JP2016017130A - Bacterium adhesion-suppressed resin - Google Patents
Bacterium adhesion-suppressed resin Download PDFInfo
- Publication number
- JP2016017130A JP2016017130A JP2014140278A JP2014140278A JP2016017130A JP 2016017130 A JP2016017130 A JP 2016017130A JP 2014140278 A JP2014140278 A JP 2014140278A JP 2014140278 A JP2014140278 A JP 2014140278A JP 2016017130 A JP2016017130 A JP 2016017130A
- Authority
- JP
- Japan
- Prior art keywords
- structural unit
- formula
- bacteria
- carbon atoms
- adhesion
- 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.)
- Pending
Links
Abstract
Description
本発明は、細菌付着抑制性樹脂に関し、詳しくは細菌が付着しにくい性質を有する樹脂に関する。 The present invention relates to a bacteria adhesion-inhibiting resin, and particularly relates to a resin having a property that bacteria do not easily adhere.
一般に、生活環境における細菌の増殖及び拡散を抑制することが、衛生的観点から求められている。特に医療・介護分野ではそれが顕著である。そのために、無機系、有機系の抗菌剤が広く用いられているが、抗菌剤の多くは高い毒性を持っているため、近年では毒性の低下を目的として、高分子型の抗菌剤が開発されている。 In general, it is required from a hygienic viewpoint to suppress the growth and spread of bacteria in the living environment. This is particularly true in the medical and nursing care fields. For this reason, inorganic and organic antibacterial agents are widely used, but since many antibacterial agents are highly toxic, in recent years, polymer antibacterial agents have been developed for the purpose of reducing toxicity. ing.
例えば特許文献１にはホスホニウム塩系ビニル単量体からなる重合体が優れた抗菌作用を有し、コンタクトレンズやアイケア製品に応用できることが記載されている。 For example, Patent Document 1 describes that a polymer composed of a phosphonium salt vinyl monomer has an excellent antibacterial action and can be applied to contact lenses and eye care products.
しかし、特許文献１に示される高分子型抗菌剤でも、従来の抗菌剤と同様に強い殺菌作用又は消毒作用によって抗菌性を示すため、毒性の低下は十分には達成されていない。 However, since the polymer antibacterial agent disclosed in Patent Document 1 exhibits antibacterial properties by a strong bactericidal action or disinfecting action as in the case of conventional antibacterial agents, reduction in toxicity has not been sufficiently achieved.
本発明は上記の点に鑑みてなされたものであり、強い殺菌作用及び消毒作用によらずに、細菌の増殖及び拡散の抑制に寄与することができる細菌付着抑制性樹脂を提供することを目的とする。 The present invention has been made in view of the above points, and an object thereof is to provide a bacterial adhesion-inhibiting resin that can contribute to the suppression of bacterial growth and diffusion without relying on a strong bactericidal and disinfecting action. And
本発明に係る細菌付着抑制性樹脂は、下記式（１）で表される第一構成単位と、下記式（２）で表される第二構成単位とのうち、少なくとも一方を含む。 The bacterial adhesion-inhibiting resin according to the present invention includes at least one of a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2).
式（１）中、Ｒ1はＨ又はメチル基であり、Ｒ3は炭素数１〜３のアルキレン基であり、Ｒ4及びＲ5の各々は独立にＨ又は炭素数１〜４のアルキル基であり、ＡはＯ又はＮＨである。 In formula (1), R 1 is H or a methyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, and each of R 4 and R 5 is independently H or an alkyl group having 1 to 4 carbon atoms. And A is O or NH.
式（２）中、Ｒ1はＨ又はメチル基であり、Ｒ7は炭素数１〜８の直鎖状または分岐鎖状のアルキレン基であり、Ｒ8はＨ又は炭素数１〜４のアルキル基であり、ＡはＯ又はＮＨである。 In Formula (2), R 1 is H or a methyl group, R 7 is a linear or branched alkylene group having 1 to 8 carbon atoms, and R 8 is H or an alkyl having 1 to 4 carbon atoms. And A is O or NH.
本発明に係る細菌付着抑制樹脂は、下記式（３）で表される第三構成単位、下記式（４）で表される第四構成単位及び下記式（５）で表される第五構成単位のうち、少なくとも一種の構成単位を更に含んでもよい。 The bacterial adhesion-inhibiting resin according to the present invention is a third constitutional unit represented by the following formula (3), a fourth constitutional unit represented by the following formula (4), and a fifth constitution represented by the following formula (5). You may further contain at least 1 type of structural unit among units.
式（３）中、Ｒ1はＨ又はメチル基であり、Ｒ3は炭素数１〜３のアルキレン基であり、Ｒ4及びＲ5の各々は独立にＨ又は炭素数１〜４のアルキル基であり、Ｒ6は炭素数１〜２のアルキレン基であり、ＡはＯ又はＮＨである。 In Formula (3), R 1 is H or a methyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, and each of R 4 and R 5 is independently H or an alkyl group having 1 to 4 carbon atoms. R 6 is an alkylene group having 1 to 2 carbon atoms, and A is O or NH.
式（４）中のＲ1はＨ又はメチル基、Ｒ2は炭素数２〜２２の範囲内の炭化水素基である。 In the formula (4), R 1 is H or a methyl group, and R 2 is a hydrocarbon group having 2 to 22 carbon atoms.
式（５）中のＲ1はＨ又はメチル基である。 R 1 in the formula (5) is H or a methyl group.
本発明に係る細菌付着抑制性樹脂では、第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位の合計に対する、第一構成単位及び第二構成単位の合計の百分比が２５モル％以上１００モル％未満の範囲内であってもよい。 In the bacterial adhesion inhibiting resin according to the present invention, the total of the first structural unit and the second structural unit with respect to the total of the first structural unit, the second structural unit, the third structural unit, the fourth structural unit and the fifth structural unit. May be within a range of 25 mol% or more and less than 100 mol%.
本発明に係る細菌付着抑制性樹脂は、サルモネラ属細菌の付着抑制作用を有することが好ましい。 The bacterial adhesion-inhibiting resin according to the present invention preferably has an adhesion-inhibiting action against Salmonella bacteria.
