JP6270440B2 - Molded body having antibacterial properties - Google Patents

Description

  The present invention relates to a molded article having antibacterial properties, and more particularly to a molded article on which a surface layer having antibacterial properties is formed.

In recent years, in addition to products used in places where bacteria and soot are prone to breed, such as containers used under hot and humid conditions such as medical supplies, kitchens, bathrooms, and washrooms, for example, public such as hanging leather Various antibacterial compositions are proposed because antibacterial performance is required for various products such as those used in places, housing-related materials such as wallpaper and joinery, air conditioner filters, stationery, etc. Has been.
Examples of such antibacterial compositions include molded products made of a thermoplastic resin or thermosetting resin containing an antibacterial agent, a coating film made of paint containing an antibacterial agent, or an antibacterial agent dispersed in a solvent. It is provided in various forms such as a dispersed liquid.

For example, the following Patent Document 1 describes a composition containing a solvent, silver nanoparticles, and a stabilizer, and the following Patent Document 2 includes an organic silver antibacterial agent and an organic antibacterial agent. An antimicrobial composition is described.
The composition described in Patent Document 1 is composed of a dispersion liquid in which silver nanoparticles are dispersed in a solvent. However, it is difficult to disperse silver nanoparticles without agglomeration, and aggregation is prevented. In order to achieve this, a stabilizer is essential, and it is not yet satisfactory in terms of transparency and efficient use of silver. In addition, in the composition described in Patent Document 2, antibacterial performance is imparted to the resin molded body itself in combination with a resin, instead of applying the above substance to a molded body molded in advance as in Patent Document 1. However, it is advantageous in terms of productivity and sustainability of the effect, but to exhibit antibacterial performance equivalent to or higher than that of conventional materials with a content less than the conventional amount of expensive materials such as silver. I'm still not fully satisfied.

  Moreover, the following patent document 3 describes a photocurable composition for antibacterial coating in which a silver salt is contained in a photocurable acrylic resin, and further, the following patent document 4 describes a photocurable resin. There have been proposed resin moldings such as various protective plates for displays having antibacterial properties, which contain antibacterial agents and / or antifungal agents.

Special table 2008-508321 JP 2010-248124 A JP-A-8-31373 International Publication No. 2011/007650

  However, as in the resin compositions described in Patent Documents 3 and 4, in a resin composition obtained by blending a silver salt with a photocurable acrylic resin, the silver salt is efficiently and uniformly dispersed in the acrylic resin. Therefore, when an antibacterial layer made of such a resin composition is used as the surface layer of a colored molded article, light is scattered on the antibacterial agent particles, resulting in a dull color or an original coloration. There is a problem of damaging the color. In addition, when the antibacterial agent itself has a color, there is also a problem that the original color tone imparted to the molded article is impaired.

  Accordingly, an object of the present invention is to provide a molded article that maintains the original color tone of the colored molded article and that is remarkably excellent in antibacterial performance.

According to the present invention, a molded body having a layer made of a curable resin containing an inorganic antibacterial agent and a metal oxide on the surface, wherein the inorganic antibacterial agent is a metal of silver, copper, or zinc. There is provided a molded article characterized in that it is a fatty acid-modified metal ultrafine particle comprising fatty acid and glyceride coordinated on the surface of the ultrafine particle .
According to the present invention, there is also provided a molded body having a surface layer made of a curable resin containing an inorganic antibacterial agent and a lower layer made of a curable resin containing a metal oxide, wherein the inorganic antibacterial agent is silver, There is provided a molded body characterized in that it is a fatty acid-modified metal ultrafine particle in which a fatty acid and a glyceride are coordinated on the surface of a metal ultrafine particle of either copper or zinc .

In the molded product of the present invention,
(1) The thickness of the layer containing the fatty acid-modified metal ultrafine particles is 0.1 to 15 μm or less,
(2) The color difference (ΔE) represented by the following formula in the layer containing the fatty acid-modified metal ultrafine particles is 1.6 or less,
ΔE = ((L ^* −L ^* ₀ ) ² + (a ^* −a ^* ₀ ) ² + (b ^* −b ^* ₀ ) ² ) ^0.5
... (1)
In the formula, L ^* ₀ , a ^* ₀ and b ^* ₀ are values when fatty acid-modified metal ultrafine particles are not contained, and L ^* , a ^* and b ^* are fatty acid-modified metal ultrafine particles 0.005 to 0.005. 0.05
The thickness of the layer containing by weight% is the value of the time of 0.1-15.
(3) pre-Symbol curing resin, it is actinic radiation-curable resin,
( 4 ) The metal oxide is at least one oxide or composite oxide selected from titanium, cobalt, aluminum, silicon, zinc, iron, nickel, antimony, barium, chromium, and vanadium.
Is preferred.

