JP2000264803A - Photopolymerizable monomer composition and solventless type ultraviolet ray or electron beam curable resin composition having antimicrobial activity - Google Patents

Photopolymerizable monomer composition and solventless type ultraviolet ray or electron beam curable resin composition having antimicrobial activity

Info

Publication number
JP2000264803A
JP2000264803A JP7402099A JP7402099A JP2000264803A JP 2000264803 A JP2000264803 A JP 2000264803A JP 7402099 A JP7402099 A JP 7402099A JP 7402099 A JP7402099 A JP 7402099A JP 2000264803 A JP2000264803 A JP 2000264803A
Authority
JP
Japan
Prior art keywords
electron beam
photopolymerizable monomer
monomer composition
ultraviolet ray
antimicrobial
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.)
Granted
Application number
JP7402099A
Other languages
Japanese (ja)
Other versions
JP3824120B2 (en
Inventor
Masaaki Maekawa
Chisako Shirai
Satoshi Takeuchi
Zenichi Yamada
正明 前川
善市 山田
千佐子 白井
聡 竹内
Original Assignee
Sintokogio Ltd
新東工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sintokogio Ltd, 新東工業株式会社 filed Critical Sintokogio Ltd
Priority to JP07402099A priority Critical patent/JP3824120B2/en
Publication of JP2000264803A publication Critical patent/JP2000264803A/en
Application granted granted Critical
Publication of JP3824120B2 publication Critical patent/JP3824120B2/en
Anticipated expiration legal-status Critical
Application status is Expired - Fee Related legal-status Critical

Links

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable monomer composition which has excellent antimicrobial fine particles-dispersing properties and storage stability and can be directly added to a non-solvent type, ultraviolet ray and electron beam-curable resin without solvent dilution with good handleability, and provide an antimicrobial, non- solvent type, ultraviolet ray and electron beam curable resin composition containing the above-stated photopolymerizable monomer composition that wholly converts to the resin form in no occurrence of any organic solvent that exerts adverse effect on the environment after polymerization curing and is capable of giving remarkable antimicrobial and antifungal activity to the resin. SOLUTION: This photopolymerizable monomer composition is obtained by dispersing silver-based inorganic antimicrobial fine grains of 0.5-1.5 μm in the average particle diameter into a photopolymerizable monomer. Further, the solventless ultraviolet ray or electron beam curing resin composition is obtained by adding the photopolymeric monomer composition into a solventless ultraviolet ray or electron beam curable resin and including the silver-based inorganic antimicrobial fine grains in a proportion of 0.05-30 wt.%.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明は,銀系無機抗菌剤の微粒子を分散した,重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じない光重合性モノマー組成物,および該光重合性モノマー組成物を添加した,抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物に関するもので,フローリング,階段,手摺,机,紙器,包装材,タッチパネル,金属容器,電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷,コーティングすることにより,それらに抗菌・防カビ性を付与できるものである。 The present invention relates to the dispersed fine particles of the silver based inorganic antibacterial agent, the photopolymerizable monomer compositions that do not produce any organic solvent which adversely affect all become resin environment after polymerization curing, and photopolymerization was added sex monomer composition, relates solventless ultraviolet and electron beam curable resin composition having antibacterial, flooring, stairs, handrails, desk, paper containers, packaging material, a touch panel, a metal container, telephone, copier , personal computer, facsimile, medical equipment, painting or printing to a hospital for a vacuum cleaner, by coating, it is those that can impart antimicrobial and antifungal properties to them.

【0002】 [0002]

【従来の技術】従来、銀イオンが抗菌・防カビ性を有していることは知られており、銀イオンを各種の無機物質に担持した銀系無機抗菌剤について種々の発明がなされている。 Conventionally, the silver ions have antibacterial and antifungal properties are known, various inventions have been made on the silver based inorganic antibacterial agent of silver ions supported on various inorganic substances . 例えば、特公昭63−54013号公報には、 For example, in JP-B-63-54013,
比表面積の大きいゼオライトにイオン交換により銀イオンを担持させた殺菌性ゼオライト組成物が、特開昭62 Bactericidal zeolite Composition Supported silver ions by ion exchange to a large zeolite specific surface area, Sho 62
−210098号公報には、酸化銀を添加溶融した抗菌性ガラスが、特開平1−221304号公報には、モンモリロナイト等の無機層状化合物の層間にアンミン銀を担持させた抗菌剤が、特開平2−96508号公報には、難溶性リン酸塩や縮合リン塩酸に銀イオンを担持させた抗菌剤が、特開平3−83906号公報には、リン酸ジルコニウムにイオン交換により銀イオンを担持させた抗菌剤が、特開平3−218765号公報には、ハイドロキシアパタイトに銀イオンを吸着保持させた後焼成して得た抗菌剤が、更に、特開平3−275627号公報には、マグネシウムアルミノケイ酸塩に銀イオンを担持させた抗菌剤が開示されている。 The -210098 discloses an antimicrobial glass doped melted silver oxide, JP-A-1-221304, antibacterial agents obtained by supporting the ammine silver layers of the inorganic layered compound such as montmorillonite, JP 2 the -96508 discloses an antimicrobial agent obtained by supporting silver ion into insoluble phosphate or condensed phosphate hydrochloric acid, JP-a-3-83906, was supported silver ions by ion exchange on a zirconium phosphate antimicrobial agents, JP-a-3-218765, an antimicrobial agent obtained by firing after being sucked and held silver ions in hydroxyapatite, further, JP-a-3-275627, magnesium aluminosilicate antibacterial agents obtained by supporting silver ions is disclosed in.

