JP7340501B2 - Protective equipment - Google Patents

Description

The present invention relates to protective equipment for protecting at least the eyes, such as face shields (or face guards) and goggles.

Traditionally, the face (particularly the eyes, mouth, nose, etc.) has been contaminated by dust and microorganisms (bacteria, viruses, etc.) at manufacturing, medical and bio-industry sites (factories, hospitals, research institutes, etc.). To prevent this, protective equipment such as goggles and face shields are worn. In particular, in the recent coronavirus pandemic, the risk of virus contamination is increasing, and there are increasing opportunities to wear protective equipment even outside of the industrial workplaces.

Transparency is required for these protective equipment because it is necessary to perform work while wearing the protective equipment, but in order to prevent the deterioration of transparency due to use and over time, it is necessary to prevent it from becoming cloudy or dirty. It is also necessary to prevent a decline in transparency.

In particular, in high-tech industries and medical settings, advanced image processing computers such as 3D images are being introduced, which reduces blurring and blurring of images observed while wearing protective equipment, and improves clarity. It also needs to be improved. In applications that require such high visibility, scratch resistance is also required because if the surface of the protective gear is damaged, high visibility cannot be guaranteed.

Furthermore, since the transparent film that constitutes the protective equipment is manufactured by a roll-to-roll method, there is also a need to improve industrial productivity.

JP-A No. 2010-60924 (Patent Document 1) discloses that an optical sheet with good contrast has a functional layer on at least one surface of a transparent base material, and a diffusion element is provided on the outermost surface and/or inside of this functional layer. An optical sheet for use on the surface of a display element is disclosed, which has the relationship represented by the following formula (I).

0.64<Q/P<0.94 (I)
(In the formula, P is the diffusion of light that is diffused and transmitted when visible light is irradiated perpendicularly from the surface opposite to the observer side of the optical sheet, measured in degrees from -85 degrees to +85 degrees. It shows the total transmission intensity, and Q (regular transmission intensity) shows the diffuse transmission intensity at 0 degrees).

JP 2016-218442A (Patent Document 2) describes a facial optical element in which the average distance between adjacent convex portions or concave portions is equal to or less than the wavelength of visible light, and which contains a (meth)acryloyl group-containing polymerizable compound. An optical element using a transparent laminate having a structure layer made of a polymer of an active energy ray-curable resin composition is disclosed, and the structure layer is used to transfer a transfer master having minute recesses or projections. It is manufactured by

Japanese Patent Application Publication No. 2010-60924 Japanese Patent Application Publication No. 2016-218442

However, Patent Document 1 does not describe protective equipment, and does not consider the contrast when the protective equipment is placed near the human eyes. On the other hand, Patent Document 2 describes a face protector, but in order to manufacture a transparent laminate, it is necessary to use a transfer master, resulting in low productivity. Furthermore, neither of Patent Documents 1 and 2 describes antibacterial properties. In particular, when antibacterial properties and scratch resistance are improved, visibility and productivity tend to decrease, and it is difficult to satisfy these properties in a well-balanced manner.

Therefore, an object of the present disclosure is to provide protective equipment with high visibility and productivity.

The present inventor has provided a transparent laminated film in which a functional layer having a specific arithmetic mean roughness Ra and a diffused transmission intensity ratio is laminated on at least one surface of a transparent base material layer, and has a specific transmitted image clarity. The present invention was completed based on the discovery that visibility and productivity can be improved by using the present invention in protective equipment worn on the head to protect at least the eyes.

That is, the protective equipment of the present disclosure is a protective equipment worn on the head to protect at least the eyes,
A transparent laminated film including a transparent base material layer and a functional layer laminated on at least one side of the transparent base material layer and having an uneven shape on the surface,
The arithmetic mean roughness Ra of the uneven shape is 0.015 μm or more, and the transparent laminated film has a transmitted image clarity of 70% or more as measured using an optical comb with a width of 0.125 μm,
The transparent laminated film is a protective device that satisfies the following formula (1).

(T5/T20)×100≧99.9 (1)
(In the formula, T5 is the diffused and transmitted light when visible light is irradiated perpendicularly from the outer surface (the surface opposite to the observer side) when the transparent laminated film is worn, from -5 degrees to +5 degrees. T20 is the sum of the diffused transmission intensity measured for each degree in the range of -20 to It shows the sum of the diffuse transmission intensity measured every 1 degree in the range up to +20 degrees).

In the transparent laminated film, the functional layer may be laminated on both sides of the transparent base layer. The functional layer may be a layer that does not contain translucent particles having a particle size of 0.5 μm or more. The antibacterial activity value R of the functional layer according to JIS Z 2801:2010 may be 2 or more. The functional layer may have a water contact angle of 20 degrees or less. The functional layer may have a pencil hardness of H or higher. The functional layer may be a hard coat layer. The functional layer may be formed of a cured product of a curable composition containing a curable resin having a plurality of (meth)acryloyl groups. The curable composition may further contain an antibacterial agent. The protective equipment may be a face shield, goggles or glasses. The protective equipment is a face shield including a main body for shielding (protecting) the face and a wearing part for wearing the main body on the head, and the main body is made of the transparent laminated film. It may be formed of.

In the present disclosure, a transparent laminated film is provided, in which a functional layer having a specific arithmetic mean roughness Ra and a diffuse transmission intensity ratio is laminated on at least one surface of a transparent base material layer, and a transparent laminated film having a specific transmitted image clarity. It is used for protective equipment worn on the head to protect the eyes, so visibility and productivity are high. In particular, it is possible to suppress blurring and blurring of observed images, and by forming the functional layer with a cured product of a specific curable composition, it is possible to improve the anti-fogging and anti-fouling properties, so it is possible to improve visual recognition after use over time. By forming functional layers on both sides, fogging caused by exhalation can also be suppressed. Furthermore, since the functional layer contains an antibacterial agent, antibacterial properties can also be improved, and the functional layer can be formed from a cured product of a specific curable composition containing a curable resin having a plurality of (meth)acryloyl groups. This also improves scratch resistance. In particular, by forming a cured product of a specific curable composition containing an antibacterial agent, antifogging properties, antifouling properties, scratch resistance, and antibacterial properties can be improved while maintaining high visibility and productivity.