サルモネラ属細菌がSalmonella enteritidisであることも好ましい。 It is also preferred that the Salmonella bacterium is Salmonella enteritidis.
本発明に係る細菌付着抑制性樹脂は、細菌が非常に付着しにくいため、高い殺菌作用及び消毒作用によらずに、細菌の増殖及び拡散の抑制に寄与することができる。 Since the bacterial adhesion-inhibiting resin according to the present invention is very difficult to adhere to bacteria, it can contribute to the suppression of bacterial growth and diffusion regardless of the high bactericidal action and disinfecting action.
本実施形態に係る細菌付着抑制性樹脂は、第一構成単位と第二構成単位とのうち、少なくとも一方を含むことで、細菌が付着しにくい性質を有する。 The bacterial adhesion-inhibiting resin according to the present embodiment has a property that bacteria are difficult to adhere by including at least one of the first structural unit and the second structural unit.
第一構成単位は下記式（１）で表される。 The first structural unit is represented by the following formula (1).
式（１）中、Ｒ1はＨ又はメチル基であり、Ｒ3は炭素数１〜３のアルキレン基であり、Ｒ4及びＲ5の各々は独立にＨ又は炭素数１〜４のアルキル基であり、ＡはＯ又はＮＨである。細菌付着抑制性樹脂が第一構成単位を含むと、細菌付着抑制性樹脂に、部分的に正電荷をもつ構造が導入される。この正電荷をもつ構造によって、細菌付着抑制性樹脂に近づいた細菌の、細胞外高分子化合物を形成する活動を、一時的に低下させることができる。そうすると、細菌の細菌付着抑制性樹脂への付着が抑制される。 In formula (1), R 1 is H or a methyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, and each of R 4 and R 5 is independently H or an alkyl group having 1 to 4 carbon atoms. And A is O or NH. When the bacterial adhesion-inhibiting resin contains the first constituent unit, a structure having a partial positive charge is introduced into the bacterial adhesion-inhibiting resin. This positively charged structure can temporarily reduce the activity of bacteria that have approached the bacterial adhesion-inhibiting resin to form extracellular polymer compounds. If it does so, adhesion to bacteria adhesion inhibitory resin will be controlled.
第二構成単位は下記式（２）で表される。 The second structural unit is represented by the following formula (2).
式（２）中、Ｒ1はＨ又はメチル基であり、Ｒ7は炭素数１〜８の直鎖状または分岐鎖状のアルキレン基であり、Ｒ8はＨ又は炭素数１〜４のアルキル基であり、ＡはＯ又はＮＨである。細菌付着抑制性樹脂が第二構成単位を含むと、細菌付着抑制性樹脂に非イオン性の親水性構造が導入される。この構造によって、細菌付着抑制性樹脂にSalmonella enteritidis等の表面が疎水性である細菌の接近することが妨げられるため、細菌付着抑制性樹脂への細菌の付着が抑制される。 In Formula (2), R 1 is H or a methyl group, R 7 is a linear or branched alkylene group having 1 to 8 carbon atoms, and R 8 is H or an alkyl having 1 to 4 carbon atoms. And A is O or NH. When the bacterial adhesion-inhibiting resin contains the second structural unit, a nonionic hydrophilic structure is introduced into the bacterial adhesion-inhibiting resin. This structure prevents bacteria having a hydrophobic surface, such as Salmonella enteritidis, from approaching the bacterial adhesion-inhibiting resin, so that bacterial adhesion to the bacterial adhesion-inhibiting resin is suppressed.
細菌付着抑制性樹脂は、第三構成単位、第四構成単位及び第五構成単位のうち、少なくとも一種の構成単位を更に含んでもよい。 The bacterial adhesion-inhibiting resin may further include at least one structural unit among the third structural unit, the fourth structural unit, and the fifth structural unit.
第三構成単位は下記式（３）で表される。 The third structural unit is represented by the following formula (3).
式（３）中、Ｒ1はＨ又はメチル基であり、Ｒ3は炭素数１〜３のアルキレン基であり、Ｒ4及びＲ5の各々は独立にＨ又は炭素数１〜４のアルキル基であり、Ｒ6は炭素数１〜２のアルキレン基であり、ＡはＯ又はＮＨである。細菌付着抑制性樹脂が第三構成単位を含むと、細菌付着抑制性樹脂に正電荷と負電荷をもつ構造が導入される。この構造によって、細菌付着抑制性樹脂と細菌の表面に存在する陰イオン性の構造との間に静電的反発力を生じさせて細菌付着抑制性樹脂への細菌の付着を抑制する作用と、細菌付着抑制性樹脂に近づいた細菌の細胞外高分子化合物を形成する活動を一時的に低下させる作用とを、両方得ることができる。これにより細菌付着抑制性樹脂への細菌の付着が抑制される。 In Formula (3), R 1 is H or a methyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, and each of R 4 and R 5 is independently H or an alkyl group having 1 to 4 carbon atoms. R 6 is an alkylene group having 1 to 2 carbon atoms, and A is O or NH. When the bacterial adhesion-inhibiting resin contains the third structural unit, a structure having a positive charge and a negative charge is introduced into the bacterial adhesion-inhibiting resin. With this structure, an action of inhibiting the adhesion of bacteria to the bacterial adhesion-inhibiting resin by generating an electrostatic repulsive force between the bacterial adhesion-inhibiting resin and the anionic structure present on the surface of the bacteria, It is possible to obtain both the action of temporarily reducing the activity of forming an extracellular polymer compound of bacteria approaching the bacterial adhesion-inhibiting resin. Thereby, the adhesion of bacteria to the bacteria adhesion-inhibiting resin is suppressed.
第四構成単位は、下記式（４）で表される。 The fourth structural unit is represented by the following formula (4).
式（４）中のＲ1はＨ又はメチル基、Ｒ2は炭素数２〜２２の範囲内の炭化水素基である。Ｒ2は、直鎖状であってよく、分枝鎖状であってもよく、環状であってもよい。 In the formula (4), R 1 is H or a methyl group, and R 2 is a hydrocarbon group having 2 to 22 carbon atoms. R 2 may be linear, branched, or cyclic.