【0003】一般的に銀系無機抗菌剤は粉末であり,塗料やインクなどにそのまま混ぜると攪拌機で分散しても,二次凝集を起こすため使用できなかった。 [0003] Generally, the silver based inorganic antibacterial agent is a powder, be dispersed in directly mixing the agitator such as paints and inks, it could not be used to cause the secondary aggregation. このような問題点を解決するものとして,特開平6−24781 In order to solve such problems, JP-A-6-24781
7号公報には、有機溶剤の中で銀系無機抗菌剤を湿式粉砕することにより,溶剤系の塗料やインキなどにそのまま添加しても二次凝集が生じないという特徴を有する, The 7 discloses, by wet milling silver based inorganic antibacterial agent in an organic solvent, it has a characteristic that even when it is added, such as the paint or ink solvent system does not cause secondary agglomeration,
平均粒子径が0.3μm以下の銀系無機抗菌剤微粒子の懸濁液が開示されている。 Suspension having an average particle diameter of 0.3μm or less of the silver based inorganic antibacterial agent particles are disclosed.

【0004】 [0004]

【発明が解決しようとする課題】しかし,有機溶剤は, The object of the invention is to be Solved However, the organic solvent,
地球温暖化やシックハウスなどの問題があり,これら有機溶剤を一切含まず,現場でそのまま塗料等に添加でき,または多品種少量生産の塗料あるいはインキ,コーティング材などにも対応できる使い勝手の極めて良い無溶剤タイプの銀系無機抗菌剤微粒子の懸濁液,または銀系無機抗菌剤微粒子を含んだ無溶剤タイプの紫外線または電子線硬化樹脂の塗料あるいはインキ,コーティング材が望まれていた。 There are problems such as global warming and sick house, without them organic solvent at all, situ can be added directly to the paint or the like, or high-mix low-volume production of paints or inks, a very good non-usability that can cope with such a coating material the suspension of the solvent type of silver-based inorganic antimicrobial agent particles, or silver-based containing inorganic antimicrobial agent particles solvent-free ultraviolet or electron beam curable resin coating material or ink, the coating material has been desired.

【0005】 [0005]

【課題を解決するための手段】上記の問題を達成するために、平均粒子径が0.5μmを越え1.5μm以下の範囲にある銀系無機抗菌剤の微粒子を光重合性モノマーに分散したことを特徴とする光重合性モノマー組成物,および無溶剤タイプ紫外線または電子線硬化樹脂に該光重合性モノマー組成物を添加して,0.05〜30重量% To achieve the above-mentioned problems SUMMARY OF THE INVENTION, by dispersing fine particles of the silver based inorganic antibacterial agent having an average particle size in the range below 1.5μm beyond 0.5μm photopolymerizable monomer it was added to the photopolymerizable monomer composition to a photopolymerizable monomer composition, and solvent-free ultraviolet or electron beam curable resin, characterized in, 0.05 to 30 wt%
の銀系無機抗菌剤微粒子を含ませたことを特徴とする, Characterized in that impregnated with the silver-based inorganic antimicrobial agent particles,
抗菌性を有する無溶剤紫外線および電子線硬化樹脂組成物を提供する。 Providing a solventless ultraviolet and electron beam curable resin composition having antimicrobial properties.

【0006】本発明に用いる銀系無機抗菌剤は、銀イオンを各種の無機物質に担持した銀系無機抗菌剤、例えば、抗菌・防カビ性リン酸塩(特願平2−418277 [0006] Silver based inorganic antibacterial agent used in the present invention, a silver based inorganic antibacterial agent of silver ions supported on various inorganic substances, for example, antibacterial and antifungal phosphate (Japanese Patent Application No. 2-418277
号、特願平3−315618号)、前述の殺菌性ゼオライト組成物、抗菌性ガラス、モンモリロナイト等の無機層状化合物の層間にアンミン銀を担持させた抗菌剤難溶性リン酸塩や縮合リン酸塩に銀イオンを担持させた抗菌剤、リン酸ジルコニウムにイオン交換により銀イオンを担持させた抗菌剤、ハイドロキシアパタイトに銀イオンを吸着保持させた後焼成して得た抗菌剤、及びマグネシウムアルミノケイ酸塩に銀イオンを担持させた抗菌剤などを,制限なく利用できるが,これらに限られるものではない。 Nos, Japanese Patent Application No. Hei 3-315618), bactericidal zeolite composition described above, the antibacterial glass, the interlayer antimicrobial sparingly soluble was supported ammine silver phosphate and condensed phosphates of the inorganic layered compound such as montmorillonite antibacterial agents obtained by supporting silver ions, an antibacterial agent obtained by supporting silver ions by ion exchange on a zirconium phosphate antimicrobial agent obtained by calcination after the silver ions were attracted to and held on hydroxyapatite, and magnesium aluminosilicate the silver ions, such as antimicrobial agents obtained by supporting on, can be used without restriction, but is not limited thereto.