FIG. 1 is a schematic diagram showing how a face shield is used as an example of the present disclosure.

[Transparent laminated film]
The protective device of the present disclosure includes a transparent laminated film including a transparent base material layer and a functional layer laminated on at least one surface of the transparent base material layer and having an uneven shape on the surface.

(Functional layer)
The functional layer has an uneven shape on the surface, and the arithmetic mean roughness Ra of the uneven shape is 0.015 μm or more, for example, 0.015 to 0.1 μm, preferably 0.02 to 0.08 μm, and It is preferably 0.03 to 0.06 μm, more preferably 0.04 to 0.05 μm, and most preferably 0.042 to 0.048 μm. If Ra is too small, blocking will occur when the transparent laminated film is wound up, reducing the productivity of the protective equipment. Moreover, if Ra is too large, there is a possibility that visibility will deteriorate.

The ten-point average roughness Rzjis of the uneven shape is, for example, 0.05 to 0.5 μm, preferably 0.08 to 0.4 μm, more preferably 0.1 to 0.37 μm, and even more preferably 0.2 to 0. 35 μm, most preferably 0.25-0.33 μm. If Rzjis is too small, blocking may occur when winding up the transparent laminated film, which may reduce the productivity of the protective equipment, and if Rzjis is too large, there is a risk of reduced visibility.

The average length RSm of the uneven-shaped roughness curve element is, for example, 20 to 300 μm, preferably 50 to 280 μm, more preferably 100 to 250 μm, more preferably 150 to 230 μm, and most preferably 200 to 220 μm. If RSm is too small, there is a risk that cloudiness will occur due to diffused light and visibility will decrease; on the other hand, if RSm is too large, the image will become blurred and visibility will decrease, or blocking will easily occur, making it difficult to protect. There is a possibility that the productivity of tools may decrease.

In this specification and claims, the arithmetic mean roughness Ra, ten-point mean roughness Rzjis, and average length RSm of roughness curve elements are defined as contact surface roughness according to JIS B 0601-2001. It can be measured using a scale meter, and more specifically, it can be measured by the method described in Examples below.

The water contact angle on the surface of the functional layer may be 100 degrees or less, but is preferably 50 degrees or less (particularly 20 degrees or less), for example 1 to 50 degrees, from the viewpoint of improving antifogging properties and antifouling properties. The temperature is preferably 3 to 30 degrees, more preferably 4 to 20 degrees, more preferably 5 to 15 degrees, and most preferably 6 to 10 degrees. The water contact angle may be 20 degrees or less (particularly 10 degrees or less) in order to improve anti-fog and stain resistance, and if the water contact angle is within this range, even if dirt adheres, it can be easily wiped off. I can do it.

Note that in this specification and claims, the water contact angle can be measured by a conventional method, for example, using an automatic dynamic contact angle meter.

The antibacterial activity value R of the functional layer may be 2 or more, preferably 3 or more, and more preferably 4 or more (for example, about 4 to 10). If the antibacterial activity value R is too low, there is a risk that the antibacterial properties will decrease.

In addition, in this specification and the claims, the antibacterial activity value R can be measured based on JIS Z 2801:2010, and in detail, it can be measured by the method described in the Examples described below.

The pencil hardness of the functional layer may be HB or higher, preferably F or higher, and more preferably H or higher (for example, about H to 2H). If the pencil hardness is too low, there is a risk that the scratch resistance will decrease.

In addition, in this specification and the claims, pencil hardness can be measured by a method based on JIS K 5400, and more specifically, by a method described in Examples described below.

The functional layer may be laminated on at least one surface of the transparent base material layer, but it is preferable to form it on both surfaces. If it is formed on both sides, when the main body of the protective equipment is formed of a transparent laminated film alone, such as a face shield, the function of the functional layer can be expressed on either the front side or the back side. When forming functional layers on both sides of the transparent base material layer, the first functional layer and the second functional layer formed on each surface may be different layers, but it may be difficult to From the point on, it is usually the same layer.

The thickness (average thickness) of the functional layer is, for example, 1 to 20 μm, preferably 2 to 10 μm, more preferably 3 to 9 μm, more preferably 4 to 8 μm, and most preferably 5 to 7 μm. If the thickness of the functional layer is too thin, there is a risk that the function will not be expressed, and if it is too thick, there is a risk that the productivity of the protective equipment will decrease.

Note that in this specification and claims, the average thickness of the functional layer can be determined by measuring any 10 points using an optical film thickness meter and calculating the average value.

The material of the functional layer is not particularly limited as long as it satisfies these characteristics. The material constituting the functional layer can be selected from various transparent organic materials (thermoplastic resins, thermosetting resins, photocurable resins, etc.) and inorganic materials (glass, ceramics, metals, etc.). The functional layer is preferably formed of a cured product of a curable composition containing a curable resin, since a functional layer having the above characteristics can be easily prepared by the presence of particles and by convection during the manufacturing process. A hard coat layer formed of the above-mentioned cured product is particularly preferable from the viewpoint of improving the hardness.

(A) Curable resin The curable resin may be either a thermosetting resin or a photocurable resin, but a photocurable resin is preferable from the viewpoint of productivity. The photocurable resin (photocurable resin precursor component) may be a compound that can be cured or crosslinked with active energy rays such as ultraviolet rays or electron beams to form a resin. Photocurable resins include monomers, oligomers (or resins, especially low molecular weight resins).