The inorganic antibacterial agent used in the present invention is a fatty acid-modified metal ultrafine particle in which a fatty acid is coordinated on the surface of the metal ultrafine particle. Has been prevented. Therefore, it is excellent in antibacterial performance and transparency, and does not impair the color imparted by the metal oxide contained in the surface layer or the metal oxide contained in the lower layer.
Moreover, since the layer containing the inorganic antibacterial agent is located on the surface of the molded article, metal ions are easily eluted from the surface, and excellent antibacterial performance is exhibited.
In addition, since glyceride is coordinated around the fatty acid coordinated on the surface of the metal ultrafine particle or on the particle surface, the glyceride is remarkably excellent in compatibility with a low boiling point solvent. It is possible to efficiently prepare a dispersion containing fatty acid-modified ultrafine metal particles consisting of a low-boiling solvent that contains a stable dispersion at a high concentration, and this can be blended with the curable resin that constitutes the surface layer with good dispersibility and handling properties. In addition, in this specification, antibacterial shows what suppresses proliferation and reproduction of a microbe.

As described above, the molded article of the present invention can be added and applied to the curable resin while maintaining the state of the fatty acid-modified metal ultrafine particles having an average primary particle diameter of 100 nm or less in the curable resin. It has excellent antibacterial properties without degrading the performance derived from the metal oxide used as a coloring material or the like. This effect is also apparent from the results of Examples described later.
That is, a curable resin layer (first layer) containing an inorganic antibacterial agent composed of fatty acid-modified silver ultrafine particles on a colored layer (second layer) containing a metal oxide composed of titanium oxide or aluminum-cobalt oxide. When the layer is applied, the fatty acid-modified silver ultrafine particles are uniformly dispersed in the curable resin without agglomeration. (Examples 1 to 5).

On the other hand, when the fatty acid-modified silver ultrafine particles are not contained, the antibacterial effect is not exhibited (Comparative Example 1). In addition, when silver ion exchange zeolite, which is a conventional inorganic antibacterial agent, is used, the antibacterial effect does not appear when the content is small, and when the content is large, the antibacterial effect is exhibited but the particle size is large. Since the color developability derived from the metal oxide is lowered, the color developability and the antibacterial property cannot be satisfied simultaneously (Comparative Examples 2 to 4).
Further, even when the content of the fatty acid-modified silver ultrafine particles is as small as 0.02% by weight, when the coating layer thickness is as large as 20 μm, the light yellowish coloration consisting of plasmon absorption of the fatty acid-modified silver ultrafine particles is remarkable. (Reference Example 1).
Even if the fatty acid-modified silver ultrafine particles and the metal oxide coexist in the same curable resin layer, the antibacterial effect can be exhibited without degrading the performance of the metal oxide (Example 6).

(Inorganic antibacterial agent)
In the present invention, an inorganic antibacterial agent comprising fatty acid-modified metal ultrafine particles having an average primary particle size of 100 nm or less and having fatty acid coordinated around metal ultrafine particles is used as the inorganic antibacterial agent.
Fatty acids in fatty acid-modified metal ultrafine particles include myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, paratoylic acid, succinic acid, malonic acid, tartaric acid, malic acid, glutaric acid, adipic acid, acetic acid, etc. Examples thereof include aliphatic carboxylic acids, phthalic acids, maleic acids, isophthalic acids, terephthalic acids, benzoic acids, aromatic carboxylic acids such as naphthenic acids, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acids.
In the present invention, the fatty acid to be used is particularly preferably a higher fatty acid such as myristic acid, stearic acid, palmitic acid, etc., and particularly preferably a branched fatty acid having a large number of carbon atoms.

Examples of the fatty acid metal salt that is a suitable starting material for the metal ultrafine particles include silver myristate and silver stearate. The metal ultrafine particles have a metal at the center and an average particle diameter of 1 to 500 μm. In particular, it is preferably in the range of 10 to 200 μm. In addition, the average particle diameter as used herein refers to an average value of a single particle having no gap between the metals.
The metal component of the ultrafine metal particles may be at least one selected from the group consisting of Cu, Ag, Au, Id, Pd, Pt, Fe, Ni, Co, Zn, Nb, Ru, and Rh. Silver, copper, and zinc are preferable from the viewpoint of antibacterial performance, and silver is particularly preferable.

  In the present invention, it is particularly preferable that the fatty acid-modified metal ultrafine particles are metal ultrafine particles in which fatty acid and glyceride are coordinated on the surface of any one of silver, copper and zinc metal ultrafine particles. Since glycerides are coordinated around the fatty acid coordinated on the surface of the fine particles or on the particle surface, they are uniformly dispersed with good dispersibility in the curable resin. In addition, since the fatty acid-modified metal ultrafine particles are metal ultrafine particles in which glycerides are coordinated around the fatty acid or on the particle surface, direct contact between the metal ultrafine particle surface and the resin in the curable resin layer is reduced. In addition, the degradation of the resin can be effectively suppressed to reduce the decrease in the molecular weight of the resin, and the moldability and workability are effectively prevented from being inhibited.