細菌付着抑制性樹脂が第四構成単位を含むと、細菌付着抑制性樹脂の側鎖同士の凝集が起こりやすくなり、細菌付着抑制性樹脂から形成される被膜又は成形体の内側に第四構成単位が偏在しやすくなる。これによって、細菌付着抑制性樹脂中の親水性の構成単位が、成形体又は被膜の表面に配向しやすくなり、成形体又は被膜の表面に親水性が付与される。このため、被膜又は成形体への、表面に疎水性構造を備える細菌の接近が妨げられる。式（４）中のＲ2の炭素数が８〜２２の範囲内であれば、特に好ましい。この範囲であれば、充分な疎水性相互作用を生じさせることができるとともに、細菌付着抑制性樹脂に柔軟性を持たせることが可能となり、細菌付着抑制性樹脂の成形性及び被覆性が向上する。 When the bacterial adhesion-inhibiting resin contains a fourth structural unit, the side chains of the bacterial adhesion-inhibiting resin are likely to aggregate together, and the fourth structural unit is formed inside the coating or molded body formed from the bacterial adhesion-inhibiting resin. Tends to be unevenly distributed. Thereby, the hydrophilic structural unit in the bacterial adhesion-inhibiting resin is easily oriented on the surface of the molded body or the film, and hydrophilicity is imparted to the surface of the molded body or the film. For this reason, the approach of bacteria with a hydrophobic structure on the surface to the coating or molded body is hindered. It is particularly preferred if R 2 in formula (4) has a carbon number in the range of 8-22. Within this range, a sufficient hydrophobic interaction can be generated, and the bacterial adhesion-inhibiting resin can be made flexible, thereby improving the moldability and covering properties of the bacterial adhesion-inhibiting resin. .
第五構成単位は、下記式（５）で表される。 The fifth structural unit is represented by the following formula (5).
式（５）中のＲ1はＨ又はメチル基である。 R 1 in the formula (5) is H or a methyl group.
細菌付着抑制性樹脂が第五構成単位を含むと、細菌付着抑制性樹脂に、部分的に負電荷をもつ構造が導入される。そのため、細菌付着抑制性樹脂における負電荷をもつ構造と細菌の表面に存在する陰イオン性の構造との間に静電的反発力を生じさせて、細菌付着抑制性樹脂への細菌の付着を抑制することができる。 When the bacterial adhesion-inhibiting resin contains the fifth structural unit, a structure having a partial negative charge is introduced into the bacterial adhesion-inhibiting resin. For this reason, an electrostatic repulsive force is generated between the negatively charged structure of the bacterial adhesion-inhibiting resin and the anionic structure existing on the surface of the bacteria, thereby preventing the bacterial adhesion to the bacterial adhesion-inhibiting resin. Can be suppressed.
細菌付着抑制性樹脂は、特に第一構成単位と第二構成単位の少なくとも一方と、第三構成単位、第四構成単位及び第五構成単位のうちのうち少なくとも一種とを含むことが好ましい。この場合、細菌付着抑制性樹脂に細菌が特に付着しにくくなる。 In particular, the bacterial adhesion-inhibiting resin preferably includes at least one of the first structural unit and the second structural unit, and at least one of the third structural unit, the fourth structural unit, and the fifth structural unit. In this case, bacteria are particularly difficult to adhere to the bacterial adhesion-inhibiting resin.
細菌付着抑制性樹脂中の、第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位の合計に対する、第一構成単位及び第二構成単位の合計の百分比は、２５モル％以上１００モル％未満の範囲内にあることが好ましい。この百分比が２５モル％以上であることで、細菌付着抑制性樹脂への細菌の付着の抑制効果を充分に得ることができる。第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位の合計に対する、第一構成単位及び第二構成単位の合計の百分比は、特に５０モル％以上１００モル％未満の範囲内であることが好ましい。この場合、細菌付着抑制性樹脂に細菌が特に付着しにくくなる。 The percentage of the total of the first structural unit and the second structural unit to the total of the first structural unit, the second structural unit, the third structural unit, the fourth structural unit, and the fifth structural unit in the bacterial adhesion inhibitory resin is , Preferably in the range of 25 mol% or more and less than 100 mol%. When this percentage is 25 mol% or more, the effect of suppressing the adhesion of bacteria to the bacteria adhesion-inhibiting resin can be sufficiently obtained. The percentage of the total of the first structural unit and the second structural unit to the total of the first structural unit, the second structural unit, the third structural unit, the fourth structural unit, and the fifth structural unit is particularly 50 mol% or more and 100 mol. It is preferable to be within the range of less than%. In this case, bacteria are particularly difficult to adhere to the bacterial adhesion-inhibiting resin.
細菌付着抑制性樹脂中の全構成単位に対する第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位の合計の百分比は、４０〜１００モル％の範囲内であることが好ましく、８０〜１００モル％の範囲内であれば更に好ましい。 The total percentage of the first structural unit, the second structural unit, the third structural unit, the fourth structural unit and the fifth structural unit with respect to all the structural units in the bacterial adhesion-inhibiting resin is within the range of 40 to 100 mol%. It is preferable that it is in the range of 80 to 100 mol%, and more preferable.
細菌付着抑制性樹脂は、例えばエチレン性不飽和単量体を重合させることで得られる。 The bacterial adhesion-inhibiting resin can be obtained, for example, by polymerizing an ethylenically unsaturated monomer.
細菌付着抑制性樹脂が第一構成単位を含む場合は、エチレン性不飽和単量体は下記（１ａ）に示す第一単量体を含むことが好ましい。細菌付着抑制性樹脂が第二構成単位を含む場合は、エチレン性不飽和単量体は下記（２ａ）に示す第二単量体を含むことが好ましい。細菌付着抑制性樹脂が第三構成単位を含む場合は、エチレン性不飽和単量体は下記（３ａ）に示す第三単量体を含むことが好ましい。細菌付着抑制性樹脂が第四構成単位を含む場合は、エチレン性不飽和単量体は下記式（４ａ）に示す第四単量体を含むことが好ましい。細菌付着抑制性樹脂が第五構成単位を含む場合は、エチレン性不飽和単量体は下記式（５ａ）に示す第五単量体を含むことが好ましい。 When the bacterial adhesion-inhibiting resin contains the first structural unit, the ethylenically unsaturated monomer preferably contains the first monomer shown in the following (1a). When the bacterial adhesion-inhibiting resin contains the second structural unit, the ethylenically unsaturated monomer preferably contains the second monomer shown in the following (2a). When the bacterial adhesion-inhibiting resin contains a third structural unit, the ethylenically unsaturated monomer preferably contains the third monomer shown in the following (3a). When the bacterial adhesion-inhibiting resin contains a fourth structural unit, the ethylenically unsaturated monomer preferably contains a fourth monomer represented by the following formula (4a). When the bacterial adhesion-inhibiting resin contains a fifth structural unit, the ethylenically unsaturated monomer preferably contains a fifth monomer represented by the following formula (5a).
