JP2002267816A - Sheet for imparting antireflection layer to be used for injection molding, injection molding method using the same and injection molded article having antireflection layer laminated - Google Patents

Abstract

PROBLEM TO BE SOLVED: To dissolve the increase of time and labor to be applied to an injection molded article and application limits in terms of a shape for preventing the reflection of the injection molded article by fine ruggedness instead of a multi- layer thin film lamination type and to dissolve the fault of being not suitable for the production of many kinds in small quantities in the method of forming the fine ruggedness on a die and imparting the fine ruggedness simultaneously with injection molding. SOLUTION: A transfer sheet for which a peeling sheet base material 5a, a peeling layer 5b with the fine ruggedness on a lower surface, a low refractive index layer 4, an antireflection layer 4 and a thermally melt-sticking layer 5 are laminated successively from the top is set inside the die so as to turn the side of the thermally melt-sticking layer 5 to an inner side and molten resin is injected. Thus, the antireflection layer 3 is integrated with a molded article in molding and the problem is solved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet for applying an antireflection layer suitable for various optical uses, an injection molding method using such a sheet for applying an antireflection layer, and a sheet for applying an antireflection layer. The present invention relates to an injection molded product obtained by the used injection molding method.

[0002]

2. Description of the Related Art Various types of display devices are known. When any type of display is used, lighting of a space in which the display is placed (natural lighting is considered as artificial lighting). It does not matter.)
Is a problem. For example, when watching a television broadcast at home, it is an everyday experience that the lighting of the room where the television is placed affects the visibility of the image. Also, depending on the position of the viewer, the illumination may appear on the screen and the video may not even be seen. In the case of an in-vehicle television, the sunrise and sunset are reflected from the screen through the window of the vehicle, and it is often difficult to see.

[0003] Of course, conventionally, such a problem has been dealt with by various methods. One of them is a multi-layered thin film type transparent film in which optical thin films having different refractive indices are stacked on each other. The use of a plate to prevent reflection has been performed. However, when using this method, the speed of forming a thin film in a vacuum such as sputtering is not sufficient, so that the production efficiency is poor, and the path length of light in each thin film changes depending on the viewing angle. It also has the disadvantage of becoming reddish or bluish. Alternatively, the surface of the transparent plate is matted to prevent reflection, but the effect is not sufficient.

[0004] Some displays, such as CRTs, emit light and have relatively high brightness.
Some liquid crystal displays do not emit light, and the visibility is secured with the help of lighting means. Even those requiring such illumination means, as described above,
Lighting in the surrounding environment is a problem, and anti-reflection means is often used. However, the anti-reflection means reflects a part of the light emitted from the display, and may reduce the apparent brightness.

The applicant has proposed, in Japanese Patent Application No. 2000-74347, an antireflection film having an uneven portion in which a myriad of fine unevennesses having a pitch equal to or less than the wavelength of light are formed. However, it is necessary to separately provide means for application, such as once manufacturing, and then attaching or fixing to an object, and application may be difficult depending on the shape.

Of course, if injection molding is performed using a mold having such fine irregularities formed on the inner surface, fine irregularities are formed only by injection molding, so that the production efficiency can be improved. However, originally, it takes time to produce fine irregularities in the mold for each shape of the product, which is troublesome to produce, so it takes time to produce the mold, so when mass-producing the same product, Even if it is suitable, it cannot always be said to be an appropriate method when a relatively small amount of products are produced in many kinds.

[0007]

In the present invention, the disadvantages of the multilayer antireflection means of the multilayer thin film type conventionally used in displays and the like, namely, production efficiency, coloring caused by the viewing angle, and satin-like surface. It is an object to eliminate unsatisfactory points in items such as antireflection properties. In addition, once an anti-reflection film with fine irregularities is manufactured, it is necessary to eliminate the increase in labor and restrictions on application when applying to an injection molded product, and to form fine irregularities on a mold. It is another object of the present invention to eliminate a disadvantage that is not suitable for multi-kind, small-quantity production in a method of providing fine irregularities simultaneously with injection molding.

[0008]

Means for Solving the Problems The same applicant as the present invention is disclosed in Japanese Patent Application No.
No. 000-74347 has already proposed an antireflection film having an uneven portion in which fine unevenness having a pitch equal to or less than the wavelength of light is formed. The means of needing, at the same time as injection molding, pasting of a layer including an antireflection layer,
Alternatively, the problem could be solved by performing transfer.