【0007】本発明に用いる光重合性モノマーとしては、2−エチルヘキシルアクリレート,2−ヒドロキシエチルアクリレート,2−ヒドロキシプロピルアクリレート,2−ヒドロキシエチルアクリロイルホスフェート,1,3−ブタンジオールジアクリレート,1,4− [0007] As the photopolymerizable monomer used in the present invention include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, 1,3-butanediol diacrylate, 1,4 -
ブタンジオールジアクリレート,1,6−ヘキサンジオールジアクリレート,ジエチレングリコールジアクリレート,トリプロピレングリコールジアクリレート,ネオベンチルグリコールジアクリレート,ポリエチレングリコール400ジアクリレート,ヒドロキシビバリン酸エステルネオベンチルグリコールジアクリレート,トリメチロールプロパントリアクリレート,ペンタエリスリトールトリアクリレート,ジペンタエリスリトールヘキサアクリレートなどの少なくとも1種を使用できるが,これらに限られるものではない。 Butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neo bench glycol diacrylate, polyethylene glycol 400 diacrylate, hydroxy Viva phosphoric acid ester neo bench glycol diacrylate, tri triacrylate, pentaerythritol triacrylate, but at least one of dipentaerythritol hexaacrylate can be used, not limited thereto.

【0008】また,これら光重合性モノマーとプレポリマーであるオリゴマーとを混ぜて使用してもよい。 [0008] It is also possible to use mixed and oligomers of these photopolymerizable monomers and prepolymers. これら光重合性モノマーは、銀系無機抗菌剤を溶解することがなく,銀イオンもほとんど光重合性モノマーに移行することがないので、懸濁液が光で変色するなどの問題がないので好都合である。 These photopolymerizable monomers, without dissolving the silver based inorganic antibacterial agent, there is no moving to silver ions almost photopolymerizable monomer, since there is no problem such as the suspension changes color with light convenient it is. なお,これら光重合性モノマーが長期の保存などで変質しないように,公知の重合防止剤を添加してもよい。 Incidentally, these photopolymerizable monomers to prevent deterioration in a long-storage, may be added a known polymerization inhibitor.

【0009】本発明に関わる平均粒子径が0.5μmを越え1.5μm以下の範囲にある銀系無機抗菌剤の微粒子を光重合性モノマーに分散する方法は,銀系無機抗菌剤および光重合性モノマーを,公知の媒体ミル、遊星ミル、振動ボ−ルミル、ボ−ルミルなどの湿式粉砕機にかけることにより得られる。 [0009] The method of average particle diameter according to the present invention is to disperse the fine particles of the silver based inorganic antibacterial agent in the range below 1.5μm beyond 0.5μm photopolymerizable monomer, a silver based inorganic antibacterial agent and photopolymerization sex monomers, known media mill, planetary mill, vibration ball - mill, ball - mill obtained by subjecting to a wet grinding machine such as a. このとき粉砕を促進させ,分散性を改善するためなどに公知の分散剤や,チタネート系,アルミニウム系およびシラン系カップリング剤などを制限なく用いてもよい。 The time to promote pulverization, or a known dispersant such as to improve the dispersibility, titanate, aluminum-based and silane coupling agents may be used without restriction.

【0010】このとき銀系無機抗菌剤の平均粒子径は、 [0010] The average particle diameter of the silver based inorganic antibacterial agent at this time,
分散性および保存安定性に優れた懸濁液を得るために0.5μmを越え1.5μm以下の範囲とすることが好ましく,0.6〜1.0μmとすることがより好ましい。 It is preferably in the following range 1.5μm beyond 0.5μm to obtain a good suspension dispersibility and storage stability, and more preferably to 0.6~1.0Myuemu.
平均粒子径が0.5μm以下とするには大きな粉砕エネルギーを必要とし,光重合性モノマーを変質させることから好ましくない。 Not preferable because the average particle size require large grinding energy to the 0.5μm or less, to alter the photopolymerizable monomer. また,平均粒子径が1.5μmを越えると抗菌剤が沈降固化し易くなり,安定した懸濁液が得られないので好ましくない。 The average the particle size exceeds 1.5μm antimicrobial agent is likely to settle solidified undesirable because not stable suspension is obtained.

【0011】本発明に係わる無溶剤タイプ紫外線または電子線硬化樹脂は,木材塗装,紙・フィルムの印刷,金属印刷,プラスチック容器の印刷,プラスチックのハードコートおよびメタライジング加工などに用いられる, [0011] solvent-free ultraviolet or electron beam curable resins for use in the present invention, wood coatings, printing paper and film, metal printing, plastic containers, used for hard coat and metallizing processing plastics,
ラジカル重合型,ラジカル付加重合型およびカチオン重合型などの無溶剤タイプ紫外線または電子線硬化樹脂を制限なく使用できる。 Radical polymerization type, a solvent-free ultraviolet or electron beam curable resins such as a radical addition polymerization and cationic polymerization type can be used without limitation.

【0012】本発明に係わる抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物は,前述の光重合性モノマー組成物を添加して,上述の無溶剤タイプ紫外線または電子線硬化樹脂に0.05〜30重量%の銀系無機抗菌剤微粒子を含ませ,より好ましくは0.2〜3 [0012] solvent-free ultraviolet or electron beam curable resin composition having antimicrobial properties according to the present invention, by adding the aforementioned photopolymerizable monomer composition, 0 to solvent-free ultraviolet or electron beam curable resin described above .05~30 not include the weight percent of the silver based inorganic antibacterial agent particles, more preferably from 0.2 to 3
重量%とする。 The percent by weight. 0.05重量%未満では,紫外線または電子線を照射して硬化させた塗膜の抗菌性が不十分であり,30重量%を越えると塗膜の物性に著しい悪影響を及ぼすので好ましくない。 Is less than 0.05 wt%, is insufficient antimicrobial coating film was cured by irradiation with ultraviolet light or an electron beam, exerts a significant adverse effect on the physical properties of the coating film exceeds 30 wt% is not preferable.