In the present invention, it is particularly preferred that such fatty acid-modified metal ultrafine particles are used as a dispersion, and particularly that glycerides are coordinated around or around the fatty acid coordinated on the surface of the metal ultrafine particles. It is remarkably excellent in dispersion stability and hardly precipitates even after a long time. In addition, since glycerides are remarkably excellent in compatibility with low-boiling solvents, extraction from high-boiling solvents to low-boiling solvents is promoted as described later, and fatty acid-modified metal ultrafine particles are dispersed at high concentrations with good dispersion stability. A dispersion containing ultrafine fatty acid-modified metal particles composed of a low-boiling solvent can be prepared.
Fatty acid-modified metal ultrafine particle-containing dispersion has an average primary particle size of 100 nm or less, particularly 10 to 50 nm, and an average secondary particle size of 900 nm or less, particularly 200 nm to 700 nm, in a low-boiling solvent such as methyl isobutyl ketone and methyl ethyl ketone. It is a dispersion in which particles are dispersed, and when used in a curable resin, the transparency of the composition itself is not lowered. In addition, the average primary particle diameter as used in this specification means the thing which made the thing without a clearance gap between a metal particle and a metal particle as one particle, and took the average. The average secondary particle diameter refers to a particle in which metal particles and metal particles are packed, and an average of the particles.
Further, since the fatty acid-modified metal ultrafine particles are uniformly dispersed without agglomeration, excellent antibacterial performance can be expressed.

[Dispersion containing fatty acid-modified metal ultrafine particles]
The above-mentioned dispersion containing fatty acid-modified metal ultrafine particles is prepared by the following two production methods.
(1) First production method (1-1) First step In the first step in the first production method, fatty acid or glyceride is coordinated to the surface of ultrafine metal particles in glycerin, which is a high-boiling solvent. Metal ultrafine particles are produced. The conditions are not limited as long as such ultrafine metal particles can be formed. Preferably, saccharin is added to glycerin as a fatty acid metal salt containing any metal of silver, copper, and zinc and an ionic stabilizer. After heating, the temperature of the high-boiling solvent is heated to 120 to 230 ° C., particularly 140 to 170 ° C. and depends on the heating temperature, but it is heated and mixed for 10 to 120 minutes, particularly 30 to 80 minutes. This makes it possible to form ultrafine metal particles in which fatty acid and glyceride are coordinated on the ultrafine metal particle surface in glycerin. That is, by heating the fatty acid metal salt in the above temperature range, the fatty acid metal salt is decomposed and reduced to fatty acid and metal, the metal forms ultrafine metal particles, and the fatty acid coordinates to the particle surface. The esterification reaction of the fatty acid and glycerin proceeds to produce glyceride, and glyceride is coordinated on the surface of the metal ultrafine particle like the fatty acid, and the metal ultrafine particle is dispersed in glycerin.
At this time, the fatty acid metal salt which is an antibacterial component is desirably blended in an amount of 0.1 to 2% by weight. When the amount of the fatty acid metal salt is less than the above range, sufficient antibacterial performance cannot be imparted to the dispersion, while when the amount of the fatty acid metal salt is larger than the above range, the antibacterial effect is further increased. However, it is not preferable in terms of economy and moldability.

(1-2) Second Step Subsequently, a low boiling point solvent is added to the metal ultrafine particle-containing glycerin, and then stirred and mixed to prepare a mixed solution. At this time, another high boiling point solvent such as ethylene glycol may be added together with the low boiling point solvent as an extraction aid.
The amount of the low-boiling solvent added cannot be generally specified, but is desirably in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the high-boiling solvent used.
Moreover, it is preferable that other high boiling point solvents, such as ethylene glycol added with a low boiling point solvent, exist in the range of 50-100 weight part with respect to 100 weight part of low boiling point solvents.
(1-3) Third step After the high-boiling solvent and the low-boiling solvent are phase-separated by allowing the mixture of the high-boiling solvent and the low-boiling solvent to stand at a temperature of 0 to 40 ° C. for 60 minutes or more, Remove boiling solvent.
When the mixed liquid is phase-separated, the ultrafine metal particles, which are present in the high-boiling solvent and coordinated with fatty acid and glyceride on the surface of the ultrafine metal particles, are extracted to the low-boiling solvent side, and unreacted fatty acid metal Aggregates and saccharin that have become metal only due to excessive progress of salt and reduction remain in the high-boiling solvent. By removing the high-boiling solvent, only the ultrafine metal particles are dispersed in the low-boiling solvent. A liquid can be obtained.
The removal of the high boiling point solvent can be carried out by a conventionally known method such as simple distillation, vacuum distillation, precision distillation, thin film distillation, extraction, membrane separation or the like.

(2) Second production method (2-1) First step In the first step of the second production method, the main purpose is to produce ultrafine metal particles in which fatty acids are coordinated in glycerol, which is a high-boiling solvent. As long as such ultrafine metal particles can be formed, the conditions are not limited. Preferably, saccharin as a fatty acid metal salt and an ionic stabilizer is added to glycerin, and the temperature of the high-boiling solvent after the addition. Is preferably 120 to 230 ° C., particularly 140 to 170 ° C., and then heated and mixed for 10 to 120 minutes, particularly 30 to 80 minutes.
In the second production method, as in the first production method, it is desirable that metal ultrafine particles formed by coordination of fatty acids and glycerides are formed on the surface of the metal ultrafine particles. The content of ultrafine metal particles in the liquid can be increased.