細菌付着抑制性樹脂が第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位以外の構成単位を備える場合、エチレン性不飽和単量体は、第一単量体、第二単量体、第三単量体、第四単量体及び第五単量体以外の単量体（以下、第六単量体という）を含有してもよい。第六単量体は、各種のアニオン性不飽和単量体、カチオン性不飽和単量体、ノニオン性不飽和単量体等を含有することができる。 When the bacterial adhesion-inhibiting resin comprises a constituent unit other than the first constituent unit, the second constituent unit, the third constituent unit, the fourth constituent unit, and the fifth constituent unit, the ethylenically unsaturated monomer You may contain monomers (henceforth a 6th monomer) other than a monomer, a 2nd monomer, a 3rd monomer, a 4th monomer, and a 5th monomer. The sixth monomer can contain various anionic unsaturated monomers, cationic unsaturated monomers, nonionic unsaturated monomers, and the like.
細菌付着抑制性樹脂に式（３）に示す第三構成単位を含ませるために式（３ａ）に示す第三単量体が使用される場合は、まず式（１ａ）に示す第一単量体を用意し、この式（１ａ）に示す第一単量体の全部を両性化することで、式（３ａ）に示す第三単量体を得ることができる。また、細菌付着抑制性樹脂に式（１）に示す第一構成単位と式（３）に示す第三構成単位を含ませるために式（１ａ）に示す第一単量体と式（３ａ）に示す第三単量体とが使用される場合は、まず式（１ａ）に示す第一単量体を用意し、この第一単量体の一部を両性化することで、式（１ａ）に示す第一単量体と式（３ａ）に示す第三単量体との混合物を得ることができる。両性化は適宜の手法でなされる。例えば式（１ａ）に示す第一単量体を含む親水性溶媒溶液を攪拌しながら、この溶液に両性化剤を含む液（水溶液、親水性溶媒溶液、懸濁液等）を滴下し、続いてこの溶液を７０〜９５℃で２〜１０時間加熱することで、式（１ａ）に示す第一単量体の一部又は全部を両性化することができる。両性化剤として、Ｘ−Ｒ6−ＣＯＯＨ（Ｘはハロゲン原子）で示される化合物、この化合物のアルカリ金属塩等が挙げられる。アルカリ金属塩が使用される場合、両性化により副次的に生成する塩は必要に応じて濾過、イオン交換、電気透析等の適宜の手法で除去される。 When the third monomer represented by the formula (3a) is used to include the third structural unit represented by the formula (3) in the bacterial adhesion-inhibiting resin, first, the first monomer represented by the formula (1a) is used. A third monomer represented by the formula (3a) can be obtained by preparing a body and amphotericizing all the first monomers represented by the formula (1a). Further, in order to include the first structural unit represented by the formula (1) and the third structural unit represented by the formula (3) in the bacterial adhesion-inhibiting resin, the first monomer represented by the formula (1a) and the formula (3a) When the third monomer shown in FIG. 1 is used, the first monomer shown in the formula (1a) is first prepared, and a part of the first monomer is amphotericized to obtain the formula (1a). ) And a third monomer represented by the formula (3a) can be obtained. Amphotericization is performed by an appropriate method. For example, while stirring a hydrophilic solvent solution containing the first monomer represented by the formula (1a), a solution containing an amphoteric agent (aqueous solution, hydrophilic solvent solution, suspension, etc.) is dropped into this solution, followed by By heating this solution at 70 to 95 ° C. for 2 to 10 hours, a part or all of the first monomer represented by the formula (1a) can be amphotericized. Examples of the amphoteric agent include a compound represented by X—R 6 —COOH (X is a halogen atom), an alkali metal salt of this compound, and the like. When an alkali metal salt is used, a salt generated as a result of amphotericization is removed by an appropriate method such as filtration, ion exchange, or electrodialysis as necessary.
エチレン性不飽和単量体の重合方法は特に制限されず、公知の種々の方法が採用され得る。特にエチレン性不飽和単量体を親水性溶媒中又は水と親水性溶媒とを含む混合溶媒中でラジカル重合させることが好ましい。重合法としては、例えば溶液重合法、乳化重合法等が採用され得る。細菌付着抑制性樹脂は、ブロック共重合体であってもグラフト共重合体であってもよい。 The polymerization method of the ethylenically unsaturated monomer is not particularly limited, and various known methods can be employed. In particular, it is preferable to radically polymerize an ethylenically unsaturated monomer in a hydrophilic solvent or a mixed solvent containing water and a hydrophilic solvent. As the polymerization method, for example, a solution polymerization method, an emulsion polymerization method and the like can be employed. The bacterial adhesion-inhibiting resin may be a block copolymer or a graft copolymer.
親水性溶媒の具体例としては、メタノール、エタノール等の低級アルコール；アセトン等の低級ケトン；等が挙げられる。これらの溶媒のうち一種のみが用いられても、二種以上が併用されてもよい。 Specific examples of the hydrophilic solvent include lower alcohols such as methanol and ethanol; lower ketones such as acetone; and the like. Of these solvents, only one kind may be used, or two or more kinds may be used in combination.