【0013】 [0013]

【作用】本発明は上記のような構成を採用することにより、銀系無機抗菌剤の微粒子を含むにも拘わらず分散性および保存安定性に優れた光重合性モノマー組成物を可能とし,該光重合性モノマー組成物を添加した抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物は,フローリング,階段,手摺,机,紙器,包装材,タッチパネル,金属容器,電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷,コーティングすることにより,重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じないで,それらに抗菌・防カビ性を付与できる。 DETAILED DESCRIPTION OF THE INVENTION The present invention by employing the configuration as described above, to allow an excellent photopolymerizable monomer composition in dispersibility and storage stability irrespective of containing fine particles of the silver based inorganic antibacterial agent, the solventless ultraviolet and electron beam curable resin composition having antimicrobial properties was added a photopolymerizable monomer composition, flooring, stairs, handrails, desk, paper containers, packaging material, a touch panel, a metal container, telephone, copying machine, personal computer, facsimile, medical equipment, painting or printing to a hospital for a vacuum cleaner, by coating, without causing any organic solvent which adversely affect the environment becomes a resin all after the polymerization curing, impart antimicrobial and antifungal properties to them it can.

【0014】 [0014]

【発明の実施の形態】1. DETAILED DESCRIPTION OF THE INVENTION 1. 銀系無機抗菌剤の調製 [参考実施例1] 抗菌・防カビ性リン酸塩の調製 25%リン酸水溶液750mlを50℃に加熱し、撹拌しながら酸化亜鉛(ZnO)194.7gを加えて反応させ、更に水酸化カルシウム(Ca(OH) )35.4 The silver-based preparation of inorganic antibacterial agents [Reference Example 1] Preparation of antibacterial and antifungal phosphate 25% phosphoric acid aqueous solution 750ml were heated to 50 ° C., was added with stirring zinc oxide (ZnO) 194.7 g reacted, further calcium hydroxide (Ca (OH) 2) 35.4
gを加えて反応させる。 In addition to the g is reacted. 反応スラリ−を温室に冷却した後、2lボ−ルミルに移し、6時間連和してから硝酸銀(AgNO )25.2gを添加し、更に4時間連和を続けた。 After cooling to the greenhouse, 2l ball - - reaction slurry was transferred to a mill, silver nitrate after continuous sum 6 hours (AgNO 3) 25.2 g was added and continued for an additional 4 hours continuous sum. 得られた反応スラリ−を水洗し、濾過した後、 The resulting reaction slurry - was washed with water, followed by filtration,
250℃で乾燥し、粉砕して粉末(以下「粉末1」という)とした。 Dried at 250 ° C., to a powder (hereinafter referred to as "Powder 1") was pulverized. 粉末1に担持された銀イオンの含有量は、 Contents of the adhered silver ion powder 1,
3.0重量%、平均粒径は2.7μmであった。 3.0 wt%, average particle diameter was 2.7 .mu.m.

【0015】[参考実施例2] ゼオライトを担持体とした抗菌剤の調製 1/20M硝酸銀水溶液1,500mlにナトリウムタイプのA型ゼオライト(東ソ−製トヨビルダ−)の乾燥物250gを加え、温室にて3時間撹拌してから濾過し、 [0015] [Reference Example 2] Zeolite carrier and the sodium type A zeolite to prepare 1 / 20M aqueous solution of silver nitrate 1,500ml of antimicrobials (Toso - manufactured Toyobiruda -) dried product 250g was added, greenhouses stirred for 3 hours and filtered from by,
水洗して過剰の銀イオンを除去した。 To remove the excess of silver ions and washed with water. これを110℃で乾燥し、粉砕して粉末(以下「粉末2」という)とした。 This was dried at 110 ° C., to a powder (hereinafter referred to as "Powder 2") was pulverized. 粉末2に担持された銀イオンの含有量は3.1重量%、平均粒径は3.1μmであった。 Contents of the adhered silver ion powder 2 3.1 wt%, average particle diameter was 3.1 .mu.m.

【0016】[参考実施例3]リン酸ジルコニウムを担持体とした抗菌剤の調整 1/20M硝酸銀水溶液1,500mlにリン酸ジルコニウム(IXE−100;東亜合成化学製)の乾燥物25 [0016] [Reference Example 3] zirconium phosphate adjusted 1 / 20M aqueous solution of silver nitrate 1,500ml of zirconium phosphate the carrier and the antimicrobial agent; dry matter (IXE-100 manufactured by Toagosei) 25
0gを加え、温室にて3時間撹拌してから濾過し、水洗して過剰な銀イオンを除去した。 0g was added, then filtered and stirred for 3 hours in a greenhouse, to remove excess silver ions by washing with water. これを110℃で乾燥し、粉砕して粉末(以下「粉末3」という)とした。 This was dried at 110 ° C., to a powder (hereinafter referred to as "powder 3") was pulverized. 粉末3に担持された銀イオンの含有量は3.0重量%、平均粒径は0.72μmであった。 Contents of the adhered silver ions in the powder 3 3.0 wt%, average particle diameter was 0.72 .mu.m.