(2-2) Second Step Subsequently, a glyceride-containing low-boiling solvent is added to and mixed with the ultrafine metal particle-containing glycerin to prepare a mixed solution. At this time, as described above, another high boiling point solvent such as ethylene glycol may be added together with the low boiling point solvent.
When the metal ultrafine particle-containing glycerin is mixed with the glyceride-containing low-boiling solvent, the fatty acid and glyceride are coordinated on the surface of the metal ultrafine particle, and the metal ultrafine particle similar to the above-mentioned first production method is produced at a high concentration.
The content of glyceride in the low boiling point solvent varies depending on the content of the antibacterial component to be used, etc., and cannot be generally specified, but may be in the range of 0.02 to 5% by weight with respect to 100 parts by weight of the low boiling point solvent. Is preferred.
The amount of the glyceride-containing low-boiling solvent varies depending on the glyceride content and the content of the antibacterial component, and cannot be generally defined, but is in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the high-boiling solvent. It is desirable.
Moreover, it is preferable that other high boiling point solvents, such as ethylene glycol added with a low boiling point solvent, exist in the range of 50-100 weight part with respect to 100 weight part of low boiling point solvents.

(2-3) Third Step Similar to the first production method, the high-boiling solvent and the low-boiling point are obtained by allowing the mixed solution of the high-boiling point solvent and the low-boiling point solvent to stand at a temperature of 0 to 40 ° C. for 60 minutes or more. After phase separation of the solvent, the high boiling point solvent is removed to obtain a dispersion in which only the ultrafine metal particles are dispersed in the low boiling point solvent.

[Ion stabilizer]
In preparation of the fatty acid-modified metal ultrafine particle-containing dispersion, it is particularly preferable to contain an ion stabilizer from the viewpoint of suppressing excessive reduction of metal ions. Thereby, the reduction | restoration of a metal ultrafine particle can be suppressed and antibacterial performance can be improved.
As such an ion stabilizer, a part or all of which is soluble in a low-boiling solvent or a high-boiling solvent and has an acid dissociation coefficient (pka) of 4.5 or less, for example, salicylic acid ( pKa 2.8), aspartic acid (pKa 1.93), citric acid (pKa 2.90), fumaric acid (pKa 2.9), benzoic acid (pKa 4.2), o-benzoic acid sulfimide (saccharin (pKa 2.2)) , M-hydroxybenzoic acid (pKa4.1), o-aminobenzoic acid (pKa2.0), m-aminobenzoic acid (pKa3.2), p-aminobenzoic acid (pKa3.1) and combinations thereof . pKa is an acid dissociation constant. In the case of a polybasic acid, pKa = −logKa, where Ka is the value of the first stage.

  As fatty acids in fatty acid metal salts used in combination with the above ion stabilizers, myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, paratoylic acid, succinic acid, malonic acid, tartaric acid, malic acid, Examples include glutaric acid, adipic acid, acetic acid, and the like, and among them, a stearic acid metal salt can be preferably used.

[High boiling point solvent]
Glycerin can be used as the high-boiling solvent used for the preparation of the fatty acid-modified ultrafine metal particle dispersion, and the high-boiling solvent that can be used with glycerin without agglomerating and precipitating the fatty acid-modified ultrafine metal particles. Although it can be used as long as it is dispersible, preferred examples include glycol solvents such as ethylene glycol, diethylene glycol, and polyethylene glycol, and ether solvents such as diethyl ether, and particularly ethylene glycol, diethylene glycol, and polyethylene. Glycol and diethyl ether can be preferably used.

[Low boiling solvent]
In the dispersion containing ultrafine metal particles, the low-boiling solvent used as a dispersion medium containing ultrafine metal particles is a solvent that is smaller than the boiling point of the high-boiling solvent and can be two-phase separated from the high-boiling solvent. It is important that the difference in SP value between the solvent and the fatty acid or glyceride coordinated on the surface of the ultrafine metal particles is small, thereby extracting the ultrafine silver particles from the high boiling point solvent and removing the high boiling point solvent as a by-product or residue. It can be removed together with the object.
The boiling point of the low-boiling solvent is preferably in the range of 40 to 120 ° C. from the viewpoints of productivity and handleability of the resin composition layer constituting the transparent material.
Such low boiling point solvents include, but are not limited to, ketones such as methyl isobutyl ketone and methyl ethyl ketone.
In the present invention, among the above low-boiling solvents, a low-boiling solvent having high compatibility with the above-mentioned fatty acid or glyceride is selected in order to enable efficient extraction of ultrafine metal particles in the high-boiling solvent during the two-phase separation. Therefore, the low boiling point solvent is selected so that the difference (absolute value) between the SP value (solubility parameter) of the fatty acid or glyceride coordinated on the particle surface and the SP value of the low boiling point solvent is 3 or less. It is desirable to do.
Specifically, when silver stearate is used as the fatty acid metal salt, methyl isobutyl ketone can be preferably used.