エチレン性不飽和単量体の重合にあたって、重合開始剤が使用されることも好ましい。重合開始剤としては特に制限されないが、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチルアミジン）等のアゾ化合物；過酸化ベンゾイル、過酸化ラウロイル等の有機過酸化物；過硫酸カリウム；過硫酸アンモニウム；過酸化水素水；等が挙げられる。 In the polymerization of the ethylenically unsaturated monomer, it is also preferable to use a polymerization initiator. The polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Azo compounds such as dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine); benzoyl peroxide, lauroyl peroxide Organic peroxides such as potassium persulfate; ammonium persulfate; hydrogen peroxide solution;
エチレン性不飽和単量体を重合させる際の反応温度はエチレン性不飽和単量体の組成、重合開始剤の種類、溶媒の種類などに依存するが、２０〜２００℃の範囲内が好ましい。反応時間はエチレン性不飽和単量体の組成、重合開始剤の種類、溶媒の種類などに依存するが、２〜２４時間の範囲内であることが好ましい。 The reaction temperature for polymerizing the ethylenically unsaturated monomer depends on the composition of the ethylenically unsaturated monomer, the type of polymerization initiator, the type of solvent, etc., but is preferably in the range of 20 to 200 ° C. The reaction time depends on the composition of the ethylenically unsaturated monomer, the type of polymerization initiator, the type of solvent, etc., but is preferably in the range of 2 to 24 hours.
式（１ａ）に示す第一単量体を含有するエチレン性不飽和単量体を重合することで式（１）に示す第一単位構造を含む中間体を合成し、この中間体中の第一単位構造の全部を両性化することで、式（３）に示す第三単位構造を含む細菌付着抑制性樹脂を得てもよい。中間体中の式（１）に示す第一単位構造の一部を両性化することで、式（１）に示す第一単位構造及び式（３）に示す第三単位構造を含む細菌付着抑制性樹脂を得てもよい。両性化は適宜の手法でなされる。例えば中間体を含む親水性溶媒溶液を攪拌しながら、この溶液に両性化剤を含む液（水溶液、親水性溶媒溶液、懸濁液等）を滴下し、続いてこの溶液を７０〜９５℃で２〜１０時間加熱することで、式（１）に示す第一単位構造の全部又は一部を両性化することができる。 By polymerizing an ethylenically unsaturated monomer containing the first monomer represented by the formula (1a), an intermediate containing the first unit structure represented by the formula (1) was synthesized. A bacterial adhesion-inhibiting resin containing the third unit structure represented by formula (3) may be obtained by amphotericizing the entire unit structure. Bacterial attachment inhibition including the first unit structure shown in Formula (1) and the third unit structure shown in Formula (3) by amphotericizing a part of the first unit structure shown in Formula (1) in the intermediate May be obtained. Amphotericization is performed by an appropriate method. For example, while stirring a hydrophilic solvent solution containing an intermediate, a solution containing an amphoteric agent (aqueous solution, hydrophilic solvent solution, suspension, etc.) is dropped into this solution, and then this solution is added at 70 to 95 ° C. By heating for 2 to 10 hours, all or part of the first unit structure represented by the formula (1) can be amphoteric.
細菌付着抑制性樹脂の重量平均分子量は、ゲル浸透クロマトグラフィーの測定によるポリスチレン換算の重量平均分子量として２０００〜７００００の範囲内であることが好ましい。この場合、細菌付着抑制性樹脂中の構成単位の構造に起因する細菌の付着を抑制する効果が充分に得られる。また、各種部材上に細菌付着抑制性樹脂製の被膜を形成する場合、成形性及び被膜の部材への被覆性に優れると同時に、被膜の充分な耐水性を保持することもできる。 The weight average molecular weight of the bacterial adhesion-inhibiting resin is preferably in the range of 2000 to 70000 as the weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography. In this case, the effect of suppressing the adhesion of bacteria due to the structure of the structural unit in the bacteria adhesion-inhibiting resin is sufficiently obtained. In addition, when a film made of a resin adhesion-inhibiting resin is formed on various members, the moldability and the coating property of the film on the member are excellent, and at the same time, sufficient water resistance of the film can be maintained.
本実施形態に係る細菌付着抑制性樹脂は、細菌が付着しにくい性質を有し、特にSalmonella enteritidis等のサルモネラ属細菌が付着しにくい性質を有する。このため、細菌付着抑制性樹脂で被覆された部材、及び細菌付着抑制性樹脂の成形体からなる部材には、細菌が付着しにくい。また、細菌が部材に付着しにくいということは、細菌が部材に付着しても部材から細菌を除去しやすいということでもある。このため、細菌付着抑制性樹脂で被覆された部材、及び細菌付着抑制性樹脂の成形体からなる部材に細菌が付着したとしても、拭き掃除などで部材から細菌を容易に除去することができる。 The bacteria adhesion-inhibiting resin according to the present embodiment has a property that bacteria are difficult to adhere, and in particular, a property that Salmonella bacteria such as Salmonella enteritidis are difficult to adhere. For this reason, bacteria do not easily adhere to a member coated with a bacteria adhesion-inhibiting resin and a member made of a molded article of the bacteria adhesion-inhibiting resin. In addition, the fact that bacteria hardly adhere to the member also means that even if the bacteria adhere to the member, it is easy to remove the bacteria from the member. For this reason, even if bacteria adhere to the member coated with the bacteria adhesion-inhibiting resin and the member made of the molded article of the bacteria adhesion-inhibiting resin, the bacteria can be easily removed from the member by wiping or the like.
細菌付着抑制性樹脂で被覆された部材、及び細菌付着抑制性樹脂の成形体からなる部材は、不特定多数の人の手に触れる機会が多い製品、例えば手すりに適用されることが好ましい。この場合、病原菌が付着している人の手が製品に触れても、製品に病原菌が付着しにくく、付着したとしても拭き掃除などで容易に除去される。そのため製品に別の人の手が触れても、この人の手に病原菌が付着しにくい。すなわち、手すりなどの製品を介して細菌が人から人へと拡散することが抑制される。そのため、生活環境における細菌の増殖及び拡散を抑制することができる。 It is preferable that the member coated with the bacterial adhesion-inhibiting resin and the member made of the molded article of the bacterial adhesion-inhibiting resin are applied to products that are frequently touched by an unspecified number of people, such as handrails. In this case, even if the hand of a person to whom the pathogen is attached touches the product, the pathogen is not easily attached to the product, and even if it is attached, it is easily removed by wiping and cleaning. For this reason, even if another person's hand touches the product, pathogens do not easily adhere to this person's hand. That is, the spread of bacteria from person to person through products such as handrails is suppressed. Therefore, the growth and spread of bacteria in the living environment can be suppressed.