【0017】2. [0017] 2. 光重合モノマー組成物の調製 [実施例1]トリプロピレングリコールジアクリレート3kgに参考実施例1で得た「粉末1」3kgを加え、 Preparation Example 1 of the photopolymerizable monomer composition to obtain a tripropylene glycol diacrylate 3kg in Reference Example 1 "Powder 1" 3kg added,
ホモジナイザ−で10分間分散混合してから、媒体ミル(容量1リットルのパ−ルミルPMIRL−V型、アシザワ製)を用いて湿式粉砕した。 Homogenizer from - mixed dispersed for 10 minutes, media mill - was wet milled using a (1-liter Pas mill PMIRL-V type, manufactured by Ashizawa). 2mm径のアルミナ製の粉砕ビ−ズ(新東Vセラックス製)1,150gを用い、500ml/minの処理スピ−ドで5パス行って光重合モノマー組成物(以下「モノマー組成物1」という) 2mm diameter alumina grinding bi - called de 5 pass performed by photopolymerization monomer composition (hereinafter "monomer composition 1" -'s used (Shinto V Serakkusu Ltd.) 1,150g, 500ml / min for processing spin )
を得た。 It was obtained. モノマー組成物1に含まれる銀系無機抗菌剤微粒子の平均粒子径は0.67μmであった。 The average particle diameter of the silver based inorganic antibacterial agent particles contained in the monomer composition 1 was 0.67 .mu.m. また,得られたモノマー組成物1をブリキ缶に入れ、1ヶ月間放置したが、沈降固化は全く見られなかった。 Also, it puts the resulting monomer composition 1 to tin cans, was allowed to stand for one month, was not seen at all settle solidified.

【0018】[実施例2]2−ヒドロキシエチルアクリレート3kgにチタネ−ト系カップリング剤(味の素(株)製、品名:プレンアクトKRTTS)30gと参考実施例2で得た「粉末2」3kgを加え、ホモジナイザ−で10分間分散混合してから、媒体ミル(容量1リットルのパ−ルミルPMIRL−V型、アシザワ製)を用いて湿式粉砕した。 [0018] [Example 2] titanate in 2-hydroxyethyl acrylate 3kg - DOO-based coupling agent (Ajinomoto Co., Ltd., product name: PLENACT KRTTS) 30 g and obtained in Reference Example 2 "powder 2" 3kg added , homogenizer from - mixed dispersed for 10 minutes, media mill - was wet milled using a (1-liter Pas mill PMIRL-V type, manufactured by Ashizawa). 2mm径のアルミナ製の粉砕ビ−ズ(新東Vセラックス製)1,150gを用い、1パス5 2mm diameter alumina grinding bi - using's (manufactured by Shinto V Serakkusu) 1,150g, 1 pass 5
00ml/minの処理スピ−ドで5パス行って光重合モノマー組成物(以下「モノマー組成物2」という)を得た。 100 ml / min of processing spin - to obtain 5 passes performed by photopolymerization monomer composition in de (hereinafter referred to as "monomer composition 2"). モノマー組成物2に含まれる銀系無機抗菌剤微粒子の平均粒子径は0.83μmであった。 The average particle diameter of the silver based inorganic antibacterial agent particles contained in the monomer composition 2 was 0.83 .mu.m. また、得られたモノマー組成物2をブリキ缶に入れ、1ヶ月間放置したが、沈降固化は全く見られなかった。 Also, put the resulting monomer composition 2 Tinplate cans, have been left for one month, it was not observed at all precipitation hardening.

【0019】[実施例3]ペンタエリスリトールトリアクリレート3kgにアルミニウム系カップリング剤(味の素(株)製,品名:プレンアクトAL−M)30gと参考実施例3で得た「粉末3」3kgを加え、ホモジナイザ−で10分間分散混合してから、媒体ミル(1Lパ−ルミルPMIRL−V型、アシザワ製)を用いて湿式粉砕した。 [0019] [Example 3] Pentaerythritol triacrylate 3kg aluminum-based coupling agent (Ajinomoto Co., Ltd., product name: PLENACT AL-M) 30 g and obtained in Reference Example 3 "powder 3" 3kg was added, homogenizer - after dispersion mixed for 10 minutes, the media mill - was wet milled using a (1L Pas mill PMIRL-V type, manufactured by Ashizawa). 2mm径のアルミナ製の粉砕ビ−ズ(新東Vセラックス製)1,150gを用い、1パス500ml/mi 2mm diameter alumina grinding bi -'s used (Shinto V Serakkusu Ltd.) 1,150g, 1 pass 500 ml / mi
nの処理スピ−ドで5パス行って光重合モノマー組成物(以下「モノマー組成物3」という)を得た。 n processing spin - to obtain 5 passes performed by photopolymerization monomer composition in de (hereinafter referred to as "monomer composition 3"). モノマー組成物3に含まれる銀系無機抗菌剤微粒子の平均粒子径は0.68μmであった。 The average particle diameter of the silver based inorganic antibacterial agent particles contained in the monomer composition 3 was 0.68 .mu.m. また、得られたモノマー組成物3をブリキ缶に入れ、1ヶ月間放置したが、沈降固化は全く見られなかった。 Also, put the resulting monomer composition 3 Tinplate cans, have been left for one month, it was not observed at all precipitation hardening.

