbial carriers, a diameter of about 1 to 5 mm and a length of about 1 to 10 mm are preferable. .
前記の製造方法で得られた発泡体は、水中へ投入した場合にpHの上昇を抑えることができ、微生物の成育環境として好適なpH6〜8に近づけることができ、微生物担体として好適なものである。 The foam obtained by the above production method can suppress an increase in pH when introduced into water, can be brought close to pH 6 to 8 suitable as a growth environment of microorganisms, and is suitable as a microorganism carrier. is there.
以下の成分を表1の配合にして、押出成形機(品名:KTX30、神戸製鋼製)で溶融混練し、直径3mmのストランド状に押し出して発泡させ、ペレタイザーで長さ3mmで切断し、各実施例及び各比較例のペレット状発泡体を製造した。溶融混練条件はバレルおよびダイ温度180℃、スクリュー回転数400rpm、吐出量20kg/hである。 The following components were blended as shown in Table 1, melted and kneaded with an extruder (product name: KTX30, manufactured by Kobe Steel), extruded into a 3 mm diameter strand, foamed, and cut with a pelletizer at a length of 3 mm. The pellet-like foam of the example and each comparative example was manufactured. The melt-kneading conditions are a barrel and die temperature of 180 ° C., a screw rotation speed of 400 rpm, and a discharge rate of 20 kg / h.
・ポリエチレン:高密度ポリエチレン(HDPE)、東ソー製「ニポロンハード2500」
・炭酸カルシウム:丸尾カルシウム製「R重炭」
・硫酸バリウム:丸尾カルシウム製「白バライト鉱石粉砕品」
・リン酸カルシウム:松尾薬品産業製「リン酸一水素カルシウム(無水物)」
(※「リン酸カルシウム」、「亜」は、不要。)
・パーライト:三井金属鉱業製「ロカヘルプ439」
・重曹:キシダ化学製「一級炭酸水素ナトリウム」
・脂肪酸グリセリン:理研ビタミン製「s−100」
・クエン酸:磐田化学製「クエン酸(結晶)」
・ポリ(メタ)アクリル酸(部分中和物)(1):ポリアクリル酸部分中和物、中和度はCOOH/COONa=65/35(モル比)、昭和電工製[ビスコメートNP−800]
・ポリ(メタ)アクリル酸(部分中和物)(2):ポリアクリル酸部分中和物、中和度はCOOH/COONa=50/50(モル比)、昭和電工製[ビスコメートNP−700]
・ Polyethylene: High-density polyethylene (HDPE), Tosoh "Nipolon Hard 2500"
・ Calcium carbonate: “R heavy coal” made by Maruo calcium
・ Barium sulfate: "White barite ore pulverized product" made by Maruo calcium
・ Calcium phosphate: “Calcium monohydrogen phosphate (anhydride)” manufactured by Matsuo Pharmaceutical Co., Ltd.
(* "Calcium phosphate" and "A" are not required.)
・ Perlite: “Loca Help 439” manufactured by Mitsui Mining & Mining
・ Baking soda: “Primary sodium bicarbonate” manufactured by Kishida Chemical
・ Fatty acid glycerin: “s-100” manufactured by Riken Vitamin
・ Citric acid: "Citric acid (crystal)" manufactured by Iwata Chemical
・ Poly (meth) acrylic acid (partially neutralized product) (1): partially neutralized polyacrylic acid, degree of neutralization is COOH / COONa = 65/35 (molar ratio), Showa Denko [Viscomate NP-800]
・ Poly (meth) acrylic acid (partially neutralized product) (2): partially neutralized polyacrylic acid, degree of neutralization is COOH / COONa = 50/50 (molar ratio), Showa Denko [Viscomate NP-700]
各実施例及び各比較例の発泡体に対し、pH、発泡セルの均一性、沈降性について測定及び判定を行った。
pHの測定は、発泡体50gを蒸留水300mlに投入し、5分間マグネチックスターラ―750rpmで撹拌した後に蒸留水のpHを堀場製作所製「pH METER F−12」で測定した。pHの測定結果に対する判定は、一般的に水棲微生物の生育に適するpH値が6〜8であることから、測定結果がpH7.9以下の場合に「◎」(最良)、pH8.0〜8.9の場合に「〇」(良)、pH9.0以上の場合に「×」(不良)とした。
発泡セルの均一性の判定は、発泡体の断面状態を目視で観察し、セルが全体に均一に分布し、且つ海綿状の場合に「◎」(最良)、セルが全体に均一に分布しているが海綿状ではない場合に「〇」(良)、セルが不均一に分布あるいは発泡していない場合に「×」(不良)とした。
沈降性の判定は、発泡体100個を300mLの水へ投入してマグネチックスターラ―750rpmにより撹拌し、撹拌開始後30分の時点と、1時間後の時点において、沈降済みの発泡体の個数を数え、撹拌開始後30分以内に沈降した発泡体個数が発泡体全個数の90%以上の場合に「◎」(最良)、撹拌開始後1時間以内に沈降した発泡体個数が発泡体全個数の90%以上の場合に「〇」(良)、撹拌開始後1時間経過しても沈降した発泡体が発泡体全個数の89%以下の場合に[×](不良)とした。
The foams of the examples and comparative examples were measured and judged for pH, foam cell uniformity and sedimentation.