The dispersion in which the fatty acid-modified metal ultrafine particles are dispersed in the above-mentioned solvent without agglomeration / precipitation is mixed with the fatty acid-modified metal ultrafine particles and the solvent, and then stirred with a blade such as a propeller blade, a turbine blade, or a paddle blade. It can be obtained by mixing and dispersing using a disperser, a mill type disperser such as a ball mill, a bead mill or a colloid mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer or the like.
In this dispersion, the content of the fatty acid-modified metal ultrafine particles is preferably in the range of 0.05 to 5 parts by weight, particularly 0.1 to 3 parts by weight with respect to 100 parts by weight of the solvent. When the content of fatty acid-modified metal ultrafine particles is less than the above range, in order to obtain the desired antibacterial properties, it is necessary to add a large amount of dispersion to the curable resin, so that the moldability is inferior. On the other hand, if the content of the fatty acid-modified metal ultrafine particles is larger than the above range, the dispersibility of the fatty acid-modified metal ultrafine particles becomes poor.
Since this dispersion has a transmittance of 80% or more, it is effective to impair the excellent transparency of the photocurable acrylic resin even when blended with the photocurable acrylic resin. Has been prevented.

(Metal oxide)
The metal oxide used in the present invention means all metal compounds used as compounding agents for various resins, but is a metal oxide used as a coloring material, specifically, titanium, cobalt, aluminum. And at least one oxide or composite oxide selected from silicon, zinc, iron, nickel, antimony, barium, chromium, and vanadium.

(Curable resin)
Examples of the curable resin used in the present invention include conventionally known thermosetting resins and active energy ray curable resins such as ultraviolet rays and electron beams, and it is particularly preferable to use an active energy ray curable resin. .
Examples of the thermosetting resin include phenol resin, epoxy resin, urethane resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, and silicone resin.
Radical polymerization type UV curable resins include, but are not limited to, polyfunctional acrylate resins such as polyhydric alcohol acrylic acid or methacrylic acid ester, diisocyanate, polyhydric alcohol and hydroxyalkyl ester of acrylic acid or methacrylic acid. Examples thereof include polyfunctional urethane acrylate resins synthesized from the above. Furthermore, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and the like can be suitably used as necessary.

  In addition, as reactive diluents for these resins, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (which have relatively low viscosity) Bi- or higher functional monomers and oligomers such as (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, and monofunctional Monomers such as acrylic esters such as N-vinylpyrrolidone, ethyl acrylate, propyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate Derivatives such as acrylate, hexyl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, nonylphenyl methacrylate, etc., tetrahydrofurfuryl methacrylate, and its caprolactone derivatives, styrene, α-methylstyrene, acrylic Acids and the like and mixtures thereof can be used.

  On the other hand, cationic polymerization type ultraviolet curable resins can be broadly classified into addition polymerization type and ring-opening polymerization type. As addition polymerization type compounds, vinyl ether compounds having high electron density vinyl groups, styrene derivatives, etc. are subjected to ring-opening polymerization. As the type of compound, various heterocyclic compounds such as epoxy compounds, lactone compounds, oxetane compounds that are 4-membered cyclic ethers, and the like can be used.

  When the active energy rays are ultraviolet rays, it is necessary to add a photosensitizer (photopolymerization initiator), and benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether are used as radical generating photopolymerization initiators. Benzoin such as benzyl methyl ketal and alkyl ethers thereof; acetophenones such as acetophenone, 2,2, -dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; methyl anthraquinone, 2-ethylanthraquinone, 2-amyl Anthraquinones such as anthraquinone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyldimethyl Ketals such as tar; benzophenone, and the like 4,4-bis benzophenones such as methylamino benzophenone and azo compounds. These can be used singly or as a mixture of two or more, and further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate, etc. It can be used in combination with an initiation aid or the like.

Photoacid generators that can be used as cationic polymerization initiators can be broadly classified into ionic compounds and nonionic compounds. Examples of ionic compounds include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, and triaryl phosphonium salts. BF ₄ —, PF ₆ —, AsF ₆ —, SbF ₆ —, and the like are used as counter ions. Such an onium salt photoacid generator can be used in combination with a photosensitizer such as anthracene or thioxanthone, if necessary. As the nonionic photoacid generator, those that generate carboxylic acid, sulfonic acid, phosphoric acid, hydrogen halide, etc. by light irradiation can be used. Specifically, 2-nitrobenzyl ester of sulfonic acid, iminosulfo acid Nate, 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative, N-hydroxyimidosulfonate, tri (methanesulfonyloxy) benzene derivative, etc. can be used, and carboxylic acid o-nitrobenzyl ester, 1-oxo-2 -Diazonaphthoquinone-5-arylsulfonate, triaryl phosphate ester derivatives and the like can be used.
The polymerization initiator can be contained in a conventionally known formulation. Specifically, it is contained in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerizable resin component. It is preferable.
Moreover, a plasticizer, a leveling agent, a thickener, a thickener, a stabilizer, antioxidant, an ultraviolet absorber etc. can be mix | blended with curable resin according to well-known prescription as needed.