【0020】[実施例4] 紫外線硬化塗料の調製 抗菌剤濃度が1重量%となるようにモノマー組成物1, [0020] [Example 4] monomer composition 1 as the preparation antimicrobial agent concentration of the ultraviolet curable coating material is 1% by weight,
2および3をそれぞれ無溶剤タイプウレタンアクリレート紫外線硬化塗料に添加し攪拌機で混合して,抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物(以下「樹脂組成物1」,「樹脂組成物2」および「樹脂組成物3」という)を得た。 By mixing 2 and 3 respectively it was added to the solvent-free urethane acrylate ultraviolet curable coating material stirrer, solvent-free ultraviolet or electron beam curable resin composition having antimicrobial (hereinafter "resin composition 1", "resin composition 2 "and as" resin composition 3 ") was obtained. また、得られた樹脂組成物をそれぞれブリキ缶に入れ、2ヶ月間放置したが、異常は全く見られなかった。 Moreover, taking into tin can obtained resin composition, respectively, were allowed to stand for 2 months, no abnormality was observed at all.

【0021】[実施例5] 試験片の作製 上で得られた樹脂組成物1,2,および3をそれぞれロールコーターでポリエステル樹脂シート(厚さ100μ [0021] [Example 5] Polyester resin sheet (thickness 100μ resin composition obtained in the preparation of test pieces 1, 2, and 3 respectively roll coater
m)に塗布してから,紫外線を照射して塗料を硬化させ,試験片(以下それぞれ「試験片1」,「試験片2」 From application to m), by irradiating ultraviolet rays to cure the coating, the test piece (hereinafter, respectively "specimen 1", "specimen 2"
および「試験片3」という)を得た。 And to obtain a) "test piece 3". また,同様にして抗菌剤が入っていない塗料で試験片(以下「試験片0」 Also, paint the test piece does not contain an antimicrobial agent in the same manner (hereinafter referred to as "test piece 0"
という)を得た。 To obtain a) that.

【0022】3. [0022] 3. 抗菌性およびカビ抵抗性試験 [実施例6] 抗菌性試験 実施例5で得られた「試験片1」,「試験片2」,「試験片3」および「試験片0」について抗菌性試験を行った。 Antibacterial and mildew resistance test Example 6 was obtained in the antibacterial property test Example 5 "specimen 1", "specimen 2", an antibacterial test for "test piece 3" and "specimen 0" went. ここでは試験片(50×50mm)2枚を塗装面を外側にして接着剤で貼り合わせたものを試験片とした。 Here were those two test pieces (50 × 50 mm) was stuck to the coated surface in with outward adhesive a test piece. 該試験片が丁度入るようにポリエチレンフィルムをヒ−トシ−ルして袋を作った。 The test piece heat the polyethylene film as just entering - tosylate - made bags and Le. この袋に試験片を入れて、大腸菌(IFO3972)および黄色ブドウ球菌(IFO1 Put the test piece in the bag, E. coli (IFO3972) and Staphylococcus aureus (IFO1
2732)を用い加圧密着法により抗菌性試験を行った。 Been antibacterial test by pressure compaction desorption method using 2732). これらの試験片を入れたポリエチレン袋の中に菌液を0.1ml滴下した後、テストピ−スの両面に菌液が隈なく行き渡るようにした後、フィルム内部の空気を排出し密閉した。 After the Kin'eki in a polyethylene bag placed in these specimens was 0.1ml dropwise, test piece - bacterial solution on both sides of the scan is after such spreads without thoroughly, and to discharge air in the film sealing. その後、重しで加圧してふ卵器に入れ、2 Then placed in a incubator pressurized with weigh, 2
4時間後にリン酸緩衝液(10ml)で袋中の生残菌を洗い出し、この洗い出し液1mlについて、SCDLP寒天培地を用い混釈平板培養法により生残菌数を測定した。 Washout raw Zankin in the bag after 4 hours with phosphate buffer (10 ml), this washout solution 1 ml, was measured the survival cell count by the pour plate culture method using a SCDLP agar medium.
その結果(表1)から、本発明による光重合モノマ−組成物を添加した紫外線硬化塗料を用いた試験片は、顕著な抗菌性が認められた。 The results (Table 1), photopolymerizable monomers according to the invention - specimens using a UV curable coating material obtained by adding the composition, remarkable antibacterial activity was observed.

【0023】 [0023]

【表1】 [Table 1]

【0024】[実施例7] カビ抵抗性試験 実施例5で得られた「試験片1」,「試験片2」,「試験片3」および「試験片0」についてカビ抵抗性試験を行った。 [0024] [Example 7] obtained in mildew resistance test Example 5 "specimen 1", "specimen 2", was performed fungus resistance test for "test piece 3" and "specimen 0" . あらかじめ滅菌しておいた寒天をシャ−レに入れ固化させた。 It was allowed to pre-sterilized agar Sha - was solidified put in Les. その寒天の上に試験片をそれぞれのシャーレに置いた。 Placing a test piece into each dish onto the agar. また,0.005%スルホコハク酸ジオクチルナトリウム水溶液10mlに別途培養したアスペルギルス・ニガ−(IFO4414)を5白金耳取り、遠心分離により胞子を分離し,その胞子を生理食塩水10 Separately cultured Aspergillus nigga to 0.005% dioctyl sulfosuccinate aqueous solution of sodium 10ml - (IFO4414) 5 platinum loop up, separating the spores by centrifugation, the spores saline 10
mlに入れた菌液をそれぞれのシャ−レの試験片の上に墳霧し、25℃、14日間ふ卵器で培養した。 ml put bacterial solution each Sha - to Funkiri on Les specimens, 25 ° C., and cultured for 14 days incubator. その結果(表2)から、本発明による光重合モノマー組成物を添加した紫外線硬化塗料を用いた試験片は、顕著なカビ抵抗性が認められた。 The results (Table 2), the test piece using an ultraviolet curable coating material obtained by adding a photopolymerizable monomer composition according to the present invention, remarkable fungus resistance was observed.