Examples of monomers include monofunctional monomers [(meth)acrylic monomers such as (meth)acrylic acid esters, vinyl monomers such as vinylpyrrolidone, isobornyl (meth)acrylate, adamantyl ( (meth)acrylates having a bridged cyclic hydrocarbon group such as meth)acrylate], bifunctional monomers [ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate , neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyoxytetramethylene glycol di(meth)acrylate; (Poly)oxyalkylene glycol di(meth)acrylate such as meth)acrylate; di(meth)acrylate having a bridged cyclic hydrocarbon group such as tricyclodecane dimethanol di(meth)acrylate and adamantane di(meth)acrylate] , trifunctional or higher polyfunctional monomers [glycerine tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxy Tri- to hexafunctional compounds such as ethyl)isocyanurate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylate, etc.].

As the oligomer or resin, for example, (meth)acrylate of bisphenol A-alkylene oxide adduct, epoxy (meth)acrylate [polyfunctional epoxy (meth)acrylate having two or more (meth)acryloyl groups], polyester (meth)acrylate ) acrylate [polyfunctional polyester (meth)acrylate having two or more (meth)acryloyl groups], urethane (meth)acrylate [polyfunctional urethane (meth)acrylate having two or more (meth)acryloyl groups], silicone Examples include (meth)acrylate [polyfunctional silicone (meth)acrylate having two or more (meth)acryloyl groups], (meth)acrylic polymer having a polymerizable group, and the like.

These photocurable resins can be used alone or in combination of two or more. Among these, a curable resin having a plurality of (meth)acryloyl groups is preferable from the viewpoint of scratch resistance, and a curable resin having a hydrophilic group in addition to a plurality of (meth)acryloyl groups is preferable from the viewpoint of improving antifogging properties. Particularly preferred are curable resins that further include. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a carboxyl group, an acid anhydride group, and a quaternary ammonium base.

Curable resins having multiple (meth)acryloyl groups include tri- to hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, urethane (meth)acrylate, and (meth)acryloyl groups having (meth)acryloyl groups. It may be an acrylic polymer, and urethane (meth)acrylate or a (meth)acrylic polymer having a (meth)acryloyl group is preferred.

The curable resin having a (meth)acryloyl group (a plurality of (meth)acryloyl groups) and a hydrophilic group is a urethane (meth)acrylate having a hydrophilic group, a (meth)acryloyl group having a (meth)acryloyl group, and a hydrophilic group. Acrylic polymers are preferred.

The curable resin may be a combination of a curable resin having a (meth)acryloyl group and a hydrophilic group and a 3- to 6-functional (meth)acrylate in order to achieve both scratch resistance and antifogging properties. . When both are combined, the ratio of the curable resin having a (meth)acryloyl group and a hydrophilic group is, for example, 10 to 100 parts by mass, preferably 15 parts by mass, per 100 parts by mass of 3-6 functional (meth)acrylate. ~80 parts by weight, more preferably 20 to 50 parts by weight.

(B) Curing agent The curable composition may further contain a curing agent depending on the type of curable resin. For example, thermosetting resins may contain curing agents such as amines and polycarboxylic acids, and photocuring resins may contain photopolymerization initiators. Examples of the photopolymerization initiator include conventional components such as acetophenones, propiophenones, benzyls, benzoins, benzophenones, thioxanthones, and acylphosphine oxides.

The proportion of the curing agent such as a photopolymerization initiator is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the curable resin. be.

The curable composition may further contain a curing accelerator. In particular, the photocurable resin may contain a photocuring accelerator, such as tertiary amines (dialkylaminobenzoic acid ester, etc.), a phosphine photopolymerization accelerator, and the like.

(C) Antibacterial agent The curable composition may further contain an antibacterial agent to improve antibacterial properties. The antibacterial agent may be an organic antibacterial agent or an inorganic antibacterial agent.

Examples of organic antibacterial agents include conventional antibiotics, such as β-lactam antibiotics such as penicillin, cephalosporin, and ampicillin; aminoglycoside antibiotics such as streptomycin and kanamycin; tetracycline antibiotics such as tetracycline and minocycline; Examples include macrolide antibiotics such as erythromycin and clarithromycin; nucleic acid antibiotics such as puromycin; and chloramphenicol antibiotics such as chloramphenicol.

Inorganic antibacterial agents include single metals or metal compounds such as silver, copper, and tin (oxides, halides, halogenates, perhalogenates, inorganic acid salts, organic acid salts, complexes, etc.), titanium oxide, etc. Examples include photocatalytic metal oxides.

These antibacterial agents can be used alone or in combination of two or more. Among these, inorganic antibacterial agents such as silver are preferred.

The antibacterial agent may be supported on a carrier. Examples of the carrier include zeolite, zirconium phosphate, calcium phosphate, calcium apatite, silica, alumina, and titanium oxide.

The shape of the carrier carrying the antibacterial agent may be fibrous, granular (spherical, ellipsoidal, polyhedral, etc.), irregular shape, etc. However, from the viewpoint of ease of handling, granular (antibacterial particles) Used for general purpose.

The number average particle diameter of the antibacterial particles (granular carrier carrying an antibacterial agent) is, for example, 0.01 to 10 μm, preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm, and even more preferably 0.3 to 10 μm. 2 μm, most preferably 0.5-1.5 μm.

Note that in this specification and claims, the number average particle diameter can be measured by a laser diffraction scattering method or the like.