  It is preferable to use ultraviolet rays or electron beams as the active energy ray source, and it is particularly preferable to use ultraviolet rays. For UV irradiation, light sources such as high-pressure mercury lamp, low-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, etc. can be used. A metal halide lamp is generally used for curing. For electron beam irradiation, 50 to 1000 KeV emitted from various electron beam accelerators such as cockloftwald type, bandecraft type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type, preferably An electron beam having an energy of 100 to 300 KeV can be used.

(Molded body)
As the molded article of the present invention, at least one surface of the molded article has a layer made of an active energy ray-curable resin containing metal oxide and fatty acid-modified metal ultrafine particles, or at least of the molded article On one surface, a lower layer made of an active energy ray-curable resin containing a metal oxide, and a surface layer made of an active energy ray-curable resin containing fatty acid-modified metal ultrafine particles on the lower layer are formed. Can be mentioned.

The material constituting the molded body in the present invention is not particularly limited as long as a layer made of an active energy ray-curable resin can be formed on the surface, and is low-, medium-, high-density polyethylene, linear low density polyethylene, wire. Ultra-low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene -1 olefin resin such as copolymer, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide resin such as nylon 6, nylon 6,6, nylon 6,10, etc., thermoplastic resin such as polycarbonate resin, Phenolic resin, epoxy resin Urethane resins, melamine resins, urea resins, alkyd resins, unsaturated polyester resins, thermosetting resins such as silicone resin, glass, can be exemplified metal, ceramics, and paper.
Also, the shape of the molded body is not particularly limited, and various shapes such as a sheet shape, a film shape, and a container shape such as a cup and a tray can be employed depending on the application.

In the present invention, the metal oxide and fatty acid-modified metal ultrafine particle-containing layer has a metal oxide content of 100 parts by weight of the resin content of the curable resin in both cases of a single layer structure and a two-layer structure. And preferably in the range of 1 to 50 parts by weight, particularly 10 to 30 parts by weight. The content of the fatty acid-modified metal ultrafine particles is preferably in the range of 0.005 to 0.05 parts by weight, particularly 0.01 to 0.03 parts by weight with respect to 100 parts by weight of the resin content of the curable resin. . If the content of fatty acid-modified metal ultrafine particles is less than the above range, the antibacterial performance will be inferior to that in the above range, whereas if the content of fatty acid-modified metal ultrafine particles is larger than the above range In this case, the transparency is inferior to that in the above range, and the color tone of the metal oxide may be impaired.
In the case where the content of the fatty acid-modified metal ultrafine particles is within the above range, the thickness of the layer containing both the metal oxide and the fatty acid-modified metal ultrafine particles is 0.1 to 15 μm, particularly 1 to 10 μm. It is preferable to be in the range. In the case of a two-layer structure, the thickness of the surface layer containing the fatty acid-modified metal ultrafine particles is preferably in the range of 0.1 to 15 μm, particularly 3 to 10 μm, and the thickness of the lower layer containing the metal oxide is 1 to 100 μm, and particularly preferably in the range of 10 to 50 μm.

In order to form a layer to be formed on the surface of the molded product in the present invention, a coating liquid composed of the above-mentioned actinic energy curable resin, a polymerization initiator, a dispersion containing fatty acid-modified metal ultrafine particles, and a metal compound is prepared, It can be formed by coating this on the surface of the molded body and irradiating it with ultraviolet ray or electron beam energy such as an electron beam and curing it. Similarly, in the case of a two-layer structure, a coating solution comprising an active ray energy curable resin, a polymerization initiator, and a metal compound, and an active ray energy curable resin, a polymerization initiator, and a dispersion containing fatty acid-modified metal ultrafine particles. Each of the coating liquids is prepared, and after the lower layer is cured and formed, the surface layer is cured and formed.
The coating method can be appropriately selected from conventionally known coating methods, for example, bar coating, gravure coating, spray coating, spin coating, dip coating and the like, depending on the shape of the molded body.
In preparing the coating liquid, it is desirable that the actinic energy curable resin is previously diluted with a solvent and then mixed with a polymerization initiator, a dispersion containing fatty acid-modified metal ultrafine particles and a diluent solvent. Examples thereof include, but are not limited to, methanol, ethanol, isopropanol, diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like.

The curing conditions cannot be generally defined by the type of resin used, the polymerization initiator, the diluent solvent or the type of fatty acid-modified metal ultrafine particles, or the type of viscosity, energy source, etc. In general, it is preferable to irradiate in the range of 100 to 500 J / cm ² .

(Color evaluation)
The color tone of the molded product was measured with SM color computer SM-4S-2 (manufactured by Suga Test Instruments Co., Ltd.), and L * value, a * value, and b * value were obtained.
(Antimicrobial test)
The antibacterial test method conformed to JIS Z 2801: 2000 antibacterial processed product-antibacterial test method. S. aureus was used as the bacterial species. The antibacterial activity value was defined as the logarithmic value of the number obtained by dividing the number of bacteria after cultivation of the unprocessed test piece by the number of bacteria after cultivation of the antibacterial processed test piece. The case where the antibacterial activity value was 2.0 or more was judged as ◯, and the case where the antibacterial activity value was less than 2.0 was judged as ×.

Example 1
To 700 g of glycerin, 3.85 g of silver stearate and 0.385 g of saccharin were added and heated at 150 ° C. for 40 minutes. After cooling glycerin to 60 ° C., 700 g of methyl isobutyl ketone was added and stirred. After standing for about 1 hour, a methyl isobutyl ketone layer was collected to obtain a dispersion containing fatty acid-modified silver ultrafine particles. A photocurable acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), a dispersion containing ultrafine fatty acid-modified silver particles, and a photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., Ltd.) mixed with a diluting solvent in advance are mixed with fatty acid-modified silver superpolymer. After mixing with a bar coater on a PET film having a 30 μm coating layer (second layer) previously containing a white pigment of titanium oxide, mixed at a weight ratio such that the fine particle content is 0.01% by weight, UV A coating film of 5 μm (first layer) made of the resin composition was formed on the PET film by curing with an irradiation apparatus. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Example 2)
A PET film having a first layer and a second layer was obtained in the same manner as in Example 1 except that the mixture was mixed at a weight ratio such that the content of fatty acid-modified silver ultrafine particles was 0.02% by weight. In the same manner as in Example 1, color tone evaluation and antibacterial test were performed. The results are shown in Table 1.

(Example 3)
Mix in a weight ratio such that the content of fatty acid-modified silver ultrafine particles is 0.01% by weight, and use a bar coater on a PET film having a 30 μm coating layer (second layer) containing a white pigment of titanium oxide in advance. After application, PET having a first layer and a second layer in the same manner as in Example 1 except that a coating film 10 μm (first layer) made of a resin composition was formed on a PET film by curing with a UV irradiation apparatus. A film was obtained. In the same manner as in Example 1, color tone evaluation and antibacterial test were performed. The results are shown in Table 1.

Example 4
To 700 g of glycerin, 3.85 g of silver stearate and 0.385 g of saccharin were added and heated at 150 ° C. for 40 minutes. After cooling glycerin to 60 ° C., 700 g of methyl isobutyl ketone was added and stirred. After standing for about 1 hour, a methyl isobutyl ketone layer was collected to obtain a dispersion containing fatty acid-modified silver ultrafine particles. A photocurable acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), a dispersion containing ultrafine fatty acid-modified silver particles, and a photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., Ltd.) mixed with a diluting solvent in advance are mixed with fatty acid-modified silver superpolymer. Mix in a weight ratio such that the fine particle content is 0.01% by weight, and use a bar coater on a PET film having a 30 μm coating layer (second layer) containing a blue pigment made of aluminum-cobalt oxide in advance. After coating, the coating film was cured with a UV irradiation device to form a coating film 5 μm (first layer) made of the resin composition on the PET film. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Example 5)
On a PET film having a 30 μm coating layer (second layer) previously mixed with a blue pigment of aluminum-cobalt oxide, mixed at a weight ratio such that the fatty acid-modified silver ultrafine particle content is 0.02% by weight. The first layer and the second layer were the same as in Example 4 except that a coating film 10 μm (first layer) made of a resin composition was formed on a PET film by curing with a UV irradiation device after coating with a bar coater. A PET film having a layer was obtained. In the same manner as in Example 4, color tone evaluation and antibacterial test were performed. The results are shown in Table 1.

(Comparative Example 1)
A photo-curing acrylic resin (manufactured by Taisei Fine Chemical Co., Ltd.) previously mixed with a diluting solvent and a photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., Ltd.) are mixed, and a 30 μm coating layer containing a white pigment made of titanium oxide in advance ( After coating with a bar coater on the PET film having the second layer), it was cured with a UV irradiation device to form a coating film 5 μm (first layer) made of the resin composition on the PET film. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Comparative Example 2)
0.7 g of silver ion exchanged zeolite and 700 g of methyl isobutyl ketone were added and stirred to obtain a silver ion exchanged zeolite-containing dispersion. Photo-curing acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), silver ion-exchanged zeolite-containing dispersion and photopolymerization initiator (Ciba Specialty Chemical Co., Ltd.) previously mixed with a diluting solvent and fatty acid-modified silver ultrafine particles for the resin component After mixing with a bar coater on a PET film having a 30 μm coating layer (second layer) containing a white pigment of titanium oxide, the mixture is mixed at a weight ratio such that the content becomes 0.02% by weight, and then irradiated with UV. A coating film of 5 μm (first layer) made of a resin composition was formed on a PET film by curing with an apparatus. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Comparative Example 3)
17.5 g of silver ion exchange zeolite and 700 g of methyl isobutyl ketone were added and stirred to obtain a silver ion exchange zeolite-containing dispersion. Photo-curing acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), silver ion-exchanged zeolite-containing dispersion liquid and photopolymerization initiator (Ciba Specialty Chemical Co., Ltd.) previously mixed with a diluting solvent UV irradiation device after mixing with a bar coater on a PET film having a 30 μm coating layer (second layer) previously mixed with a titanium oxide white pigment, mixed in a weight ratio such that the amount is 0.5 wt% The coating film 5 μm (first layer) made of the resin composition was formed on the PET film by curing with a PET. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Comparative Example 4)
A film was obtained in the same manner as in Comparative Example 3 except that a PET film having a 30 μm coating layer (second layer) containing a blue pigment made of aluminum-cobalt oxide in advance was used. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Reference Example 1)
After coating with a bar coater on a PET film having a 30 μm coating layer (second layer) containing a titanium oxide white pigment in advance, a coating film of 20 μm (first layer) made of a resin composition is cured by a UV irradiation device. ) Was formed on a PET film in the same manner as in Example 1 to obtain a PET film. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 1.

(Example 6)
To 700 g of glycerin, 3.85 g of silver stearate and 0.385 g of saccharin were added and heated at 150 ° C. for 40 minutes. After cooling glycerin to 60 ° C., 700 g of methyl isobutyl ketone was added and stirred. After standing for about 1 hour, a methyl isobutyl ketone layer was collected to obtain a dispersion containing fatty acid-modified silver ultrafine particles. A photo-curing acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), a dispersion containing fatty acid-modified silver ultrafine particles, a titanium oxide pigment, and a photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., Ltd.) previously mixed with a diluent solvent The fatty acid-modified silver ultrafine particle content is mixed at a weight ratio of 0.01% by weight and titanium oxide is 15% by weight, coated on a PET film with a bar coater, and then cured with a UV irradiation device to obtain a resin composition. A 10 μm thick coating film was formed on a PET film. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 2.

(Comparative Example 6)
Photo-curing acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), titanium oxide pigment and photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., Ltd.) previously mixed with a diluting solvent so that titanium oxide is 15% by weight based on the resin content. The mixture was mixed at an appropriate weight ratio, applied onto a PET film with a bar coater, and then cured with a UV irradiation device to form a 10 μm coating film of the resin composition on the PET film. About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 2.

(Comparative Example 7)
17.5 g of silver ion exchange zeolite and 700 g of methyl isobutyl ketone were added and stirred to obtain a silver ion exchange zeolite-containing dispersion. Photo-curing acrylic resin (manufactured by Taisei Fine Chemical Industry Co., Ltd.), silver ion-exchanged zeolite-containing dispersion liquid and photopolymerization initiator (Ciba Specialty Chemical Co., Ltd.) previously mixed with a diluting solvent The mixture was mixed at a weight ratio such that the amount was 0.5% by weight, coated on a PET film with a bar coater, and then cured with a UV irradiation device to form a coating film 10 μm composed of a resin composition on the PET film. . About the obtained film, color tone evaluation and the antibacterial test were implemented. The results are shown in Table 2.

  The molded article having antibacterial properties of the present invention is excellent in antibacterial performance and transparency because a surface layer containing fatty acid-modified metal ultrafine particles in which fatty acids are coordinated is formed on the surface of the metal ultrafine particles. It is excellent in economic efficiency because it can efficiently impart excellent antibacterial performance to the molded product without impairing the color tone imparted by the metal oxide contained together or the metal oxide contained in the lower layer. By using it as a coating material for a product, it becomes possible to impart antibacterial properties to the product.

Claims (6)

A molded body having a layer made of a curable resin containing an inorganic antibacterial agent and a metal oxide on the surface, wherein the inorganic antibacterial agent has fatty acid on the surface of ultrafine metal particles of silver, copper, or zinc. A molded article characterized in that it is a fatty acid-modified metal ultrafine particle formed by coordination of glycerides . A molded body having a surface layer made of a curable resin containing an inorganic antibacterial agent and a lower layer made of a curable resin containing a metal oxide, wherein the inorganic antibacterial agent is one of silver, copper, and zinc A molded article characterized in that it is a fatty acid-modified metal ultrafine particle in which fatty acid and glyceride are coordinated on the surface of the metal ultrafine particle.   The molded body according to claim 1 or 2, wherein the layer containing the fatty acid-modified metal ultrafine particles has a thickness of 0.1 to 15 µm or less. Molded body according to any one of claims 1 to 3 color difference represented by the following formula (Delta] E) is below 1.6 or less in the layer containing the fatty acid-modified metal ultrafine particles;
ΔE = ((L ^* −L ^* ₀ ) ² + (a ^* −a ^* ₀ ) ² + (b ^* −b ^* ₀ ) ² ) ^0.5
In the formula, L ^* ₀ , a ^* ₀ and b ^* ₀ are values when fatty acid-modified metal ultrafine particles are not contained, and L ^* , a ^* and b ^* are fatty acid-modified metal ultrafine particles 0.005 to 0.005. 0.05
The thickness of the layer containing by weight% is the value of the time of 0.1-15. The curable resin molded article according to any one of claims 1-4 which is an active energy ray-curable resin. Wherein the metal oxide is titanium, cobalt, aluminum, silicon, zinc, iron, nickel, antimony, barium, chromium, claim 1-5 is at least one oxide or composite oxide selected from vanadium The molded product according to 1.