【0025】 [0025]

【表2】 [Table 2]

【0026】 [0026]

【発明の効果】以上の説明から明らかなように、本発明に係わる光重合性モノマー組成物にあっては,分散性および保存安定性に優れ,取扱いも容易で,無溶剤タイプ紫外線および電子線硬化樹脂にそのまま添加することにより簡単に得られる,抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物は,分散性に優れ、長期保存しても沈降・固化することがなく,フローリング, As apparent from the above description, in the photopolymerizable monomer composition according to the present invention, excellent dispersibility and storage stability, handling is easy, solvent-free ultraviolet or electron beam obtained simply by directly added to the curable resin, solvent-free ultraviolet or electron beam curable resin composition having antimicrobial properties is excellent in dispersibility, without having to settle and solidified even if long-term storage, flooring,
階段,手摺,机,紙器,包装材,タッチパネル,金属容器,電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷,コーティングすることにより,重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じないで,それらに顕著な抗菌・防カビ性を付与できる。 Stairs, handrails, desk, paper containers, packaging material, a touch panel, a metal container, telephones, copying machines, personal computers, facsimile, medical equipment, painting or printing in a hospital vacuum cleaner, by coating, all be resin after polymerization curing without causing any organic solvent which adversely affect the environment, it can impart significant antibacterial and antifungal properties thereto.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4H011 AA02 BA01 BB18 BC18 BC19 DA01 DH16 4J038 FA011 FA111 KA20 PA17 ────────────────────────────────────────────────── ─── front page of continued F-term (reference) 4H011 AA02 BA01 BB18 BC18 BC19 DA01 DH16 4J038 FA011 FA111 KA20 PA17

Claims (2)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 平均粒子径が0.5μmを越え1.5μm 1. A 1.5μm beyond the average particle diameter of 0.5μm
    以下の範囲にある銀系無機抗菌剤の微粒子を光重合性モノマーに分散したことを特徴とする光重合性モノマー組成物。 Photopolymerizable monomer composition characterized by containing dispersed fine particles of the silver based inorganic antibacterial agent in the range of the photopolymerizable monomer.
  2. 【請求項2】 無溶剤タイプ紫外線若しくは電子線硬化樹脂に請求項1記載の光重合性モノマー組成物を添加して,0.05〜30重量%の銀系無機抗菌剤微粒子を含ませたことを特徴とする,抗菌性を有する無溶剤紫外線および電子線硬化樹脂組成物。 2. A by adding a photopolymerizable monomer composition according to claim 1, wherein the non-solvent type ultraviolet ray or electron beam curing resin, it was contained 0.05 to 30% by weight of silver based inorganic antibacterial agent particles wherein the solventless UV and electron beam curing resin composition having antimicrobial properties.
JP07402099A 1999-03-18 1999-03-18 Photopolymerizable monomer composition having antimicrobial, and non-solvent type ultraviolet ray and electron beam curable resin composition having antibacterial properties Expired - Fee Related JP3824120B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP07402099A JP3824120B2 (en) 1999-03-18 1999-03-18 Photopolymerizable monomer composition having antimicrobial, and non-solvent type ultraviolet ray and electron beam curable resin composition having antibacterial properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP07402099A JP3824120B2 (en) 1999-03-18 1999-03-18 Photopolymerizable monomer composition having antimicrobial, and non-solvent type ultraviolet ray and electron beam curable resin composition having antibacterial properties

Publications (2)

Publication Number Publication Date
JP2000264803A true JP2000264803A (en) 2000-09-26
JP3824120B2 JP3824120B2 (en) 2006-09-20

Family

ID=13535026

Family Applications (1)

Application Number Title Priority Date Filing Date
JP07402099A Expired - Fee Related JP3824120B2 (en) 1999-03-18 1999-03-18 Photopolymerizable monomer composition having antimicrobial, and non-solvent type ultraviolet ray and electron beam curable resin composition having antibacterial properties

Country Status (1)

Country Link
JP (1) JP3824120B2 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007113013A (en) * 2005-10-18 2007-05-10 Dreve-Otoplastik Gmbh Low-viscosity radiation-curable formed article for producing ear adaptor having germicidal property
JP2010173115A (en) * 2009-01-27 2010-08-12 Panasonic Electric Works Co Ltd Woody plate
JP2011057855A (en) * 2009-09-10 2011-03-24 Nippon Synthetic Chem Ind Co Ltd:The Active energy ray-curable composition, coating agent and resin film
JP2012510367A (en) * 2008-12-01 2012-05-10 ベクトン・ディキンソン・アンド・カンパニーBecton, Dickinson And Company System and method for applying an antimicrobial coating on a medical device
KR101312882B1 (en) * 2007-12-07 2013-09-30 (주)엘지하우시스 Kitchen furniture having superior stain resistance
JP2013203935A (en) * 2012-03-29 2013-10-07 Fujicopian Co Ltd Hard coat film
JP2016511787A (en) * 2013-02-13 2016-04-21 ベクトン・ディキンソン・アンド・カンパニーBecton, Dickinson And Company Uv curable solventless antimicrobial composition
US9352119B2 (en) 2012-05-15 2016-05-31 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9579486B2 (en) 2012-08-22 2017-02-28 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9675793B2 (en) 2014-04-23 2017-06-13 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US9750928B2 (en) 2013-02-13 2017-09-05 Becton, Dickinson And Company Blood control IV catheter with stationary septum activator
US9789279B2 (en) 2014-04-23 2017-10-17 Becton, Dickinson And Company Antimicrobial obturator for use with vascular access devices
US10232088B2 (en) 2014-07-08 2019-03-19 Becton, Dickinson And Company Antimicrobial coating forming kink resistant feature on a vascular access device