According to a first aspect of the present invention, an antireflection layer comprising a myriad of fine irregularities having a pitch equal to or less than the wavelength of light and having a refractive index of light varying in a thickness direction is laminated on a base sheet. Injection molding, wherein the surface of the material sheet opposite to the side on which the antireflection layer is laminated is at least heat-fusible, and both the base sheet and the antireflection layer have transparency. The present invention relates to an antireflection layer-providing sheet to be used in the present invention. According to a second aspect, in the first aspect, the base sheet is a non-heat-fusible layer on the antireflection layer side, and a heat-fusible layer on the side opposite to the antireflection layer side. The surface of the base sheet opposite to the side on which the antireflection layer is laminated is heat-fusible, and the non-heat-fusible layer and the heat-fusible layer both have transparency. The present invention relates to an antireflection layer-providing sheet for use in injection molding, wherein the base sheet has transparency. According to a third aspect, in the first or second aspect, a low refractive index layer having transparency is laminated on an exposed surface of the antireflection layer, wherein the antireflection layer is used for injection molding. The present invention relates to a sheet for providing a layer. According to a fourth aspect of the present invention, the releasable surface of the releasable sheet in which at least one surface is a releasable surface constitutes a mold surface having an inverse shape to the fine irregularities of the antireflection layer according to claim 1. 2. The anti-reflection layer according to claim 1, wherein a transparent resin layer is filled and laminated on the mold surface so as to fill the inverse shape. On the surface opposite to the surface, a heat-fusible layer is laminated, at least, for use in injection molding characterized in that the transparent resin layer and the heat-fusible layer have transparency The present invention relates to a sheet for providing an antireflection layer. Fifth
The invention of the fourth invention is directed to the fourth invention, wherein one side of the base sheet is
The peelable sheet, the peelable surface, and the mold surface are formed by laminating a cured product layer of a curable resin having a surface having a shape opposite to that of the fine irregularities of the antireflection layer according to claim 1. The present invention relates to an antireflection layer-providing sheet for use in injection molding. Sixth
The invention of the fourth or fifth aspect is characterized in that a low refractive index layer having transparency is laminated along the fine irregularities on the molding surface side of the antireflection layer. The present invention relates to an antireflection layer-providing sheet for use in molding. According to a seventh aspect, the antireflection layer-imparting sheet according to any one of the first to third aspects is set in a mold such that the heat-fusible side of the base sheet faces the inside of the cavity. After that, the mold is closed, and then, a molding resin having transparency is injected and filled into the mold, cooled after filling, the mold is opened after cooling, and the molded product is taken out. The present invention relates to a method for producing a molded article having an antireflection layer. According to an eighth aspect of the present invention, the antireflection layer-providing sheet according to any one of the fourth to sixth aspects is set in a mold so that the heat-fusible layer side faces the inside of the cavity. And then injecting and filling a molding resin having transparency into the mold, cooling after filling, opening the mold after cooling, taking out a molded product, and peeling the release sheet. And a method for producing a molded article having an antireflection layer. A ninth invention is the molded article having an antireflection layer according to the seventh or eighth invention, wherein the antireflection layer-providing sheet is preformed in advance, and then set in the mold. And a method for producing the same. According to a tenth invention, in the seventh or eighth invention, the antireflection layer-providing sheet is set in the mold by preforming using the mold. The present invention relates to a method for producing a molded article having an antireflection layer. An eleventh invention is characterized in that the heat-fusible surface side of the antireflection layer-providing sheet according to any one of the first to third inventions is laminated along the surface of the injection-molded article. Injection molded product with a prevention layer laminated. According to a twelfth aspect, the heat-fusible layer side is laminated along the surface of the injection-molded product from the antireflection layer-providing sheet of any of the fourth to sixth aspects without the release sheet. The present invention relates to an injection molded article having an antireflection layer laminated thereon.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The sheet 1 for imparting an antireflection layer according to the present invention will be described with reference to the drawings. FIG. 1 shows a sticking sheet, and FIG. 2 shows a so-called transfer sheet. It is.

As shown in FIG. 1 (a), an antireflection layer-providing sheet 1 of the present invention has an antireflection layer 3 laminated on a base sheet 2, and the base sheet 2 The lower surface side is heat-fusible, and the antireflection layer 3 has an antireflection structure in which the upper surface side is made up of countless fine irregularities with a pitch equal to or less than the wavelength of light and the refractive index of light changes in the thickness direction. It is. The antireflection layer-imparting sheet 1 is a sticking sheet for applying antireflection properties to an appropriate object. The antireflection layer 3 is always transparent to exhibit such properties. The base sheet 2 may be opaque as long as such an antireflection layer-imparting sheet 1 is attached to an object and only imparts antireflection properties, but the object itself to be applied is usually transparent. Thus, the substrate sheet 2 is preferably transparent because it exhibits a function.

The antireflection layer-providing sheet 1, which is a sticking sheet, may be modified as shown in FIG. 1 (b). First, the base sheet 2 has a single layer in FIG. 1A, but the antireflection layer 3 has two layers of a non-heat-fusible layer 2a and a lower surface has a heat-fusible layer 2b. You may. With this two-layer structure, from various transparent plastic films, a non-thermally fusible and variously suitable one that is suitable as the non-thermally fusible layer 2a is selected. Separately, since the heat-fusible layer 2b can be formed using a plastic known as a heat sealant, there is an advantage that a wider range of materials can be selected as compared with a single layer. When it is preferable to use a transparent material as the base sheet, the two layers of the non-heat-fusible layer 2a and the heat-fusible layer 2b are both formed by selecting a transparent material. . Further, the anti-reflection layer 3 may have a low refractive index layer 4 laminated thereon, and the lamination has an advantage that the anti-reflection layer 3 can be protected from contamination and damage. The low-refractive-index layer 4 is, as shown in FIG.
May be laminated along the fine irregularities, or may be laminated so as to fill the fine irregularities of the antireflection layer 3. The low refractive index layer 3 may be laminated on the uppermost surface of the antireflection layer-providing sheet 1 shown in FIG.

As shown in FIG. 2A, the antireflection layer-providing sheet 1 of the present invention has an antireflection layer 3 and a heat-sealable sheet on at least the lower surface of a releasable sheet 5 whose lower surface is releasable. The layers 6 may be stacked. Such an antireflection layer-providing sheet 1 is usually called a transfer sheet. Such a releasable sheet 5 can be manufactured using an embossing plate having a predetermined shape on an appropriate plastic film. The peelable sheet 5 is
On the lower surface side, the anti-reflection layer 3 has an inverted shape of the fine unevenness that should be provided, and the lower surface of the inverted shape is filled with a transparent resin layer and laminated. The upper surface of the resin layer has fine irregularities, and constitutes the antireflection layer 3 in which the refractive index of light changes in the thickness direction. The antireflection layer-imparting sheet 1 includes layers other than the peelable sheet 5,
That is, the anti-reflection layer 3 and the heat-fusible layer 6 can be attached to each other by using the adhesive property of the heat-fusible layer 6 to provide the object with anti-reflection properties. Such an antireflection layer-providing sheet 1 is usually called a transfer sheet. Therefore, the antireflection layer 3 is necessarily transparent, and the heat-fusible layer 6 is preferably transparent when utilizing the transparency of the object to be stuck.

The sheet 1 for imparting an antireflection layer, which is a transfer sheet, may be modified as shown in FIG. 2 (b). The releasable sheet 5 shown in FIG. 2A may be constituted by a laminate of a releasable sheet base material 5a and a releasable layer 5b. From various plastic films that do not have, a material selected in consideration of handling aptitude such as strength is used as the releasable sheet substrate 5a, and a suitable release agent is applied to form a releasable sheet. There are advantages that can be configured. further,
The antireflection layer 3 may have a low refractive index layer 4 laminated thereon, that is, between the peelable sheet 5 and the peelable layer 5b when there is a peelable layer 5b. Thereafter, there is an advantage that the antireflection layer 3 can be protected from contamination and damage. The low-refractive-index layer 4 is, as shown in FIG.
It is preferable that the anti-reflection layer 3 is buried along the fine irregularities. This is because the lower surface of the antireflection layer 3 and the peelable sheet 5 or the lower surface of the peelable layer 5b provides the shape of the fine unevenness of the reflective layer 3. This low refractive index layer 4 may be applied to the antireflection layer-providing sheet shown in FIG.

The anti-reflection layer 3 has fine irregularities having a pitch equal to or less than the wavelength of light, as shown in FIG. 3a has an arc shape, the rising portion 3b has a linear shape, and the shape is tapered toward the top (FIG. 3).
(B)), a triangular wave shape with a sharp upper side (FIG. 3)
(C)), a trapezoidal shape having an upwardly tapering cross section (FIG. 3)
There can be various variations such as (d)).

The shape of the fine irregularities is shown in FIG.
3A, 3B, 3C, and 3D are preferable. When the cross-sectional shape is used, the thickness of the antireflection layer 3 is reduced. The property that the refractive index of light changes continuously depending on the position in the direction is imparted.

3 (a), 3 (b) and 3
When a shape as shown in (c) is present in the air, the ratio of the transparent resin layer present at the uppermost portion of the antireflection layer 3 is almost 0%, so that the refractive index at this portion is:
Surrounding substances (air in normal living space,
It is clearly lower than the refractive index of the transparent layer, which is approximately 1.0. ), And at the lowermost part of the unevenness, the ratio of the transparent resin layer present is infinitely close to 100%, so it is equal to the refractive index of the material constituting the transparent resin layer,
The intermediate portion has a refractive index proportional to the area ratio of the transparent resin layer at that height (that is, the ratio of the cross-sectional area of the transparent resin layer at the slice level to the whole), and
The antireflection layer 3 composed of the fine irregularities of the transparent resin layer has a refractive index continuously changing in the thickness direction between the refractive index of air and the refractive index of the transparent layer.

3 (a), 3 (b) and 3
In the case of the structure of the anti-reflection layer 3 shown in FIG. 3C and FIG. 3D, the refractive index in the portion below the bottom of the unevenness is constant as the refractive index of the transparent resin layer itself.

As is clear from the above description, on the contrary,
Given the desired relationship between the position in the thickness direction and the refractive index, the cross-sectional shape of the antireflection layer 3 can be designed. Depending on the cross-sectional shape, either a continuous or discontinuous change in the refractive index can be formed, but for a discontinuous refractive index, layers with different refractive indices should be stacked. In the present invention, it is preferable that the antireflection layer 3 is manufactured so that the refractive index changes continuously, and
More preferably, the refractive index continuously changes from the refractive index of air to the refractive index of the molded article 2. When the low refractive index 4 is laminated so as to fill the fine irregularities of the antireflection layer 3, the refractive index continuously changes from the refractive index of air to the refractive index of the material of the low refractive index layer 4. It is more preferable that

The antireflection layer 3 having these cross-sectional shapes is
When observing from the side having the irregularities, the arrangement of the fine irregularities may be one in which concave portions 3 ′ shown in FIG. 4A (a perspective view) are arranged in parallel, or FIG. 4B or FIG. (C)
As shown in the figure viewed from above (concentric circles indicate contour lines), there may be one formed by being arranged side by side in a plane. Both types have anti-reflective properties,
Since the groove type shown in FIG. 4A has directionality, the reflectance changes depending on the direction of incident light.
On the other hand, those having two-dimensionally arranged fine unevenness as shown in FIG. 4B or FIG. 4C are preferable because they have virtually no directionality. Of course, FIG.
As shown in FIG. 4B or FIG. 4C, the shape of the projections of the two-dimensionally arranged irregularities is changed to an elliptical shape (in this figure, the projections are circular), and the directionality is changed. You can also have it.

The shape of the fine irregularities of the antireflection layer 3 can be various, but the pitch (= period) of the waves of the irregularities appearing in the cross-sectional shape needs to be fine not more than the wavelength of light. Yes, the pitch is preferably 300 nm or less. In consideration of the accuracy of the mold and the reproducibility of the mold in the product, the pitch is preferably 100 nm or more, but there is no particular lower limit, and the pitch may be finer.

It is preferable that the anti-reflection layer 3 has a height difference of 50 nm or more, because the higher the difference between the heights of the fine unevenness, the lower the reflectance and the antireflection effect. There is no particular upper limit, but a normal pitch of 100 nm to 300 nm
Assuming nm, the pitch value is preferably about 50% to 200%, and more preferably about 50 nm to 600 nm. Of course, some may fall outside these ranges.

The fine irregularities of the antireflection layer 3 described above are as follows.
Laser light interference method for the photosensitive resin layer, preferably,
Exposure by splitting the laser beam into two or more parts to cause interference and exposure, and fine irregularities obtained by developing, fine irregularities obtained by laser or electron beam exposure to glass or a metal thin film on glass,
Or fine irregularities obtained by sandblasting,
Or the reverse shape is used as a prototype, and replication is performed using this prototype, or these prototypes are usually
Manufactured using a duplicating mold replicated by plating or the like, preferably a thermoplastic resin, preferably a curable resin, more preferably ultraviolet light, between the plastic film and the surface having fine irregularities of the duplicating mold. The resin is cured by sandwiching an ionizing radiation-curable resin that is cured by an electron beam.

The surface of the fine irregularities formed of a cured product of a curable resin, preferably a cured product of an ionizing radiation-curable resin, has poor adhesion, that is, has a peeling property.
A layer obtained by further laminating and curing a thermoplastic resin, preferably a curable resin, more preferably an ionizing radiation curable resin on the fine irregularities can be peeled off.

When the antireflection layer-providing sheet 1 of the present invention is a sticking sheet, the base sheet 2 or the non-heat-fusible layer 2a can be opaque except that they can be opaque.
It is preferable to use a transparent plastic film. When the antireflection layer-providing sheet 1 of the present invention is a transfer sheet, the peelable sheet 5 or the peelable sheet base 5a may be opaque. Except for the above, all can be configured using a transparent plastic film.

The transparent plastic film preferably has transparency and smoothness and does not contain foreign matter, and preferably has mechanical strength for reasons of processing and use of the product. Furthermore, when the heat of an object (eg, a display) is transmitted when the sheet for applying an antireflection layer is manufactured, adhered or transferred, or adhered to an appropriate object, heat resistance Are preferred. In the present invention, the base sheet 2, the releasable sheet 5, and the releasable sheet base 5a must have thermoformability at a molding temperature because of the necessity of following the shape of the mold. Is preferred.

Preferred are cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, Plastic films such as polymethyl methacrylate, polycarbonate, and polyurethane can be given. As for those having thermoformability, any of the above, regardless of the degree, have thermoformability, but especially when high thermoformability is required, polyvinyl chloride, ABS, polystyrene, polypropylene, etc. It is preferred to use Of these, those with relatively low heat fusion temperatures are:
It can be used as it is as a base sheet of a sticking sheet, and can be heat-fused with an object without a heat-fusible layer as another layer.

In the case of a photographic film coated with a photographic emulsion, a polyester which is often used is preferred in terms of mechanical strength and coating suitability. Cellulose triacetate and the like are preferable in terms of high transparency, no optical anisotropy, and low refractive index. Polycarbonate is preferred in terms of transparency and heat resistance.

Although these plastic films are flexible and easy to use, there is no need to bend them even during handling, and when a hard film is desired, a plate-like material such as the above resin plate or glass plate can be used. Can be used. The thickness is preferably about 8 to 1000 μm, and is preferably 25 to 30 μm.
About 0 μm is more preferable. In the case of a plate, it may exceed this range.

In order to improve the adhesiveness between the plastic film and the layers formed on the upper surface or the upper and lower surfaces, various treatments which can be usually performed, that is,
In addition to a physical treatment such as a corona discharge treatment and an oxidation treatment, a primer layer (not shown) may be formed by applying a paint called an anchor agent or a primer in advance.

In order to provide the above-mentioned plastic film with heat-sealing property, a plastic film itself having heat-sealing property may be used, or a heat-sensitive adhesive may be applied to a plastic film having no heat-sealing property. A so-called heat sealant is laminated as a heat-fusible layer.

As the heat sealant, polyester,
Acrylics, polyolefins, chlorinated polyolefins, rubbers, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, or ethylene / vinyl alcohol copolymers or other resins can be used. These heat sealing agents are dissolved or dispersed in an appropriate solvent or diluent, applied by a coating method such as gravure coating or roll coating, and dried to form a heat-fusible layer 6.
And the thickness is 2 to 10 μm, more preferably 3 to 5 μm.

The above-mentioned plastic film may originally have releasability depending on the material to be applied. For example, a polyester resin film or a polyolefin-based resin film has releasability from almost all binder resins of ink or paint. In general, it is common that a release layer 5b, which is a coating film made of a release paint or a release ink, is laminated on a plastic film, and the surface after the lamination is made releasable.

As the peelable paint or the peelable ink for forming the peelable layer 5b, a general thermoplastic resin or thermosetting resin is used as a binder resin, and wax,
It is preferable to use a mixture of a material that imparts releasability such as silicone.

As described above, the antireflection layer 3 is formed of a cured product of a thermoplastic resin, preferably a cured resin, and more preferably a cured product of an ionizing radiation-curable resin that is cured by ultraviolet rays or electron beams. Is preferably formed from a cured product of an ionizing radiation-curable resin in terms of production speed, heat resistance, hardness and the like.

As the ionizing radiation-curable resin, specifically, a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule are appropriately mixed. It is a conductive resin composition. Ionizing radiation refers to electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or crosslinking molecules, and usually uses ultraviolet rays or electron beams.

Examples of prepolymers and oligomers in the ionizing radiation-curable resin composition include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, polyether methacrylates, polyol methacrylates, melamines. Methacrylates such as methacrylate, polyester acrylate,
Examples include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of the monomer in the ionizing radiation-curable resin composition include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, and acrylic acid-2-
Acrylic esters such as ethylhexyl, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, methacrylic acid Methacrylic esters such as ethoxymethyl, phenyl methacrylate and lauryl methacrylate; 2- (N, N-diethylamino) ethyl acrylate; 2- (N, N-dimethylamino) ethyl acrylate; -2 acrylic acid -(N, N-dibenzylamino) methyl, unsaturated substituted substituted alcoholic esters such as 2- (N, N-diethylamino) propyl acrylate, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene Guri Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, and other compounds, dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol Polyfunctional compounds such as dimethacrylate and / or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycolate, etc. Is mentioned.

Usually, as the monomer in the ionizing radiation-curable resin composition, one or a mixture of two or more of the above compounds may be used, if necessary. In order to provide suitability, it is preferable that the content of the prepolymer or oligomer is 5% by weight or more and the content of the monomer and / or polythiol compound is 95% by weight or less.

When flexibility is required when the ionizing radiation-curable resin composition is cured, the amount of the monomer may be reduced or an acrylate monomer having one or two functional groups may be used. When abrasion resistance, heat resistance, and solvent resistance are required when the ionizing radiation-curable resin composition is cured, an ionizing radiation-curable resin such as an acrylate monomer having three or more functional groups is used. Composition design is possible. Here, assuming that the functional group is 1, 2-
Hydroxy acrylate, 2-hexyl acrylate,
Phenoxyethyl acrylate is exemplified. As those having two functional groups, ethylene glycol diacrylate;
1,6-hexanediol diacrylate is exemplified. As those having three or more functional groups, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
And dipentaerythritol hexaacrylate.

In order to adjust physical properties such as flexibility and surface hardness when the ionizing radiation-curable resin composition is cured, a resin which is not cured by ionizing radiation irradiation is added to the ionizing radiation-curable resin composition. Can also. Examples of specific resins include the following. Thermoplastic resins such as polyurethane resin, cellulose resin, polyvinyl butyral resin, polyester resin, acrylic resin, polyvinyl chloride resin, and polyvinyl acetate. Above all, addition of a polyurethane resin, a cellulose resin, a polyvinyl butyral resin or the like is preferable from the viewpoint of improving flexibility.

When the ionizing radiation-curable resin composition is cured by ultraviolet irradiation, a photopolymerization initiator or a photopolymerization accelerator is added. As the photopolymerization initiator, in the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like is used alone or as a mixture. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. . The addition amount of the photopolymerization initiator is 0.1 to 1 with respect to 100 parts by weight of the ionizing radiation-curable resin composition.
0 parts by weight.

The ionizing radiation-curable resin composition may be used in combination with the following organic reactive silicon compound.

One of the organosilicon compounds has the general formula R _m Si
(OR ') _n and R and R' have 1 carbon atom
Represents an alkyl group of 10 to 10, and the suffix m of R and the suffix n of R ′ are each an integer satisfying a relationship of m + n = 4.

Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane , Tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-
Butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, dimethylethoxysilane,
Dimethylmethoxysilane, dimethylpropoxysilane,
Examples include dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, and the like.

The organosilicon compound 2 which can be used in combination with the ionizing radiation-curable resin composition is a silane coupling agent.

More specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Methacryloxypropylmethoxysilane, N-β-
(N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane and the like can be mentioned.

The organosilicon compound 3 which can be used in combination with the ionizing radiation-curable resin composition is an ionizing radiation-curable silicon compound. Specific examples include a plurality of functional groups that react and crosslink by irradiation with ionizing radiation, for example, an organosilicon compound having a molecular weight of 5,000 or less and having a polymerizable double bond group, and more specifically, one end. Examples include vinyl-functional polysilanes, vinyl-functional polysilanes at both ends, vinyl-functional polysiloxane at one terminal, vinyl-functional polysiloxane at both terminals, and vinyl-functional polysilane or vinyl-functional polysiloxane obtained by reacting these compounds.

More specifically, the following compounds are used.

[0050]

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Other organic silicon compounds that can be used in combination with the ionizing radiation-curable resin composition include (meth) acrylic compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane. Acryloxysilane compounds and the like can be mentioned. As the ionizing radiation curable resin, the hardness after curing is JIS K
Those showing a hardness of “H” or more in a pencil hardness test indicated by 5400 are more preferable.

It is preferable that the resin of any type has a low refractive index in order to exhibit antireflection performance.
For long-term use as an anti-reflective molded product, the surface must have durability, especially scratch resistance, and it is advantageous to increase the hardness. Therefore, it is necessary to increase the density to increase the hardness. The refractive index of the antireflection structure is 1.4 to 1.7,
More preferably, it is 1.6 or less.

The low-refractive-index layer 4 also has the function of preventing reflection, but when the present invention is applied to an injection-molded product, the surface of the obtained injection-molded product is prevented from being scratched or contaminated by careless contact. It is made of a resin composition having a lower refractive index of light than the antireflection layer 3.

In particular, when the low refractive index layer 4 is formed of a fluorine-based resin or a silicone-based resin, the refractive index of light is 1.3 to 1.4. It is preferable because the refractive index is lower than a general refractive index (a cured product of an acrylate-based resin composition, and the refractive index of light is 1.5 or more) when the reflective layer 3 is made of a cured product. Since these materials have a contact angle with water of 100 degrees or more, they also have antifouling properties and are therefore preferable. When it is not necessary to provide the low refractive index layer 4 with a special function by using the above-mentioned fluororesin or silicone resin, the fluororesin selected in consideration of the adhesion to the antireflection layer 3. The low refractive index layer may be formed using a thermoplastic resin other than the silicone resin.

These materials may be formed by either a dry process such as vapor deposition or a wet process such as ordinary coating.

The antistatic treatment can be specifically performed by applying an antistatic agent or conductive fine particles, and may be blended into the material constituting the injection molded article main body 10 or may constitute the outermost surface of the final product. This is done by blending into a layer to be coated.
Alternatively, an antistatic treatment can be performed by forming a metal oxide thin film on the outermost surface.

The injection-molded article of the present invention is obtained by using the above-described sheet for providing an antireflection layer of the present invention at the time of injection molding. FIG. 5A shows an injection molded product of the present invention.
As shown in FIG. 1, a sheet 1 for applying an antireflection layer shown in FIG.
Is a sheet obtained by laminating the base material sheets 2 facing the injection molded article body 10 side. Although not shown, as shown in FIG. 1B, the base sheet 2 may be formed by laminating two layers of a non-heat-fusible layer 2a and a heat-fusible layer 2b. Alternatively, the portion of the antireflection layer-providing sheet 1, which is the transfer sheet shown in FIG. 1A, except for the release sheet 5, is laminated with the heat-fusible layer 6 side facing the injection molded article body 10 side. is there. Although not shown, a portion obtained by laminating portions excluding the releasable sheet substrate 5a and the releasable layer 5b from the one shown in FIG. 2B may be used.

As shown in FIG. 5 (b), in the injection molded article of the present invention, in any of the cases described with reference to FIG. 5 (a), a low refractive index layer 4 is further laminated on the uppermost surface. It may be.

As shown in FIG. 5C, the injection-molded article of the present invention is not only provided on the upper side of the injection-molded article body 10 but also on the upper side.
The base sheet 2 (or the heat-fusible layer 6), the antireflection layer 3, the low refractive index layer 4, and the like may be laminated on the lower side.
FIG.
Any of the types described with reference to FIG. 5A and FIG. 5B may be stacked, and the same or different ones may be stacked above and below.

The injection-molded article of the present invention may be composed of a thermoplastic resin, but may be composed of a thermosetting resin (cured in a product state), and is conceptually included in the latter. Or an ionizing radiation-curable resin (which is already cured in the state of a product). These types of different resins may be used in combination. The injection-molded article may be opaque at least for the purpose of imparting antireflection properties to the surface, but the injection-molded article has transparency because it often imparts antireflection properties to light-transmitting products. It is preferred that

When a thermoplastic resin is used as the transparent material, polystyrene, ABS resin, ACS resin, AE
S resin, cellulose resin, polyarylate, polybutadiene, polybutylene, ionomer, polyethylene, polypropylene, polymethylpentene, methacrylic resin such as polymethyl methacrylate and polyethyl methacrylate,
Acrylic resin such as polybutyl acrylate, methacrylic /
Polyester resins such as styrene copolymer, nitrile resin, polyacetal, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / isophthalate copolymer, polybutylene terephthalate, polycarbonate, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoride Ethylene, ethylene
Polyethylene resin such as tetrafluoroethylene copolymer, polyamide resin such as nylon 6, nylon 66, polyimide resin, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene vinyl alcohol copolymer, etc. Cellulose resins such as vinyl resins, cellulose triacetate, and cellophane can be used alone or as a mixture, or as a copolymer thereof.

When a thermosetting resin is used as the transparent material, an unsaturated polyester resin, an epoxy resin or the like can be used.

The injection molded article of the present invention is preferably manufactured by using an injection molding apparatus 20 as shown in FIG. FIG. 4 is a diagram showing an outline of the injection molding apparatus 20, in which a movable mold plate 21 and a fixed mold plate 22 are respectively attached to the left and right, and a cavity 23 is provided between the mold plates 21 and 22.
Is formed.

The reflection layer-providing sheet 1 of the present invention is unwound from above between the two mold plates 21 and 22, and is supplied to the portion where the cavity 23 is formed. As shown in FIG. 6 (b), the supplied sheet 1 for reflecting layer application is formed into a schematic shape of the cavity 23 by vacuum forming or the like using one of the mold plates 21, and is fixed to the cavity. The mold plates 21 and 22 are closed, and the fixed side mold plate 2 is
The molten resin is injected into the cavity 23 through the cavity 2, and the heat and the injection pressure at the time of the injection further deform the reflection layer-imparting sheet 1 along the shape of the template. In close contact. After cooling, when the two mold plates 21 and 22 are opened, an injection-molded article in which the reflection layer-imparting sheet 1 is laminated on one side is obtained. It is punched into a shape to obtain a product in which the reflective layer applying sheet 1 is laminated. When the reflection layer-imparting sheet 1 is a transfer sheet, the releasable sheet 5 or the releasable sheet substrate 5a and the releasable layer 5b are peeled off to obtain a product.

In the above, the molding of the reflection layer-imparting sheet 1 in advance is performed by a molding device outside the injection molding machine.
It may be supplied into the cavity 23. In addition, depending on the shape, it is possible that the pre-molding of the reflection layer-imparting sheet 1 prior to the injection molding may not be performed, but the pre-molding is more suitable for the mold of the reflection layer-imparting sheet 1. Is less likely to occur, such as increased followability and partial extreme stretching.

In order to remove the gas generated from the injected resin so that no distortion remains in the obtained molded product, an injection molding machine capable of evacuating the inside of the cavity 23 may be used.

The injection-molded article obtained by the present invention can be used in various applications, and can reduce the glare by suppressing the reflection of the illuminated light. It can also be used in applications that effectively emit light. For the purpose of suppressing reflection and reducing glare,
There is also a balance with the essential functions, but windows of transportation such as automobiles, railway cars, ships, aircraft, etc., observation windows, doors, etc., or windows of buildings, skylights, doors, windows of killing, lights There is a window, etc. (collectively referred to as windows, etc.).
These windows and the like may reflect sunlight or nighttime automobile headlights and may cause glare in an unexpected case. Therefore, the present invention may be applied to the outside of these windows or the like or by replacing them with these. Can be applied. In these, the anti-reflection structure is set to the outside or outside.

Of course, in these windows and the like, since the lighting installed inside the transportation means or the building reflects inside, there is a case where it hinders the view of the outdoors. In some cases, the injection molded article of the present invention may be applied to a window or the like with the antireflection structure facing inward. Therefore, in some cases, an anti-reflection structure may be required on the outside and inside of the window or the like, and separate injection molded products may be applied to both the outside and inside of the window or the like,
An injection-molded article having an antireflection layer on both sides as described with reference to FIG. 5C may be used.

In the transportation system as described above, the injection-molded article of the present invention is placed on the surface of instruments and displays provided in the driver's seat, cockpit and other places with the antireflection structure facing the observation side. Can be applied. It can reduce glare and improve the visibility of instruments and displays.

In addition, the injection molded product of the present invention can be applied to various display portions of devices such as general electric appliances, audio equipment, watches, cameras, and the like. Examples include calculators, personal computer displays (CRTs,
There are a liquid crystal display and a PDP. ) And portable terminal devices, mobile phones, IC recorders, CD players, DVD players, MD players, video tape recorders, various audio devices, video cameras, and digital cameras.
For the purpose of preventing reflection of external light, the injection molded article of the present invention is applied with the antireflection layer side facing out. When applied to these, the substrate may be a polarizing plate or may have antistatic properties, or the substrate may be a touch panel.

Although these instruments and displays may be of a self-luminous type, they are usually illuminated with a backlight or a front light to provide visibility, and are described in the examples of windows and the like. Similarly to the above, an injection molded product having a reflective layer on both surfaces may be used. As one example, in a front light type liquid crystal display,
It is preferable to use an injection molded product in which an antireflection structure is applied to the liquid crystal side of the light guide plate. The observation side is usually formed with a prism array which is inclined or has been abolished so that the ridge lines are parallel. However, if necessary, an antireflection layer may be applied to the observation side.

[0072]

According to the first aspect of the present invention, the antireflection property of the multilayer thin film lamination type or the satin finish can be eliminated, the antireflection property can be immediately provided by lamination at the time of injection molding, and the shape following property can be improved. In addition, it is possible to provide an antireflection layer-providing sheet in which it is not necessary to perform fine irregularities on a mold for each product shape. According to the invention of claim 2, claim 1
In addition to the effects of the invention, since the base sheet is formed by laminating a non-heat-fusible layer and a heat-fusible layer, an antireflection layer-providing sheet that can be used by selecting one having high suitability is used. Can be provided. According to the third aspect of the present invention, in addition to the effects of the first or second aspect of the present invention, since a low-refractive-index layer is further provided, the antireflection layer-imparting sheet has an antireflection effect and an increased surface durability. Can be provided. According to the fourth aspect of the present invention, it is possible to provide an antireflection layer-providing sheet which has substantially the same effect as the first aspect of the invention, and can immediately provide an antireflection property by lamination at the time of injection molding. According to the invention of claim 5, in addition to the effect of the invention of claim 4, the unevenness reproducibility is good, and the fine unevenness is less likely to be impaired when the sheet for reflecting layer addition is stored. Sheets can be provided. Claim 6
According to the invention, in addition to the effect of the invention according to claim 4 or 5, since the low refractive index is laminated along the fine irregularities, the antireflection layer has an antireflection effect and improved surface durability. An application sheet can be provided. Claim 7
According to the invention, by setting the antireflection layer-providing sheet according to any one of claims 1 to 3 in a mold, it is possible to impart an antireflection property to the surface of the molded article by molding. Further, it is possible to provide a method for producing a molded article having an antireflection layer. According to the invention of claim 8, the antireflection layer-providing sheet according to any one of claims 4 to 6 is set in a mold at the time of molding, and after the molding, the release sheet is peeled off. Further, it is possible to provide a method for producing a molded article having an antireflection layer, which can impart antireflection properties to the surface of the molded article. According to the ninth aspect of the present invention, in addition to the effects of the seventh or eighth aspect, the antireflection layer-providing sheet is preliminarily molded, so that the antireflection layer-providing sheet can follow the mold. It is possible to provide a method for producing a molded article having an antireflection layer, which has an improved antireflection layer. According to the tenth aspect, in addition to the effect of the seventh or eighth aspect, there is provided a method of manufacturing a molded article having an antireflection layer, which can be preformed without preparing another mold. can do. According to the eleventh aspect of the present invention, there is provided a molded article having an anti-reflection layer, wherein the sheet for imparting an anti-reflection layer having the effects of any one of the first to third aspects is laminated on the surface of an injection molded article. can do. According to the twelfth aspect of the present invention, the reflection-reflecting layer has a portion obtained by removing the releasable sheet from the antireflection layer-providing sheet having the effect of any one of the fourth to sixth aspects on the surface of the injection-molded article. A molded article having the prevention layer can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing a cross-sectional structure of an adhesive sheet type sheet for imparting an antireflection layer.

FIG. 2 is a view showing a cross-sectional structure of a transfer sheet type sheet for imparting an antireflection layer.

FIG. 3 is a view showing an example of fine irregularities of an antireflection molded article.

FIG. 4 is a view showing an arrangement of fine irregularities of an antireflection molded product.

FIG. 5 is a diagram showing an example of an injection molded product.

FIG. 6 is a diagram showing a method for manufacturing an injection molded product.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 antireflection layer-providing sheet 2 substrate sheet (2a; non-heat-fusible layer, 2b; heat-fusible layer) 3 antireflection layer 4 low-refractive-index layer 5 peelable sheet (5a; peelable sheet substrate) , 5
b; peelable layer) 6 heat-fusible layer 10 injection-molded product main body 20 injection molding machine 21 movable-side mold plate 22 fixed-side mold plate 23 cavity

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H042 BA04 BA12 BA20 2K009 AA02 AA12 BB24 BB25 BB28 CC24 CC34 CC42 DD15 EE03 4F100 AJ06A AK01A AK01D AK17C AK25B AK41A AK46A AK52C AR00B AT10BA10 BA03 BA03 BA03 BA03 JL12A JN01A JN01B JN01C JN06B JN18C 4F206 AA16 AA24 AA33 AA43 AG03 AH33 JA07 JB13

Claims (12)

[Claims] 1. An anti-reflection layer comprising a myriad of fine irregularities having a pitch equal to or less than the wavelength of light and having a refractive index of light varying in a thickness direction is laminated on a substrate sheet. The surface opposite to the side on which the anti-reflection layer is laminated is at least heat-fusible, and the base sheet and the anti-reflection layer are both used for injection molding characterized by having transparency. Sheet for applying an anti-reflection layer. 2. The anti-reflection layer of the base sheet, wherein the anti-reflection layer side is a non-heat fusible layer and the opposite side to the anti-reflection layer side is a heat fusible layer. The surface on the side opposite to the side on which the layers are laminated is heat-fusible, and the non-heat-fusible layer and the heat-fusible layer are both transparent, so that the base sheet is transparent. The sheet for imparting an antireflection layer for use in injection molding according to claim 1, wherein the sheet has a property. 3. An antireflection layer for use in injection molding according to claim 1, wherein a low refractive index layer having transparency is laminated on an exposed surface of the antireflection layer. Application sheet. 4. The releasable surface of a releasable sheet having at least one surface being a releasable surface constitutes a mold surface having an inverse shape to the fine irregularities of the antireflection layer according to claim 1. The anti-reflection layer according to claim 1, wherein a transparent resin layer is filled in the inverse shape and laminated on the molding surface, and the peelable surface of the anti-reflection layer is formed. A heat-fusible layer is laminated on the surface on the opposite side, and at least the reflection for use in injection molding is characterized in that the transparent resin layer and the heat-fusible layer have transparency. A sheet for providing a prevention layer. 5. The release sheet by laminating on one side of a base sheet a cured product layer of a curable resin whose surface has an inverse shape to the fine irregularities of the antireflection layer according to claim 1. The antireflection layer-providing sheet for use in injection molding according to claim 4, wherein the sheet comprises the peelable surface and the mold surface. 6. The low-refractive-index layer having transparency is laminated along the fine irregularities on the molding surface side of the antireflection layer. A sheet for providing an antireflection layer for use in injection molding. 7. The antireflection layer-providing sheet according to claim 1, which is set in a mold such that the heat-fusible side of the base sheet faces the inside of the cavity. After that, the mold is closed, and then, the molding resin having transparency is injected and filled into the inside of the mold, cooled after filling, the mold is opened after cooling, and the molded product is taken out. Of manufacturing a molded article having an anti-reflection layer. 8. The mold after setting the antireflection layer-providing sheet according to claim 4 in a mold such that the heat-fusible layer side faces the inside of the cavity. And then injecting and filling a molding resin having transparency into the mold, cooling after filling, opening the mold after cooling, taking out a molded product, and peeling the release sheet. A method for producing a molded article having an antireflection layer. 9. The molded article having an anti-reflection layer according to claim 7, wherein the anti-reflection layer-providing sheet is preliminarily molded and set in the mold. Production method. 10. The method according to claim 7, wherein the antireflection layer-providing sheet is set in the mold by preforming using the mold.
A method for producing a molded article having the antireflection layer according to the above. 11. The method according to claim 1, wherein the surface of the injection molded article is provided.
An injection-molded article having an anti-reflection layer laminated thereon, wherein the heat-fusible surface side of the anti-reflection layer application sheet according to any one of claims 3 to 3 is laminated. 12. The method according to claim 4, wherein the surface of the injection molded article is provided.
7. An injection-molded article having an anti-reflection layer laminated thereon, wherein the heat-fusible layer side is laminated without the release sheet from the anti-reflection layer application sheet according to any one of claims 6 to 6.