The pH was measured by adding 50 g of foam to 300 ml of distilled water, stirring for 5 minutes with a magnetic stirrer at 750 rpm, and then measuring the pH of the distilled water with “pH METER F-12” manufactured by Horiba. The determination for the measurement result of pH is generally 6 to 8 at a pH value suitable for the growth of aquatic microorganisms. Therefore, when the measurement result is pH 7.9 or less, “」 ”(best), pH 8.0 to 8 In the case of .9, “◯” (good), and in the case of pH 9.0 or higher, “×” (bad).
The uniformity of the foam cell is determined by visually observing the cross-sectional state of the foam, and when the cell is uniformly distributed throughout the cell, and when it is spongy, “◎” (best), the cell is evenly distributed throughout. However, when the cells were not spongy, “◯” (good), and when the cells were not unevenly distributed or foamed, “×” (bad).
The determination of sedimentation is carried out by adding 100 foams to 300 mL of water and stirring them with a magnetic stirrer at 750 rpm, and the number of foams that have settled at 30 minutes after the start of stirring and 1 hour later. When the number of foams settled within 30 minutes after the start of stirring is 90% or more of the total number of foams, “◎” (best), the number of foams settled within 1 hour after the start of stirring is the total number of foams When it was 90% or more of the number, “◯” (good), and when the foam that settled even after 1 hour from the start of stirring was 89% or less of the total number of foams, it was judged as “x” (bad).
実施例1〜8は、pHの判定、発泡体セルの判定及び沈降性の判定が何れも「◎」又は「〇」であり、微生物担体として好適な発泡体であった。 In Examples 1 to 8, the determination of pH, the determination of foam cells, and the determination of sedimentation were all “◎” or “◯”, and were suitable foams as microbial carriers.
一方、比較例1〜8は、実施例1〜8に対応した例であって、ポリ(メタ)アクリル酸(部分中和物)を使用しない例である。なお、比較例6では、ポリ(メタ)アクリル酸(部分中和物)に代えてクエン酸を使用した。ポリ(メタ)アクリル酸(部分中和物)およびクエン酸を使用しない比較例1〜5及び比較例7、8は、少なくともpHの判定が「×」であり、微生物担体として好ましくなかった。
また、ポリ(メタ)アクリル酸(部分中和物)に代えてクエン酸を使用した比較例6は、pHの判定では「◎」であったが、発泡セル均一性の判定及び沈降性の判定が何れも「×」であり、微生物担体として好ましくなかった。
On the other hand, Comparative Examples 1-8 are examples corresponding to Examples 1-8, and are examples which do not use poly (meth) acrylic acid (partially neutralized product). In Comparative Example 6, citric acid was used in place of poly (meth) acrylic acid (partially neutralized product). In Comparative Examples 1 to 5 and Comparative Examples 7 and 8 which do not use poly (meth) acrylic acid (partially neutralized product) and citric acid, at least the pH was judged as “x”, which was not preferable as a microorganism carrier.
Further, Comparative Example 6 using citric acid instead of poly (meth) acrylic acid (partially neutralized product) was “の” in the determination of pH, but the determination of foamed cell uniformity and the determination of sedimentation Are “x”, which is not preferable as a microorganism carrier.
比較例9〜12は、ポリ(メタ)アクリル酸(部分中和物)を含まない他の比較例であり、何れもpHの判定が「×」であり、微生物担体として好ましくなかった。 Comparative Examples 9 to 12 are other comparative examples that do not contain poly (meth) acrylic acid (partially neutralized product), and any of the pH determinations was “x”, which was not preferable as a microorganism carrier.
このように、本発明の樹脂組成物、および発泡体の製造方法によって得られる発泡体は、発泡セルの均一性が良好であり、かつ水に投入した場合にpHの上昇を抑えることができ、しかも沈降性が良好なため、微生物担体として好適なものである。なお、本発明によって得られる発泡体は、微生物担体に限られるものではなく、水に投入した場合にpHの上昇が好ましくない用途、例えば、漁礁、藻礁、防波壁等にも適するものである。 Thus, the foam obtained by the resin composition of the present invention and the method for producing a foam has good foam cell uniformity, and can suppress an increase in pH when poured into water, Moreover, since the sedimentation property is good, it is suitable as a microorganism carrier. The foam obtained by the present invention is not limited to a microbial carrier, and is suitable for applications in which the increase in pH is not preferable when it is put into water, for example, fishing reefs, algal reefs, wave barriers, etc. is there.
Claims (7)
前記発泡剤は重曹であり、
前記発泡助剤はポリ(メタ)アクリル酸(部分中和物)であることを特徴とする樹脂組成物。 A resin composition obtained by melt-kneading a raw material containing a thermoplastic resin, an inorganic powder, a foaming agent, and a foaming aid used for foam molding,
The blowing agent is baking soda,
The foaming aid is poly (meth) acrylic acid (partially neutralized product), a resin composition.
前記発泡剤に重曹を使用し、
前記発泡助剤にポリ(メタ)アクリル酸(部分中和物)を使用することを特徴とする発泡体の製造方法。 In the foam production method in which a raw material containing a thermoplastic resin, an inorganic powder, a foaming agent, and a foaming aid is melt-kneaded and foam-molded,
Use baking soda as the foaming agent,
A method for producing a foam, characterized in that poly (meth) acrylic acid (partially neutralized product) is used as the foaming aid.
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