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007113013A (en) * 2005-10-18 2007-05-10 Dreve-Otoplastik Gmbh Low-viscosity radiation-curable formed article for producing ear adaptor having germicidal property
KR101312882B1 (en) * 2007-12-07 2013-09-30 (주)엘지하우시스 Kitchen furniture having superior stain resistance
JP2012510367A (en) * 2008-12-01 2012-05-10 ベクトン・ディキンソン・アンド・カンパニーBecton, Dickinson And Company System and method for applying an antimicrobial coating on a medical device
JP2010173115A (en) * 2009-01-27 2010-08-12 Panasonic Electric Works Co Ltd Woody plate
JP2011057855A (en) * 2009-09-10 2011-03-24 Nippon Synthetic Chem Ind Co Ltd:The Active energy ray-curable composition, coating agent and resin film
JP2013203935A (en) * 2012-03-29 2013-10-07 Fujicopian Co Ltd Hard coat film
US9770580B2 (en) 2012-05-15 2017-09-26 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9352119B2 (en) 2012-05-15 2016-05-31 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9579486B2 (en) 2012-08-22 2017-02-28 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9695323B2 (en) 2013-02-13 2017-07-04 Becton, Dickinson And Company UV curable solventless antimicrobial compositions
US9750928B2 (en) 2013-02-13 2017-09-05 Becton, Dickinson And Company Blood control IV catheter with stationary septum activator
JP2016511787A (en) * 2013-02-13 2016-04-21 ベクトン・ディキンソン・アンド・カンパニーBecton, Dickinson And Company Uv curable solventless antimicrobial composition
US9675793B2 (en) 2014-04-23 2017-06-13 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US9789279B2 (en) 2014-04-23 2017-10-17 Becton, Dickinson And Company Antimicrobial obturator for use with vascular access devices
US9956379B2 (en) 2014-04-23 2018-05-01 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US10232088B2 (en) 2014-07-08 2019-03-19 Becton, Dickinson And Company Antimicrobial coating forming kink resistant feature on a vascular access device

Also Published As

Publication number Publication date
JP3824120B2 (en) 2006-09-20

Similar Documents

Publication Publication Date Title
Kong et al. Photocatalytic antibacterial capabilities of TiO2− biocidal polymer nanocomposites synthesized by a surface-initiated photopolymerization
DE69935677T2 (en) Antibiotic hydrophilic coating
US6815489B1 (en) Nanocomposite coatings
DE60029205T2 (en) Resin composition and cured product
Busolo et al. Novel silver-based nanoclay as an antimicrobial in polylactic acid food packaging coatings
JP4512531B2 (en) Antibacterial of the dried coating
US20040156918A1 (en) Anti-microbial packaging materials and methods for making the same
CN100462414C (en) Ultraviolet light curing nano antibacterial woodenware paint and preparation method thereof
KR20110044981A (en) Active nanocomposite materials and methods for their preparation
EP1137537A1 (en) Antibiotic high-pressure laminates
CN1470574A (en) Anion antibacterial paint
WO2002055612A1 (en) Coating composition, coating film thereof, antireflection coating, antireflection film, image display, and intermediate product
JP3486919B2 (en) Glass flakes having antimicrobial
JP3530085B2 (en) Metal oxide particles, their preparation and use
JP5812488B2 (en) Antimicrobial and antiviral compositions and a method of manufacturing the same
EP2716605A1 (en) Nanocomposite materials based on metal oxides having multi-functional properties
JP5777337B2 (en) Antibacterial material
Konwar et al. Vegetable oil based highly branched polyester/clay silver nanocomposites as antimicrobial surface coating materials
Bugatti et al. Modified layered double hydroxides in polycaprolactone as a tunable delivery system: in vitro release of antimicrobial benzoate derivatives
CN100471569C (en) Photocatalyst apatite-containing film, method for forming the same, coating fluid, and electronic apparatus having member covered with photocatalyst apatite-containing film
JP3806061B2 (en) An electronic device having a method of forming a metal-modified apatite-containing film, a coating solution used in this and the coated portion of a metal-modified apatite-containing film
US20120010345A1 (en) Pigment for laser marking
KR101007152B1 (en) Anti-statically coated moulded body and method for the production thereof
KR100765083B1 (en) Ag-Containing Solution, Antibacterial Resin Composition Comprising the Solution and Antibacterial Resin Coated Steel Plate
KR101094836B1 (en) Coating composition, films thereof, antireflection coatings, and image displays

Legal Events

Date Code Title Description
A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20050318

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20050520

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20050707

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20060317

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20060515

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20060608

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20060621

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090707

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100707

Year of fee payment: 4

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100707

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110707

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110707

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120707

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130707

Year of fee payment: 7

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees