JP2001071653A - Antidazzling surface protective transferring material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antidazzling surface protective (layer) transferring material, which can give antidazzling properties to a body to be transferred together with scuffing resistance, stain resistance, solvent resistance and water resistance to a body to be transferred. SOLUTION: A hard coating layer mainly made of at least particles having the average particle diameter of 0.6 to 20 μm, fine particles having the average particle diameter of 1 to 500 nm and an ionizing radiation curing resin is provided on a releasable base film surface. Further, an intermediate layer made of butyral resin and isocyanate is provided on the hard coating layer. Furthermore, an adhesive bond is provided on the intermediate layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior / exterior building materials, molded parts for automobile interior / exterior use, miscellaneous goods, cards, cosmetic container caps, general-purpose packages, displays (display bodies), etc., weak electric appliances, woodwork, crafts and crafts. In the essential fields such as scratch resistance, stain resistance, solvent resistance, water resistance, etc., such as products, the scratch resistance, stain resistance, The present invention relates to a surface protection transfer material that imparts anti-glare properties and solvent resistance and water resistance.

[0002]

2. Description of the Related Art Hitherto, it has been generally difficult to obtain strong interlayer adhesion when laminating a layer made of an ionizing radiation-curable resin on another substrate. Therefore, the curing of the ionizing radiation-curable resin layer during the processing of the ionizing radiation-curable resin layer is controlled to an incomplete state, and after processing the next layer such as an adhesive layer, a method of completely curing with ionizing radiation again or a tacky adhesive is used. Methods for obtaining adhesion with an ionizing radiation-curable resin layer and the like have been performed. Recently, a first intermediate layer made of a polyurethane resin, an acrylic resin and an isocyanate is provided between an ionizing radiation-curable resin and an adhesive layer, and a second intermediate layer made of an acrylic resin is provided next. A method for obtaining the adhesion between the cured resin layer and the adhesive layer has been proposed.

[0003]

In the conventionally proposed laminate of the ionizing radiation-curable resin layer, the purpose, if not sufficient, of achieving the lamination of the ionizing radiation-curable resin layer as a hard coat layer has been achieved. However, in recent years, in the surface modification of liquid crystals and other display bodies,
It is not satisfied only with the lamination of the hard coat layer, scratch resistance,
It is required to provide anti-glare properties as well as stain resistance, solvent resistance, and water resistance. Therefore, an object of the present invention is to solve the problems such as control of the curing of the ionizing radiation-curable resin layer in the conventional method and re-curing by the ionizing radiation after the next layer processing, and appearance and the decrease in resistance due to the use of the adhesive, An object of the present invention is to provide a surface protection transfer material which is excellent in interlayer adhesion between an ionizing radiation-curable resin layer and an adhesive layer, and can simultaneously provide antiglare properties.

[0004]

Means for Solving the Problems The surface protective transfer material of the present invention has been made to solve the above-mentioned problems, and has at least an average particle diameter on one surface of a base film (1) having releasability. A hard coat layer (5) containing 0.6 to 20 μm particles (2), fine particles (3) having an average particle diameter of 1 to 500 nm, and an ionizing radiation curable resin (4) as main components;
Butyral resin and isocyanate
And an adhesive layer on the intermediate layer.
(7) An antiglare surface protective transfer material characterized by comprising (7), wherein particles (2) are 0.05 to 30% by weight based on the ionizing radiation-curable resin (4), and fine particles (3) are The anti-glare surface protective transfer material having a content of 0.001 to 80% by weight based on the ionizing radiation-curable resin (4), and the anti-glare surface wherein the fine particles (3) are colloidal silica. The anti-glare surface protective transfer material described above, wherein the weight ratio of the butyral resin to the isocyanate in the intermediate layer (7) is in the range of 95: 5 to 50:50.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The releasable base film (1) used in the antiglare surface protective transfer material of the present invention is not particularly limited, and has a releasability and a sufficient self-holding property. Any material can be used as long as it is used as a base material of a normal transfer material having the same. For example, synthetic resin films such as polyethylene terephthalate film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamide imide film, polyethylene film, polyvinyl chloride film and the like, and synthetic resin films such as cellulose acetate film, cellophane paper, glassine paper, etc. Film-like materials such as Western paper and Japanese paper, or composite film-like materials or composite sheet-like materials thereof, or those obtained by subjecting them to a release treatment, or those provided with a release layer.

The thickness of the base film (1) is not particularly limited, and is usually in the range of 4 to 100 μm, preferably in the range of 9 to 50 μm. This is preferable because the transfer material can be easily manufactured. The ionizing radiation curable resin (4), which is one of the main components of the hard coat layer (5) used for imparting surface protection in the antiglare surface protection transfer material of the present invention, is not particularly limited, and is, for example, urethane acryl. -Polyester, polyester acrylate, epoxy acrylate, unsaturated polyester, silicone acrylate, other special acrylate
And a mixture mainly containing particles (2), fine particles (3), and the like, and a coating material obtained by dissolving them in an organic solvent, using a gravure printing method, a screen printing method, or an offset printing method. A hard coat layer formed by coating, drying, and curing with ionizing radiation on the base film (1) by a normal printing method such as the above is preferable. The hard coat layer in the present invention has a pencil hardness of 1H or more.

In the antiglare surface protective transfer material of the present invention, the smaller the particle size of the particle (2), which is one of the main components of the hard coat layer (5) used for imparting the surface protective property, from the viewpoint of transparency and the like. Although good, it is necessary to be 0.6 μm or more in order to obtain a sufficient anti-glare property due to the unevenness of the surface, and it is preferably 20 μm or less from the appearance such as surface smoothness, more preferably 1.0 μm or more and 10 μm or less. Things. The particles (2) used in the present invention are not particularly limited, but include silica,
Silicone resin particles, acrylic resin particles, styrene resin particles, nylon resin particles and the like, the shape of the particles,
In order to diffuse light efficiently, a spherical or nearly spherical shape is preferable.

As the fine particles (3) used in the present invention, those having an average particle diameter of 1 to 500 nm are used, and particularly preferable are fine particles having an average particle diameter of 5 to 200 nm. When the average particle size exceeds 500 nm, the transmittance tends to be impaired,
If it is less than 1 nm, the effect of preventing interference becomes extremely small. As the fine particles (3), inorganic oxide fine particles dispersed in a colloidal form are preferable, and as the inorganic oxide fine particles, silicon oxide, antimony oxide, tin oxide, indium oxide, zinc oxide, alumina, titania, zirconia and the like can be mentioned. In particular, considering the price and color, silicon oxide,
For example, colloidal silica is preferable. It is more preferable that these fine particles (3) are treated with a coupling agent such as acryloxy-functional silane or the like and then subjected to acrylate modification so as to be crosslinked with ionizing radiation, and then mixed with the ionizing radiation-curable resin. Since the surface acrylated inorganic oxide fine particles participate in the crosslinking with the ionizing radiation-curable resin, even if they are blended in a large amount, the hardness does not decrease and the hardness tends to increase. In addition, mixing is easy without the need for a step of dispersing the resin in the ionizing radiation-curable resin, and the transparency after mixing is excellent. Inorganic oxide fine particles subjected to acrylate surface treatment and fine particles not subjected to acrylate surface treatment may be used in combination.

According to the present invention, as described above, the particles (2) and the fine particles (3) are contained in the hard coat layer (5), whereby the density of the particles is increased at the expense of transparency, and the occurrence of interference is suppressed. (This caused the haze to rise and the screen became very difficult to see.) The problem of the conventional technology was solved, and the occurrence of interference was suppressed, and an antiglare hard coat layer having a haze of 30% or less was obtained. It is something that can be done. In the present invention, an antiglare hard coat layer having sufficient suppression of the occurrence of interference and a haze of 20% or less, and more preferably 10% or less is obtained. The amount of the particles (2) imparting antiglare properties is affected by the specific gravity of the particles (2) used, but is usually 0.05 to 30% by weight based on the solid content of the ionizing radiation-curable resin (4). Preferably it is in the range of 0.2 to 5% by weight. The added amount of the fine particles (3) is 0.001 of the solid content of the ionizing radiation-curable resin (4).
To 80% by weight, preferably 0.2 to 40% by weight. The thickness of the hard coat layer (5) is not particularly limited, and is usually selected as appropriate from a range of about 1.0 to 10 μm. If the thickness is less than 1.0 μm, it is difficult to cure, which is not preferable. On the other hand, when the thickness exceeds 10 μm, cracks in the coating film occur, and conversely, poor curing occurs.

The intermediate layer (6) in the anti-glare surface protective transfer material of the present invention comprises a gravure printing method, a screen printing method, and a coating method in which a mixture of butyral resin and isocyanate is dissolved in an organic solvent. It is formed by applying, drying and forming on the hard coat layer (5) by a normal printing method such as an offset printing method. The degree of polymerization of the butyral resin is not particularly limited, but is preferably about 800 to 2,000. Butler
The mixing ratio of the resin to the isocyanate is 98: 2 to 5
A range of 0:50 is preferred. If the ratio of the isocyanate is 2 or less or the ratio of the butyral resin is 50 or less, it is difficult to obtain strong adhesion to the hard coat layer (5). In the present invention, the intermediate layer may be the above-mentioned one intermediate layer, but it is more preferable to further provide a second intermediate layer on the intermediate layer. The second intermediate layer preferably contains butyral resin as a main component. For example, a gravure printing method, a screen printing method, an offset printing method or the like is obtained by dissolving the above-mentioned butyral resin alone in an organic solvent. Formed on the intermediate layer (6) by the ordinary printing method described above.

The thickness of the intermediate layer (6) is 0.1
If it is less than 0.1 μm, strong adhesion to the ionizing radiation-curable resin layer, that is, the hard coat layer (5) cannot be obtained, and if it is 2.0 μm or more, the intermediate layer Properties often have a bad influence on the physical properties of the surface protection transfer material, and are not preferred in terms of cost.

The adhesive layer (7) used in the anti-glare surface protective transfer material of the present invention is formed by coating a coating material obtained by dissolving an adhesive resin in an organic solvent by a usual printing method such as a gravure printing method, a screen printing method and an offset printing method. It is formed by applying and drying on an intermediate layer by a method. The adhesive resin used for the adhesive layer (7) used in the antiglare surface protection transfer material of the present invention is not particularly limited, and may be appropriately selected from resins used for ordinary transfer materials. For example, acrylic, vinyl acetate, vinyl chloride, styrene butadiene, vinyl chloride-vinyl acetate, ethylene-vinyl acetate, polyester, chloride rubber, chlorinated polypropylene,
The resin is appropriately selected from emulsion resins, organic solvent resins, and water-soluble resins containing a urethane-based resin alone or a mixture thereof as a main component. The adhesive layer (7) is formed by applying a coating liquid obtained by diluting the resin with water or an organic solvent to an intermediate layer (6) by a gravure printing method, a screen printing method, or an offset printing method.
Alternatively, it is formed by applying and drying on a second intermediate layer, a printing layer, a coloring layer, or the like added as necessary. The thickness of the adhesive layer is not particularly limited, and is usually appropriately selected and adopted from a range of about 0.3 to 20 μm according to the surface condition of the transfer object. The anti-glare surface protective transfer material thus obtained has all the problems of the conventional surface protective transfer material having an ionizing radiation-curable resin layer, namely, interlayer adhesion, appearance, workability, and post-transfer resistance. By solving all of the above problems, it is excellent in scratch resistance, stain resistance, solvent resistance, water resistance, etc. and also has an antiglare effect.

[0013]

The present invention will be described in detail below with reference to examples. Hereinafter, all parts in Examples are parts by weight. ** Example 1 A coating solution consisting of 94 parts of melamine resin, 50 parts of toluene and 50 parts of methyl ethyl ketone was applied on a biaxially stretched polyethylene terephthalate film having a thickness of 25 μm by a Meyer bar coating method, dried and dried to a thickness of 3 μm. A release layer was formed. Then, on this release layer, 20 parts of urethane acrylate, 10 parts of epoxy acrylate, 3 parts of silica particles having an average particle diameter of 5 μm, 3 parts of colloidal silica having an average particle diameter of 10 nm, 40 parts of toluene, 20 parts of methyl ethyl ketone, and 10 parts of isopropyl alcohol Was applied by a Meyer bar coating method, dried, and cured by ionizing radiation to form a 3.5 μm thick hard coat layer (5). On this hard coat layer (5), 8 parts of butyral resin, 2 parts of isocyanate, and 50 parts of toluene
And a coating solution consisting of 40 parts of methyl ethyl ketone by a gravure coating method and dried to form an intermediate layer (6) having a thickness of 0.2 μm. On this intermediate layer (6), a coating solution composed of 10 parts of acrylic resin, 50 parts of toluene and 40 parts of methyl ethyl ketone was applied by a gravure coating method and dried to form an adhesive layer (7) having a thickness of 1.5 μm. An antiglare surface protective transfer material of the present invention was obtained.