The proportion of antibacterial particles is, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and particularly preferably 0. .15 to 1 part by weight, more preferably 0.2 to 1 part by weight, most preferably 0.25 to 0.5 part by weight. If the proportion of antibacterial particles is too small, there is a risk that antibacterial properties will be reduced, and if it is too large, there is a possibility that visibility will be reduced.

(D) Antifogging agent The curable composition may further contain an antifogging agent in order to improve antifogging properties. The antifogging agent may be a conventional antifogging agent, such as a nonionic surfactant. Nonionic surfactants include, for example, polyhydric alcohol fatty acid esters such as sucrose fatty acid esters, polyglycerin fatty acid esters, and glycerin fatty acid esters, and their ethylene oxide adducts; ethylene oxide adducts of higher alcohols; ethylene oxide adducts of aromatic hydroxy compounds. Adducts; ethylene oxide adducts of fats and oils; polyoxyethylene-polyoxypropylene copolymers, and the like. These antifogging agents can be used alone or in combination of two or more. The proportion of the antifogging agent can be selected, for example, from a range of about 0.01 to 100 parts by mass based on 100 parts by mass of the curable resin.

(E) Other components The curable composition may further contain other components. Other ingredients include conventional additives, such as leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, coupling agents (titanium coupling agents, silane coupling agents, etc.). fillers, crosslinking agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, thickeners, antifoaming agents, etc. The total proportion of other components is, for example, 0.01 to 100 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the curable resin.

From the viewpoint of improving visibility, the functional layer preferably does not substantially contain light-transmitting particles with a particle size of 0.5 μm or more, and particularly does not contain light-transparent particles with a particle size of 0.5 μm or more. preferable.

(Transparent base layer)
The transparent base material layer (light-transmitting base material layer) only needs to be made of a transparent material, and can be selected depending on the intended use.It may also be made of an inorganic material such as glass, but there are certain considerations such as strength and moldability. Therefore, organic materials are widely used. Examples of the organic material include cellulose ester, polyester, polyamide, polyimide, polycarbonate, and (meth)acrylic polymer. Among these, cellulose esters, polyesters, polycarbonates, etc. are commonly used, and cellulose derivatives, polyesters, and polycarbonates are preferred.

Examples of the cellulose ester include cellulose acetate such as cellulose triacetate (TAC), cellulose acetate _C3-4 acylate such as cellulose acetate propionate, and cellulose acetate butyrate.

Examples of the polyester include polyalkylene arylates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

Examples of the polycarbonate include bisphenol type polycarbonates such as bisphenol A type polycarbonate.

Among these, cellulose acetate such as TAC and polyester such as PET are preferred, and cellulose acetate is particularly preferred, in view of their excellent balance of mechanical properties, transparency, optical isotropy, and the like.

The transparent substrate layer may also contain the conventional additives exemplified in the functional layer section. Preferred embodiments and ratios are also the same as those for the functional layer.

The transparent base layer may be a uniaxially or biaxially stretched film, but may also be an unstretched film because it has low birefringence and excellent optical isotropy.

The transparent base material layer may be surface-treated (for example, corona discharge treatment, flame treatment, plasma treatment, ozone or ultraviolet irradiation treatment, etc.), and may have an easily adhesive layer.

The thickness (average thickness) of the transparent base layer is, for example, 5 to 2000 μm, preferably 15 to 1000 μm, more preferably 20 to 500 μm, more preferably 100 to 400 μm, and most preferably 188 to 350 μm.

(Characteristics of transparent laminated film)
The transparent laminated film may have a diffuse transmission intensity ratio [(T5/T20)×100] that satisfies the above formula (1) and is 99.9 or more, for example, 99.9000 to 99.9999, preferably 99. .9300 to 99.9995, more preferably 99.9500 to 99.9993, more preferably 99.990 to 99.999, most preferably 99.992 to 99.997. If the diffused transmission intensity ratio is too small, a cloudy feeling is likely to occur due to diffused light, and there is a possibility that visibility may be reduced.

In addition, in this specification and the claims, the diffuse transmission intensity ratio can be measured using a variable angle photometer, and in detail, it can be measured by the method described in the Examples described later.

The total light transmittance of the transparent laminated film is, for example, 70% or more (for example, 70 to 100%), preferably 80 to 99%, more preferably 85 to 98%, and even more preferably 88 to 97%. If the total light transmittance is too low, there is a risk that transparency will decrease.

Note that in this specification and claims, the total light transmittance can be measured in accordance with JIS K 7361.

The transmitted image clarity (0.125 mm width optical comb) of the transparent laminated film may be 70% or more, for example 70 to 99%, preferably 75 to 95%, more preferably 78 to 92%, more preferably 80-88%, most preferably 82-86%. If the transmitted image clarity is too low, the observed image will be blurred and visibility will be reduced.

Transmitted image clarity is a measure that quantifies the blurring and distortion of light transmitted through a film. The transmitted image clarity is determined by measuring the transmitted light from the film through a moving optical comb, and calculating the value based on the amount of light in bright and dark areas of the optical comb. In other words, when the film blurs the transmitted light, the slit image formed on the optical comb becomes thicker, so the amount of light in the transparent part is less than 100%, while in the non-transparent part, the light leaks and is 0%. That's all. The value C of the transmitted image clarity is defined by the following equation from the maximum value M of transmitted light in the transparent part of the optical comb and the minimum value m of transmitted light in the opaque part.

C (%) = [(M-m)/(M+m)] x 100

That is, the closer the value of C is to 100%, the smaller the blurring of the image caused by the anti-glare film [Reference: Suga, Mitamura, Painting Technology, July 1985 issue].

In addition, in this specification and the claims, the transmitted image sharpness can be measured in accordance with JIS K 7105, and in detail, it can be measured by the method described in the Examples described later.

Note that in this specification and claims, the glossiness of 60° can be measured in accordance with ISO 2813, and more specifically, by the method described in the Examples described below.