勿論、細菌付着抑制性樹脂で被覆された部材、及び細菌付着抑制性樹脂の成形体からなる部材は、手すりに限らず、種々の製品に適用可能である。 Of course, the member covered with the bacteria adhesion-inhibiting resin and the member made of the molded article of the bacteria adhesion-inhibiting resin are not limited to the handrails and can be applied to various products.
また、従来の抗菌剤のように殺菌作用又は消毒作用を利用するのではなく、細菌が付着しにくい性質を利用するため、細菌の増殖及び拡散を抑制するために本実施形態に係る細菌付着抑制性樹脂を利用しても、人体に害がおよびにくい。 In addition, in order to suppress the growth and spread of bacteria in order to utilize the property that bacteria do not adhere easily, rather than using bactericidal action or disinfecting action as in the case of conventional antibacterial agents, bacterial adhesion suppression according to this embodiment Even if the resin is used, the human body is hardly damaged.
以下、本発明の具体的な実施例を示す。但し、本発明はこの実施例に制限されず、種々の設計変更が可能である。 Specific examples of the present invention will be described below. However, the present invention is not limited to this embodiment, and various design changes are possible.
［樹脂の合成及び樹脂被覆シートの作製］
還流冷却器、温度計、窒素ガス導入管及び撹拌機が取り付けられた容量１リットルの四つ口フラスコに、表１に示すエチレン性不飽和単量体１００質量部とイソプロパノール１８５質量部を仕込むことで溶液を調製した。この溶液を、窒素気流下、昇温した。約８３℃で還流状態となった時点で、溶液に２，２’−アゾビスイソブチロニトリル０．８質量部を添加し、４時間還流状態を維持することで重合反応を進行させた。次いで、溶液から溶媒を留去した後、再度イソプロパノールを加えることでこの溶液の溶媒含有量を調整した。これにより、固形分濃度４０質量％の樹脂溶液を得た。
[Synthesis of resin and preparation of resin-coated sheet]
Into a 1-liter four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube and stirrer is charged 100 parts by mass of the ethylenically unsaturated monomer and 185 parts by mass of isopropanol shown in Table 1. A solution was prepared. The solution was heated under a nitrogen stream. When the reflux state was reached at about 83 ° C., 0.8 part by mass of 2,2′-azobisisobutyronitrile was added to the solution, and the polymerization state was allowed to proceed by maintaining the reflux state for 4 hours. Next, after the solvent was distilled off from the solution, the solvent content of this solution was adjusted by adding isopropanol again. Thereby, a resin solution having a solid concentration of 40% by mass was obtained.
表１中のエチレン性不飽和単量体の組成はモル比（モル％）で示した。 The composition of the ethylenically unsaturated monomer in Table 1 is shown in molar ratio (mol%).
尚、表１中のエチレン性不飽和単量体の詳細は次の通りである。
ＤＭＭＡ：メタクリル酸２−（ジメチルアミノ）エチル（CAS No.2867-47-2）。
ＨＥＡ：アクリル酸２−ヒドロキシエチル（CAS No.818-61-1）。
ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル（CAS No. 868-77-9）。
ＨＰＭＡ：メタクリル酸２−ヒドロキシプロピル（CAS No. 27813-02-1）。
ＭＥＢ：メタクリロイルオキシエチルジメチルカルボキシベタイン（CAS No.62723-61-9）
ＢＭＡ：メタクリル酸ｎ−ブチル（CAS No. 97-88-1）。
ＥＨＭＡ：メタクリル酸２−エチルヘキシル（CAS No.688-84-6）。
ＳＭＡ：メタクリル酸ステアリル（CAS No.32360-05-7）。
ＭＡＡ：メタクリル酸（CAS No.79-41-4）。
The details of the ethylenically unsaturated monomer in Table 1 are as follows.
DMMA: 2- (dimethylamino) ethyl methacrylate (CAS No. 2867-47-2).
HEA: 2-hydroxyethyl acrylate (CAS No. 818-61-1).
HEMA: 2-hydroxyethyl methacrylate (CAS No. 868-77-9).
HPMA: 2-hydroxypropyl methacrylate (CAS No. 27813-02-1).
MEB: Methacryloyloxyethyldimethylcarboxybetaine (CAS No.62723-61-9)
BMA: n-butyl methacrylate (CAS No. 97-88-1).
EHMA: 2-ethylhexyl methacrylate (CAS No.688-84-6).
SMA: stearyl methacrylate (CAS No. 32360-05-7).
MAA: Methacrylic acid (CAS No. 79-41-4).
得られた樹脂溶液を、アプリケーターを用いてＰＥＴフィルム（三菱樹脂株式会社製、品名ダイアホイルＴ１００−７５）の片面上に塗布することで、厚み１００μｍの塗膜を形成し、この塗膜を一晩放置して自然乾燥させた。次いで、ＰＥＴフィルムのもう一方の面上に樹脂溶液を塗布することで、厚み１００μｍの塗膜を形成し、この塗膜も一晩放置して自然乾燥させた。次に、これらの塗膜を７０℃の熱風で３時間加熱した。これにより、ＰＥＴフィルムの両面上に、それぞれ樹脂製の被膜を形成した。これにより、樹脂被覆シートを得た。各被膜の厚みを厚み測定機ＭＧ−５００Ａで測定したところ、平均２５μｍであった。尚、比較例１ではＰＥＴフィルムに被膜を形成しなかった。 By applying the obtained resin solution on one side of a PET film (product name: Diafoil T100-75, manufactured by Mitsubishi Plastics Co., Ltd.) using an applicator, a coating film having a thickness of 100 μm is formed. It was left to stand overnight and air dried. Subsequently, the resin solution was applied on the other surface of the PET film to form a coating film having a thickness of 100 μm, and this coating film was also allowed to stand overnight to be naturally dried. Next, these coating films were heated with hot air at 70 ° C. for 3 hours. Thereby, the resin-made films were formed on both surfaces of the PET film. Thereby, a resin-coated sheet was obtained. When the thickness of each coating film was measured with a thickness measuring machine MG-500A, it was an average of 25 μm. In Comparative Example 1, no film was formed on the PET film.