** Example 2 On a biaxially oriented polypropylene film having a thickness of 12 μm,
3 parts of silica particles having an average particle diameter of 5 μm, and an average particle diameter of 10 n
m, 3 parts of colloidal silica, urethane acrylate 20
Parts, epoxy acrylate 10 parts, toluene 40 parts, M
A solution consisting of 20 parts of EK and 10 parts of IPA was applied by reverse coating, dried, and cured by ionizing radiation to form a 3.5 μm thick hard coat layer (5). A solution comprising 8 parts of butyral resin, 2 parts of isocyanate, 50 parts of toluene and 40 parts of MEK is applied on the hard coat layer (5) by a gravure coating method and dried to form an intermediate layer having a thickness of 0.2 μm. (6) was formed. On this intermediate layer, 5 parts of butyral resin, 5 parts of acrylic resin, 5 parts of toluene
A solution consisting of 0 parts and 40 parts of MEK was applied by a gravure coating method and dried to form an intermediate second layer having a thickness of 0.3 μm. Further, an acrylic resin 20 is formed on the intermediate second layer.
, 60 parts of toluene and 30 parts of MEK were applied by a reverse coating method and dried to a thickness of 1.0 μm.
Was formed to obtain an antiglare surface protective transfer material of the present invention.

** Comparative Example [0015] In Example 1, except that 3 parts of silica particles having an average particle diameter of 5 µm and 3 parts of colloidal silica having an average particle diameter of 10 nm were not added in the formation of the hard coat layer, all other steps were performed. In the same manner as in the above, a transfer material was obtained. <Evaluation method> Interlayer adhesion was evaluated by transferring the transfer material obtained in each of the above Examples and Comparative Examples to an acrylic plate, and using a Nichiban cello tape in accordance with the degree of peeling according to the cross-cut peeling method shown below. Was done. <Cross-cut peeling method> Draw 11 lines and 11 lines 2mm apart on the transfer surface with a cutter knife, make a total of 100 squares, and put a 24mm-wide Nichibancello tape on the squares, and quickly apply them. The tape was forcibly peeled in the direction of 180 degrees, and the evaluation was made in five steps according to the number of the remaining squares as shown below. [Adhesion Rank] (Rank) (Number of remaining squares) 5 ... 95 to 100/100 (peeled squares 0 to 5) 4 ... 80 to 94/100 (peeled squares 6 to 20) 3 60-79 / 100 (peeled squares 21-40) 2 ... 30-59 / 100 (peeled squares 41-70) 1 ... 0-29 / 100 (peeled squares 71) ~ 100) <Evaluation of interlayer adhesion> Example 1 ... 5 Example 2 ... 5 Comparative example ... 5 In each of Example 1, Example 2, and Comparative Example,
The light transmittance at 550 nm was 80% or more, and the haze value in the haze meter was 5.5% or less. When the reflection of the light source by visual judgment is measured, the first embodiment is explained. Both of the examples 2 were excellent in anti-glare properties with almost no reflection of the light source, but the comparative examples had a problem in the anti-glare property in which reflection of the light source was observed.

[0016]

The antiglare surface protective transfer material of the present invention uses a butyral resin and an isocyanate for the intermediate layer, and contains an ionizing radiation-curable resin layer and two kinds of particles having a specific particle size. It is a transfer material that uses a coat layer.It has excellent interlayer adhesion, which was difficult to obtain in the past, and also has anti-glare properties such as scratch resistance, stain resistance, solvent resistance, water resistance, etc. It can be provided.

Claims (4)

[Claims] 1. One side of a base film (1) having releasability, at least particles (2) having an average particle diameter of 0.6 to 20 μm, fine particles (3) having an average particle diameter of 1 to 500 nm, and ionizing radiation curing. A hard coat layer (5) containing a resin (4) as a main component, an intermediate layer (6) comprising butyral resin and isocyanate on the hard coat layer, and an adhesive layer on the intermediate layer. (7) An anti-glare surface protection transfer material characterized by having (7). 2. The particles (2) are 0.05 to 30% by weight based on the ionizing radiation-curable resin (4), and the fine particles (3) are 0.001 to 80% by weight based on the ionizing radiation-curable resin (4). The anti-glare surface protective transfer material according to claim 1, which is a content ratio of: 3. The anti-glare surface protective transfer material according to claim 1, wherein the fine particles (3) are colloidal silica. 4. The antiglare surface protective transfer material according to claim 1, wherein the weight ratio of the butyral resin to the isocyanate in the intermediate layer (7) is in the range of 95: 5 to 50:50.