The transparent laminated film of the present disclosure may be combined with a low refractive index layer, a polarizing layer, a refractive index adjusting layer, an adhesive layer, etc. in addition to the functional layer and the transparent base layer.

The thickness (average thickness) of the transparent laminated film is, for example, 5 to 2000 μm, preferably 15 to 1000 μm, more preferably 20 to 500 μm, more preferably 100 to 400 μm, and most preferably 188 to 350 μm.

[Method for manufacturing transparent laminated film]
As a method for manufacturing the transparent laminated film of the present disclosure, it is sufficient that the above-mentioned surface shape can be imparted to the functional layer, and a conventional method can be used depending on the material of the functional layer. When the functional layer is formed of a cured product of a curable composition, the manufacturing method includes, for example, a method of forming an uneven shape using particles (for example, forming a convex shape by following the shape of the particles). method, etc.), and a method of forming irregularities on the surface by generating convection (such as Marangoni convection) in the drying process of the curable composition. In either method, in the production method using a curable composition, a curable composition containing a curable resin is applied to at least one surface of the transparent base layer and dried, thereby forming a functional layer precursor. may be prepared.

The curable composition may contain a solvent. The solvent can be selected depending on the type and solubility of the curable resin, and any solvent may be used as long as it can uniformly dissolve at least the solid content (for example, the curable resin, curing agent, and other additives). Examples of such solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves [methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc.], cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.). Further, the solvent may be a mixed solvent. Among these solvents, cellosolves such as 1-methoxy-2-propanol are preferred.

The concentration of the solute (curable resin, curing agent, other additives) in the composition can be selected within a range that does not impair flowability, coating properties, etc., for example, 1 to 80% by mass, preferably 10 to 70% by mass, More preferably 15 to 50% by weight, most preferably 20 to 30% by weight.

As a coating method, conventional methods such as a roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip/squeeze coater, die coater, gravure coater, microgravure coater, and silk screen coater can be used. method, dip method, spray method, spinner method, etc. Among these methods, the bar coater method and the gravure coater method are commonly used. Note that, if necessary, the coating liquid may be applied multiple times.

After the composition is cast or coated, it may be dried to evaporate the solvent. Drying may be air drying, but depending on the boiling point of the solvent, for example, 30 to 200 °C, preferably 40 to 150 °C, more preferably 45 to 120 °C, more preferably 50 to 100 °C, most preferably may be dried at a temperature of 55-70°C. By heating and drying, convection of the curable composition can be controlled and the desired uneven shape can be adjusted.

The functional layer precursor thus obtained is cured by actinic light (ultraviolet rays, electron beams, etc.), heat, or the like to obtain a transparent laminated film. The curable composition may be cured by a combination of heating, light irradiation, etc. depending on the type of curable resin.

The heating temperature can be selected from an appropriate range, for example, about 50 to 150°C. The light irradiation can be selected depending on the type of photocuring component, etc., and typically, ultraviolet rays, electron beams, etc. can be used. A general-purpose light source is usually an ultraviolet irradiation device.

As a light source, for example, in the case of ultraviolet light, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a laser light source (a light source such as a helium-cadmium laser or an excimer laser), etc. can be used. The amount of irradiation light (irradiation energy as an integrated amount of light) varies depending on the thickness of the coating film, and is, for example, 10 to 10,000 mJ/cm ² , preferably 20 to 5,000 mJ/cm ² , and more preferably 30 to 3,000 mJ/cm ² . Light irradiation may be performed in an inert gas atmosphere, if necessary.

[Protective equipment]
The protective equipment of the present disclosure is a protective equipment worn on the head to protect at least the eyes, and includes the transparent laminated film. The transparent laminated film is used to protect at least the eyes, and preferably to protect the eyes, nose, and mouth.

Examples of protective equipment using a transparent laminated film to protect the eyes include goggles and glasses. In goggles and glasses, it is sufficient that the protective part (lens in the case of glasses) for protecting the eyes contains a transparent laminated film, and the protective part itself such as the lens may be formed of the transparent laminated film. From the viewpoint of productivity and the like, it is preferable to laminate a transparent laminate film on the surface of the protective portion.

Examples of protective equipment that uses a transparent laminated film to protect the eyes, nose, and mouth include face shields (face guards).

FIG. 1 is a schematic diagram showing how a face shield is used as an example of the present disclosure. As shown in FIG. 1, the face shield 1 of the present disclosure includes a main body part 1a for shielding (protecting) the face, and a wearing part 1b for wearing the main body part 1a on the head. The main body part 1a is formed of the transparent laminated film, has a rectangular film curved to follow the face, and has the wear part 1b at the upper end. The wearing part 1b is made of flexible plastic and has a partial ring shape that can be fitted (latched) to the head. Therefore, by fitting the wearing part 1b to the head, the protective equipment can be fixed to the head, and the face can be protected by the main body part 1a.

The face shield of the present disclosure is not limited to the face shield shown in FIG.

The planar shape of the main body is not particularly limited as long as it can protect the face, and may be not only rectangular but also square, diamond-shaped, circular, elliptical, etc. Further, the main body portion is not limited to a curved shape as shown in FIG. 1, but may have a non-curved planar shape. Furthermore, the shape of the main body may be a shape that protects not only the eyes, mouth, and nose, but also the ears, and may be a curved shape that covers the ears or a cylindrical shape that extends to the back of the head.

The material (structure) of the main body portion may be formed of the transparent laminate film alone, or may be a laminate with other transparent films. Among these, from the viewpoint of productivity etc., it is preferable to form the transparent laminated film alone, and a transparent laminated film in which a first functional layer and a second functional layer are laminated on both sides of a transparent base layer, respectively. It is particularly preferable to form it alone. When a transparent laminated film with a functional layer laminated on both sides is formed alone, the function of the functional layer can be expressed on either the inside (face side) or the outside of the main body.For example, if the functional layer has antibacterial properties, , it can antibacterialize microorganisms originating from the wearer, and it can also antibacterialize microorganisms from the outside.

The wearing part is also not limited to the structure shown in FIG. In other words, the wearing part is not limited to a partial ring-shaped wearing part made of flexible plastic and fitted onto the head, but also a wearing part that is worn on the head by hanging on the ear, or a wearing part with a string tied at the back of the head. It may also be a string-like wearing part, a hat-like wearing part (a wearing part for fixing the main body part as a brim part of a hat), etc.

The fixation site of the wearing part to the main body part is not limited to the upper end of the main body part, and can be selected as appropriate depending on the type of the wearing part. For example, in the case where a wearing part having a structure to be hung on an ear is applied to a main body having a rectangular planar shape, the wearing part may be provided between the upper end and the lower end of the main body.

The material of the wearing part is not particularly limited either, and plastics, metals, fibers, etc. can be used as appropriate depending on the structure.

A conventional method can be used for manufacturing the protective equipment. For example, the main body portion may be formed by bending (curving) a transparent laminated film.

Note that each aspect disclosed in this specification can be combined with any other feature disclosed in this specification.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited by these Examples. The raw materials used in the Examples and Comparative Examples are as follows, and the obtained coating films were evaluated by the following methods.

[material]
Acrylic group-containing polymer: “8WX-030” manufactured by Taisei Fine Chemical Co., Ltd.
Dipentaerythritol hexaacrylate: “DPHA” manufactured by Daicel Allnex Co., Ltd.
Hydrophilic hard coating agent: “Nostra RA-FS2” manufactured by Mitsui Chemicals, Inc.
UV-curable acrylic polymer: “8KX-078” manufactured by Taisei Fine Chemical Co., Ltd.
Polyester-urethane copolymer resin: “UR-3200” manufactured by Toyobo Co., Ltd.
Ultraviolet curable hard coating agent: “Z7503” manufactured by Arakawa Chemical Industry Co., Ltd.
Acrylic polymer with polymerizable group: “Cyclomer P” manufactured by Daicel Allnex Co., Ltd.
Cellulose acetate propionate: Eastman “CAP-482-20”
UV curing coating agent A: “FA-3201M” manufactured by Nippon Kako Toyo Co., Ltd.
UV curing coating agent B: “FA-3201 Clear” manufactured by Nippon Kako Toyo Co., Ltd.
Urethane acrylate: “UA-1100H” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Silver ion-supporting inorganic ion exchanger: “Novaron IV1000” manufactured by Toagosei Co., Ltd. (particle size 1 μm)
Silver-containing inorganic antibacterial agent: "Bacterite MP-102SVC615" manufactured by Fuji Chemical Co., Ltd. (particle size 1 μm)
Silicone acrylate: “EB1360” manufactured by Daicel Allnex Co., Ltd.
Fluorine compound having a polymerizable group: “KY-1203” manufactured by Shin-Etsu Chemical Co., Ltd.
Photoinitiator: IGM Resins B. “Omnirad184” made by V
Polyethylene terephthalate (PET) film: "Diafoil" manufactured by Mitsubishi Plastics Co., Ltd., 188 μm.

[Transmission image clarity (IC)]
It was measured in accordance with JIS K 7105 using a mapping measuring device (manufactured by Suga Test Instruments Co., Ltd., ICM-1T). The optical comb widths were 0.125 mm, 0.250 mm, and 0.500 mm.

[Scattered intensity of transmitted light]
Using a variable angle photometer (manufactured by Murakami Color Research Institute, model: GP-200), the scattering intensity of transmitted light was evaluated according to the following procedure. Visible light is irradiated perpendicularly from the back side of the coating film (the surface that becomes the outside when the coating film is worn), the light flux enters the coating film, and the diffusely transmitted light is measured every degree in the range of -20 degrees to +20 degrees. The diffuse transmission intensity was measured by scanning the receiver. T20 is defined as the sum of the diffuse transmission intensity measured every degree in the range from -20 degrees to +20 degrees, and T5 is defined as the sum of the diffuse transmission intensity measured every degree in the range from -5 degrees to +5 degrees. T5/T20 was calculated.

[Surface shape]
In accordance with JIS B 0601-2001, Ra, Rzjis, and RSm were measured using a contact type surface roughness meter ("Surfcom 1400G" manufactured by Tokyo Seimitsu Co., Ltd.) under the following conditions.

・Cutoff wavelength λc=0.8mm
・Cutoff ratio λc/λs=300
・Feeding speed of stylus = 0.3mm/sec
・Evaluation length: 5 times cutoff value λc ・Preliminary length: (cutoff value λc) x 2
・Cutoff filter type: Gaussian.

[Water contact angle]
Using an automatic dynamic contact angle meter (“Model DCA-UZ” manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of approximately 5 μL of each liquid was measured at 5 points on the functional layer surface of the coating film. Averaged.

[Anti-fog]
The coating film was placed on top of a glass container containing water at 50° C. with the functional layer facing inside (so that the functional layer could come into contact with the water in the container), and evaluated based on the following criteria.

3 points: No clouding is seen on the film surface even after 5 minutes or more 2 points: No clouding is seen on the film surface after 1 minute, but clouding is seen after 5 minutes 1 point: Less than 1 minute The film surface becomes cloudy.

[Pencil hardness]
The hardness of the functional layer of the coating film was measured according to JIS K 5400 under a load of 750 g.

[Scratch resistance]
Using a steel wool durability tester, rub #0000 steel wool with a diameter of 1.0 cm on the surface of the functional layer of the coating film at a load of 0.2 kg/cm ² for 10 or 100 cycles, and then transfer the coating film to a black acrylic board. The surface condition was observed under a fluorescent lamp equipped with a 3-wavelength fluorescent tube, and evaluated using the following criteria.

3 points: No scratches can be seen even after 100 round trips. 2 points: Scratches can be seen after 100 round trips, but no scratches can be seen after 10 round trips. 1 point: Scratches can be seen after 10 round trips.

[Antibacterial]
The antibacterial activity value R of the film against E. coli (strain NBRC3972) on a 1/500 ordinary bouillon medium was determined in accordance with JIS Z 2801:2010, and evaluated using the following criteria.

3 points: Antibacterial activity value R is 4 or more. 2 points: Antibacterial activity value R is 2 or more and less than 4. 1 point: Antibacterial activity value R is less than 2.

[Blurred image]
The coating film was placed 5 cm in front of the evaluator's eyes, and a lit fluorescent lamp located 5 m ahead of the evaluator was observed and evaluated using the following criteria. Note that there is no problem with using any object other than a fluorescent light, and the relative relationship of the evaluation results will not change, but it must be noted that the difference will not be clear even when observing a dark object.

3 points: The outline of the fluorescent light can be clearly recognized. 2 points: The outline of the fluorescent light is slightly blurred, but there is no problem in recognizing the outline. 1 point: The outline of the fluorescent light is blurred and cannot be recognized.

[Cloudy feeling due to diffused light]
The coating film was placed 5 cm in front of the evaluator's eyes, and the illuminated fluorescent lamp and its surroundings were observed 5 m ahead of the evaluator, and evaluated using the following criteria. Note that there is no problem with using any object other than a fluorescent light, and the relative relationship of the evaluation results will not change, but it must be noted that the difference will not be clear even when observing a dark object.

3 points: The light from the fluorescent lamps is not scattered, and things around the fluorescent lamps look the same as without the film. 2 points: The light scattering from the fluorescent lamps is observed, but the degree is weak, and the objects around the fluorescent lamps look the same as if there was no film. Objects look the same as they would without the film. 1 point: The light from the fluorescent lamps is strongly scattered, and objects around the fluorescent lamps appear cloudy.

[Watermark]
The coating film was attached to a black acrylic board with the functional layer side facing up via a transparent adhesive. A TAC film (manufactured by Fuji Film Co., Ltd., product number TG60UL) was placed on the uneven surface and pressed with a finger to observe whether a watermark was observed and evaluated based on the following criteria.

3 points: The watermark cannot be seen while pressing or after the finger is released. 2 points: The watermark can be seen immediately after the finger is removed, but it becomes invisible after 1 minute. 1 point: 1 minute after the finger is removed. The watermark can be seen even after the elapsed time.

Example 1
26.3 parts by weight of an acrylic group-containing polymer, 90 parts by weight of DPHA, and 2 parts by weight of a photoinitiator were dissolved in 84 parts by weight of 1-methoxy-2-propanol. 0.3 parts by mass of an inorganic ion exchanger supporting silver ions was added to this solution, and the mixture was well suspended. This liquid was cast onto a PET film using a #14 wire bar, and then left in an oven at 100° C. for 1 minute to evaporate the solvent and form a 9 μm thick coating layer. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Example 2
166.7 parts by mass of a hydrophilic hard coating agent and 2 parts by mass of a photoinitiator were dissolved in 166 parts by mass of 1-methoxy-2-propanol. This liquid was cast onto a PET film using a #18 wire bar, and then left in an oven at 60° C. for 1 minute to evaporate the solvent and form a coat layer with a thickness of 6 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Example 3
166.7 parts by mass of a hydrophilic hard coating agent and 2 parts by mass of a photoinitiator were dissolved in 166 parts by mass of 1-methoxy-2-propanol. 0.3 parts by mass of an inorganic ion exchanger supporting silver ions was added to this solution, and the mixture was well suspended. This liquid was cast onto a PET film using a #18 wire bar, and then left in an oven at 60° C. for 1 minute to evaporate the solvent and form a coat layer with a thickness of 6 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Example 4
166.7 parts by mass of a hydrophilic hard coating agent and 2 parts by mass of a photoinitiator were dissolved in 166 parts by mass of 1-methoxy-2-propanol. This liquid was cast onto a PET film using a wire bar #20, and then left in an oven at 60° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 7 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Example 5
26.8 parts by mass of UV-curable acrylic polymer, 12.0 parts by mass of polyester-urethane copolymer resin, 158.7 parts by mass of UV-curable hard coating agent, 1 part by mass of silicone acrylate, 2 parts by mass of photoinitiator, 1 -Methoxy-2-propanol was dissolved in 168 parts by mass. This liquid was cast onto a PET film using a #14 wire bar, and then left in an oven at 80° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 4 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Example 6
26.8 parts by mass of UV-curable acrylic polymer, 12.0 parts by mass of polyester-urethane copolymer resin, 158.7 parts by mass of UV-curable hard coating agent, 1 part by mass of silicone acrylate, 2 parts by mass of photoinitiator, 1 -Methoxy-2-propanol was dissolved in 168 parts by mass. 1 part by mass of a silver-containing inorganic antibacterial agent was added to this solution and well suspended. This liquid was cast onto a PET film using a #14 wire bar, and then left in an oven at 80° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 4 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Comparative example 1
26.3 parts by weight of an acrylic group-containing polymer, 90 parts by weight of DPHA, and 2 parts by weight of a photoinitiator were dissolved in 84 parts by weight of 1-methoxy-2-propanol. 0.3 parts by mass of an inorganic ion exchanger supporting silver ions was added to this solution, and the mixture was well suspended. This liquid was cast onto a PET film using a wire bar #8, and then left in an oven at 100° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 5 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Comparative example 2
26.3 parts by weight of an acrylic group-containing polymer, 90 parts by weight of DPHA, and 2 parts by weight of a photoinitiator were dissolved in 84 parts by weight of 1-methoxy-2-propanol. 0.3 parts by mass of an inorganic ion exchanger supporting silver ions was added to this solution, and the mixture was well suspended. This liquid was cast onto a PET film using a wire bar #10, and then left in an oven at 100° C. for 1 minute to evaporate the solvent and form a coat layer with a thickness of 6 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm 2 to obtain a coating film.

Comparative example 3
49.5 parts by mass of an acrylic polymer having a polymerizable group, 10.9 parts by mass of cellulose acetate propionate, 61.5 parts by mass of DPHA, 6.8 parts by mass of silicone acrylate, 2 parts by mass of photoinitiator, 1- It was dissolved in 3 parts by mass of methoxy-2-propanol, 219.8 parts by mass of methyl ethyl ketone, and 44.6 parts by mass of 1-butanol. This liquid was cast onto a PET film using a #14 wire bar, and then left in an oven at 100° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 5 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Comparative example 4
After casting a liquid mixture of 116 parts by mass of UV curable coating agent A, 174 parts by mass of UV curable coating agent B, and 2 parts by mass of fluorine-based compound having a polymerizable group onto a PET film using wire bar #10, The film was left in an oven at 100° C. for 1 minute to evaporate the solvent and form a coat layer with a thickness of 6 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Comparative example 5
113.5 parts by mass of urethane acrylate, 1.0 parts by mass of cellulose acetate propionate, 2 parts by mass of photoinitiator, 0.6 parts by mass of a fluorine-based compound having a polymerizable group, and 31.5 parts by mass of 1-methoxy-2-propanol. 9 parts by mass, 149.0 parts by mass of methyl ethyl ketone, and 31.9 parts by mass of 1-butanol. This liquid was cast onto a PET film using a #14 wire bar, and then left in an oven at 100° C. for 1 minute to evaporate the solvent and form a coating layer with a thickness of 5 μm. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a high-pressure mercury lamp at a cumulative light intensity of 120 mJ/cm ² to obtain a coating film.

Table 1 shows the evaluation results of the coating films obtained in Examples and Comparative Examples.

As is clear from the results in Table 1, the coating films of Examples were excellent in various properties. In particular, the coating films of Examples 1 to 4 not only had excellent antifogging properties, but also oily stains such as fingerprints could be easily wiped off with a cloth, and had excellent antifouling properties.

On the other hand, in the coating films of Comparative Examples 1 and 2, the observed images were blurred and the visibility was low. In addition, the coating films of Comparative Examples 3 and 4 had low scratch resistance and antibacterial properties, and the observed images had a cloudy appearance and low visibility. Furthermore, the coating of Comparative Example 5 has low antibacterial properties and also generates water marks, so blocking is likely to occur, making it difficult to improve productivity.

The protective equipment of the present disclosure can be used as protective equipment (e.g., face shields, glasses, goggles, etc.) worn on the head to protect at least the eyes, and in particular, the protective equipment to protect the eyes, nose, and mouth. It can be suitably used as a tool (for example, a face shield).

1... Face shield 1a... Main body part 1b... Wearing part

Claims (11)

Protective equipment worn on the head to protect at least the eyes,
A transparent laminated film including a transparent base material layer and a functional layer laminated on at least one side of the transparent base material layer and having an uneven shape on the surface,
When the functional layers are laminated on both sides of the transparent base layer, the first functional layer and the second functional layer laminated on each surface are the same layer,
The arithmetic mean roughness Ra of the uneven shape is 0.015 to 0.1 μm , and the transparent laminated film has a transmitted image clarity of 70% or more as measured using an optical comb with a width of 0.125 μm. and
A protective device in which the transparent laminated film satisfies the following formula (1).
(T5/T20)×100≧99.9 (1)
(In the formula, T5 is the diffusion of light that is diffused and transmitted when the transparent laminated film is irradiated with visible light perpendicularly from the outer surface when worn, measured in degrees from -5 degrees to +5 degrees. T20 indicates the total transmission intensity, and T20 is the value of the diffused and transmitted light when visible light is perpendicularly irradiated from the outer surface when the transparent laminated film is worn, at 1 degree increments in the range of -20 degrees to +20 degrees. (indicates the sum of the measured diffuse transmission intensity) 2. The protective device according to claim 1, wherein in the transparent laminated film, the first functional layer and the second functional layer are laminated on both sides of the transparent base layer, respectively . The protective device according to claim 1 or 2, wherein the functional layer does not contain translucent particles having a particle size of 0.5 μm or more. The protective device according to any one of claims 1 to 3, wherein the functional layer has an antibacterial activity value R of 2 or more according to JIS Z 2801:2010. The protective device according to any one of claims 1 to 4, wherein the functional layer has a water contact angle of 20 degrees or less. The protective device according to any one of claims 1 to 5, wherein the functional layer has a pencil hardness of H or higher. The protective device according to any one of claims 1 to 6, wherein the functional layer is a hard coat layer. The protective device according to any one of claims 1 to 7, wherein the functional layer is formed of a cured product of a curable composition containing a curable resin having a plurality of (meth)acryloyl groups. 9. The protective device of claim 8, wherein the curable composition further comprises an antibacterial agent. The protective equipment according to any one of claims 1 to 9, which is a face shield, goggles or glasses. Claim 1: A face shield comprising a main body part for shielding the face and a wearing part for wearing the main body part on the head, and the main body part is formed of the transparent laminated film. The protective equipment according to any one of items 1 to 10.

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