［細菌の付着量の評価］
樹脂被覆シートから１ｃｍ×１ｃｍの寸法の試験片を切り出した。対数増殖期の細菌として、Salmonella enteritidis CL#15-1の細菌株を用意した。この細菌をＬＢ培地中に懸濁してから、試験片とともに試験管に分注し、試験管内で細菌を４℃で４時間培養した。次いで試験片をリン酸緩衝生理食塩水（ＰＢＳ）で洗浄した後、０．１質量％のＴｒｉｔｏｎ Ｘ−１００を含むＰＢＳで洗浄することで、試験片に付着した細菌を除去した。洗浄に使用した後のＴｒｉｔｏｎ Ｘ−１００を含むＰＢＳを回収し、これをＬＢ寒天培地に塗布してコロニーを形成させ、生菌数を計測した。この結果から、試験片における細菌の付着量を評価した。
[Evaluation of bacterial adhesion]
A test piece having a size of 1 cm × 1 cm was cut out from the resin-coated sheet. A bacterial strain of Salmonella enteritidis CL # 15-1 was prepared as a logarithmic growth bacterium. The bacteria were suspended in LB medium, dispensed into a test tube together with a test piece, and the bacteria were cultured at 4 ° C. for 4 hours in the test tube. Next, the test piece was washed with phosphate buffered saline (PBS), and then washed with PBS containing 0.1% by mass of Triton X-100 to remove bacteria attached to the test piece. PBS containing Triton X-100 after being used for washing was collected, applied to LB agar medium to form colonies, and the number of viable bacteria was counted. From this result, the amount of bacteria attached to the test piece was evaluated.
結果を図１及び図２に示す。尚、図１及び図２のグラフの縦軸は、比較例１における細菌の付着量を１とみなした場合の細菌の付着量の相対値である。 The results are shown in FIGS. The vertical axis of the graphs of FIGS. 1 and 2 is a relative value of the amount of bacteria attached when the amount of bacteria attached in Comparative Example 1 is regarded as 1.
図１及び図２に示すように、実施例１〜１０の樹脂被覆シートは、被膜を備えないＰＥＴフィルム（比較例１）並びにＢＭＡのみから形成された被膜を備える比較例２と比べて、細菌の付着量が少ないことがわかった。 As shown in FIGS. 1 and 2, the resin-coated sheets of Examples 1 to 10 are bacteria as compared to PET film (Comparative Example 1) that does not have a coating and Comparative Example 2 that has a coating formed only from BMA. It was found that the adhesion amount of was small.
このうち、第二単量体のみを用いた実施例１及び２、第一単量体のみを用いた実施例３、並びに第一構成単位、第二構成単位、第三構成単位、第四構成単位及び第五構成単位の合計に対する、第一構成単位及び第二構成単位の合計の百分比が２５モル％以上１００モル％未満の範囲内にある実施例４〜６では、細菌の付着量が特に少なかった。 Among these, Examples 1 and 2 using only the second monomer, Example 3 using only the first monomer, and the first constitutional unit, the second constitutional unit, the third constitutional unit, the fourth constitution In Examples 4 to 6 in which the percentage of the total of the first structural unit and the second structural unit with respect to the total of the unit and the fifth structural unit is in the range of 25 mol% or more and less than 100 mol%, the bacterial adhesion amount is particularly There were few.
［培養液中の細菌の増殖量の評価］
樹脂被覆シートから１ｃｍ×１ｃｍの寸法の試験片を切り出した。対数増殖期の細菌として、Salmonella enteritidis CL#15-1の細菌株を用意した。この細菌をＬＢ培地中に懸濁してから、試験片とともに試験管に分注し、試験管内で細菌を３７℃で４時間培養した。次いで、試験片を取り出したそれぞれの培養液を、細菌量の指標として波長５５０ｎｍの吸光度を測定した。
[Evaluation of the amount of bacterial growth in the culture medium]
A test piece having a size of 1 cm × 1 cm was cut out from the resin-coated sheet. A bacterial strain of Salmonella enteritidis CL # 15-1 was prepared as a logarithmic growth bacterium. The bacteria were suspended in LB medium, dispensed into a test tube together with a test piece, and the bacteria were cultured at 37 ° C. for 4 hours in the test tube. Next, the absorbance at a wavelength of 550 nm was measured for each culture solution from which the test piece was taken out as an indicator of the amount of bacteria.
殺菌効果を示さないＰＥＴフィルム（比較例１）とともに分注した培養液の吸光度と比べて、いずれの実施例の樹脂被覆シートとともに分注した培養液の吸光度は同等であった。このことから、いずれの実施例の樹脂被覆シートもＰＥＴフィルム（比較例１）と同様に、殺菌作用や消毒作用を示さないことがわかった。 Compared to the absorbance of the culture solution dispensed with the PET film (Comparative Example 1) that does not show the bactericidal effect, the absorbance of the culture solution dispensed with the resin-coated sheet of any Example was equivalent. From this, it was found that the resin-coated sheet of any of the examples did not show a bactericidal action or a disinfecting action, like the PET film (Comparative Example 1).
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014140278A JP2016017130A (en) | 2014-07-08 | 2014-07-08 | Bacterium adhesion-suppressed resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014140278A JP2016017130A (en) | 2014-07-08 | 2014-07-08 | Bacterium adhesion-suppressed resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2016017130A true JP2016017130A (en) | 2016-02-01 |
Family
ID=55232600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014140278A Pending JP2016017130A (en) | 2014-07-08 | 2014-07-08 | Bacterium adhesion-suppressed resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2016017130A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021177201A1 (en) * | 2020-03-02 | 2021-09-10 | 京セラ株式会社 | Copolymer, method for producing same, measurement device, and measurement carrier |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274205A (en) * | 1989-04-17 | 1990-11-08 | Ipposha Oil Ind Co Ltd | Brush or the like |
| JPH10195390A (en) * | 1997-01-03 | 1998-07-28 | Huels Ag | Production of bacteria-repellent polymer surface, water-insoluble bacteria-repelled polymer, production thereof, product comprising the polymer, and production thereof |
| JPH10259109A (en) * | 1997-03-18 | 1998-09-29 | Nippon Chem Ind Co Ltd | Antimicrobial and dental composition and antimicrobial and dental polymer |
| JP2001504531A (en) * | 1996-11-14 | 2001-04-03 | レーム ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Antibacterial polymer |
| JP2002544348A (en) * | 1999-05-12 | 2002-12-24 | クレアヴィス ゲゼルシャフト フュア テヒノロギー ウント イノヴェイション ミット ベシュレンクテル ハフツング | Antimicrobial copolymer |
| JP2007277431A (en) * | 2006-04-07 | 2007-10-25 | Kochi Prefecture | Organism antifouling agent, antifouling treatment method and antifouling treated article |
| JP2009102314A (en) * | 2007-10-05 | 2009-05-14 | Kochi Prefecture | Antifouling or antimicrobial agent, antifouling or antimicrobial composition and method for antifouling or antimicrobial treatment |
| JP2011033701A (en) * | 2009-07-30 | 2011-02-17 | Seed Co Ltd | Solution for contact lens |
| JP2012017473A (en) * | 2004-07-23 | 2012-01-26 | Trustees Of The Univ Of Pennsylvania | Antibacterial copolymer and use thereof |
| JP2014012861A (en) * | 2007-11-19 | 2014-01-23 | Univ Of Washington | Cationic betaine precursor to zwitterionic betaine having controlled biological property |
| JP2016147808A (en) * | 2013-06-11 | 2016-08-18 | 株式会社Ｌｉｘｉｌ | Antibacterial/antifouling material and molding |
-
2014
- 2014-07-08 JP JP2014140278A patent/JP2016017130A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274205A (en) * | 1989-04-17 | 1990-11-08 | Ipposha Oil Ind Co Ltd | Brush or the like |
| JP2001504531A (en) * | 1996-11-14 | 2001-04-03 | レーム ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Antibacterial polymer |
| JPH10195390A (en) * | 1997-01-03 | 1998-07-28 | Huels Ag | Production of bacteria-repellent polymer surface, water-insoluble bacteria-repelled polymer, production thereof, product comprising the polymer, and production thereof |
| JPH10259109A (en) * | 1997-03-18 | 1998-09-29 | Nippon Chem Ind Co Ltd | Antimicrobial and dental composition and antimicrobial and dental polymer |
| JP2002544348A (en) * | 1999-05-12 | 2002-12-24 | クレアヴィス ゲゼルシャフト フュア テヒノロギー ウント イノヴェイション ミット ベシュレンクテル ハフツング | Antimicrobial copolymer |
| JP2012017473A (en) * | 2004-07-23 | 2012-01-26 | Trustees Of The Univ Of Pennsylvania | Antibacterial copolymer and use thereof |
| JP2007277431A (en) * | 2006-04-07 | 2007-10-25 | Kochi Prefecture | Organism antifouling agent, antifouling treatment method and antifouling treated article |
| JP2009102314A (en) * | 2007-10-05 | 2009-05-14 | Kochi Prefecture | Antifouling or antimicrobial agent, antifouling or antimicrobial composition and method for antifouling or antimicrobial treatment |
| JP2014012861A (en) * | 2007-11-19 | 2014-01-23 | Univ Of Washington | Cationic betaine precursor to zwitterionic betaine having controlled biological property |
| JP2011033701A (en) * | 2009-07-30 | 2011-02-17 | Seed Co Ltd | Solution for contact lens |
| JP2016147808A (en) * | 2013-06-11 | 2016-08-18 | 株式会社Ｌｉｘｉｌ | Antibacterial/antifouling material and molding |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021177201A1 (en) * | 2020-03-02 | 2021-09-10 | 京セラ株式会社 | Copolymer, method for producing same, measurement device, and measurement carrier |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Antonucci et al. | Synthesis and characterization of dimethacrylates containing quaternary ammonium functionalities for dental applications | |
| CN102803350B (en) | Phosphorylcholine-based amphiphilic silicones for medical applications | |
| US8821910B2 (en) | Alkylaminoalkyl oligomers as broad-spectrum antimicrobial agent | |
| KR100752150B1 (en) | Photocurable monomoers having imidazolium salts, antibacterial photocurable compositions comprising the same, and antibacterial polymer materials prepared therefrom | |
| JP6305429B2 (en) | Polyoxazoline copolymer | |
| JP2008510843A5 (en) | ||
| JPH0426669A (en) | Biologically lethal polymeric agent | |
| JP2012532935A (en) | Chitosan hydrogel derivatives as coating agents with a wide range of antibacterial activity | |
| JP2017206441A (en) | Bactericidal composition | |
| JP6961587B2 (en) | Slippery imparting agent and slippery imparting method | |
| WO2017043500A1 (en) | Composition, contact lens coating agent, method for producing contact lens, and contact lens | |
| JP2010215619A5 (en) | ||
| JPWO2018212061A1 (en) | Laminate, kit, and method for producing laminate | |
| Kolewe et al. | Fouling-resistant hydrogels prepared by the swelling-assisted infusion and polymerization of dopamine | |
| JP7341126B2 (en) | Antimicrobial resins and coatings | |
| Kanth et al. | Recent advances in development of poly (dimethylaminoethyl methacrylate) antimicrobial polymers | |
| JP2016017130A (en) | Bacterium adhesion-suppressed resin | |
| JP2016216426A5 (en) | ||
| JP2002544346A (en) | Method for producing an endogenous microbicidal polymer surface | |
| CA2384427A1 (en) | Copolymers of acryloylaminoalkyl compounds | |
| JP6852419B2 (en) | Polymer-type antibacterial and antifungal agents, and their use | |
| JP5044993B2 (en) | Additives for surface segregation plastics and their applications | |
| JPWO2018003821A1 (en) | Copolymer and its use | |
| JP2002544348A (en) | Antimicrobial copolymer | |
| JP2003507542A (en) | Aminopropyl vinyl ether copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20160712 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180227 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180501 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180529 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180727 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20180911 |