WO2012063637A1

WO2012063637A1 - Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film

Info

Publication number: WO2012063637A1
Application number: PCT/JP2011/074504
Authority: WO
Inventors: 裕明山田; 禎寿後藤; 敬一林
Original assignee: 新日鐵化学株式会社
Priority date: 2010-11-10
Filing date: 2011-10-25
Publication date: 2012-05-18

Abstract

Provided are: a multilayered hardcoat film for injection molding which, as a hardcoat for molded resin articles, has an extremely high surface hardness, excellent adhesion, and excellent conformability to molds; a process for producing the multilayered hardcoat film; and a process for producing an injection-molded object using the multilayered hardcoat film. A hardcoat layer which has a thickness of 20 µm or more, a transmittance measured at a wavelength of 550 nm of 90% or higher, and a glass transition temperature of 230ºC or higher is formed by applying a photocurable resin composition containing a cage silsesquioxane resin that has photocurability to one surface of a base-layer film constituted of, for example, a polycarbonate resin and curing the composition. Thus, a multilayered hardcoat film for injection molding is obtained. This multilayered hardcoat film is placed in a mold for injection molding, and a resin is molded. Simultaneously therewith, the multilayered hardcoat film is integrated with the surface of the molded resin object.

Description

Hard coat film laminate for injection molding, method for producing the same, and method for producing injection molded article using the hard coat film laminate

The present invention relates to a hard coat film laminate for injection molding, a method for producing the same, and a method for producing an injection molded article using the hard coat film laminate, for example, windows for automobiles, aircraft, buildings, schools, shops, etc. In addition to glass, lamp covers and lighting covers for automobiles, aircraft, etc., polycarbonate resin, PMMA (polymethyl methacrylate) resin, which is widely used for housings and various parts such as personal computers and portable electronic devices, or The present invention relates to a hard coat film laminate for injection molding necessary for the production of a molded article of PET (polyethylene terephthalate) resin, a method for producing the same, and a method for producing an injection molded article using the same.

Conventionally, injection molded products of thermoplastic resins such as polycarbonate have been widely used as alternative materials because of their lighter weight than glass or metal. However, polycarbonate resin has a lower surface hardness than glass and is easily scratched. To prevent this, the surface is protected by applying paint or pasting a curable film on it. Yes.

For example, Japanese Patent Application Laid-Open No. 2008-260202 (Patent Document 1) discloses a base material layer made of a mixed resin composition containing a polycarbonate resin and a polyester resin, and an ultraviolet curable resin composition containing an acrylic polymer. An invention relating to a hard coat film for injection molding provided with a hard coat layer made of a cured product is described. Japanese Patent Application Laid-Open No. 2002-1759 (Patent Document 2) discloses that a curable coating agent is applied to a resin film, the coating agent is semi-cured, and then mounted in a mold to obtain a polycarbonate resin. An invention relating to a method for producing a polycarbonate resin molded article obtained by injection molding, peeling off a resin film, and further curing the coating agent to cure the surface is described. In Patent Document 2, a silicone coating agent obtained by adding colloidal silica to an organosilane having a structure of R _n Si (OH) _4-n and an acrylic coating agent are mentioned as preferable ones.

However, acrylic and silicone coating agents that have been used mainly as hard coats to protect the surface of injection-molded resin until now are not sufficient in terms of scratch resistance. In addition, in order for resin molded products to be used in a wider range of applications, the surface hardness can be fully expressed, but the adhesiveness to injection molded products is excellent, and at the same time, the ability to follow the mold is satisfied. There is a further need for such a hard coat film laminate.

JP 2008-260202 A JP 2002-1759 A

The present invention has been made in order to solve the above-described problems, and has a very high surface hardness as a hard coat of a molded article of polycarbonate resin, PMMA resin, or PET resin. An object of the present invention is to provide a hard coat film laminate for injection molding that is excellent in followability. Moreover, an object of this invention is to provide the method of manufacturing such a hard coat film laminated body for injection molding. Furthermore, this invention aims at providing the manufacturing method of the injection molded object using this hard coat film laminated body.

As a result of intensive studies by the present inventors in order to achieve the above object, preferably, a photocurable resin composition containing a photocurable siliceous silsesquioxane resin is cured to form a hard coat layer. , By stacking and integrating with a base material layer containing at least one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, and mounting it in a mold, a molded product of polycarbonate resin, PMMA resin, or PET resin It has been found that a hard coat having a high surface hardness can be formed on the surface with a good adhesion through a base material layer, and that the following property to the mold can be satisfied, and the present invention has been completed.

That is, the gist of the present invention is as follows.
[1] A single layer of a resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more layers, and a single layer laminated on one side of the base layer A hard coat film laminate for injection molding comprising a hard coat layer, wherein the hard coat layer comprises a photocurable resin composition containing a photo-curing cage silsesquioxane resin. A hard coat film laminate for injection molding characterized by being cured and having a thickness of 20 μm or more, a transmittance at a wavelength of 550 nm of 90% or more, and a glass transition temperature of 230 ° C. or more.

[2] The cage silsesquioxane resin has the following general formula (1):
RSix ₃ (1)
[In Formula (1), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group. In the presence of an organic polar solvent and a basic catalyst, the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The hard coat film laminate for injection molding as described in [1], which is obtained.

[3] The cage silsesquioxane resin is represented by the following general formula (2):
[RSiO _3/2 ] _n (2)
[In Formula (2), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, and

n shows

8, 10, 12, or 14. The hard coat film laminate for injection molding according to [1] or [2], wherein the laminate is a cage-type silsesquioxane resin represented by

[4] R is the following general formula (3):

[In the formula (3), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. The hard coat film laminate for injection molding according to [2] or [3], which is an organic functional group represented by

[5] The injection-coated hard coat film laminate according to any one of [1] to [4], further comprising a plastic film cover layer on the surface of the hard coat layer.

[6] The hard coat film laminate for injection molding according to any one of [1] to [5], wherein the thickness of the base material layer is in the range of 30 to 300 μm.

[7] A single layer of one type of resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more types and a hard coat layer were laminated and integrated. A method for producing a hard coat film laminate for injection molding, wherein a photocurable resin composition containing a photocurable siliceous silsesquioxane resin is applied to one side of a base material layer and cured. A hard coat film for injection molding characterized by forming a hard coat layer having a thickness of 20 μm or more, a transmittance of 90% or more at a wavelength of 550 nm, and a glass transition temperature of 230 ° C. or more A manufacturing method of a layered product.

[8] A single layer of a single resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more types of layers, and laminated on one side of the base layer The hard coat film laminate for injection molding provided with the hard coat layer formed is placed in an injection mold, and in that state, one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is injected into the mold A method for producing an injection-molded product, wherein the molding of the resin is performed at the same time and the hard coat film laminate is integrated with the surface of the resin molded product.

[9] The hard coat layer is formed by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin and has a thickness of 20 μm or more, and has a transmittance of 90% at a wavelength of 550 nm. The method for producing an injection-molded article according to [8], wherein the glass transition temperature is 230 ° C. or higher.

[10] The cage silsesquioxane resin has the following general formula (1):
RSix ₃ (1)
[In Formula (1), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group. In the presence of an organic polar solvent and a basic catalyst, the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The method for producing an injection-molded article according to [9], which is obtained.

[11] The cage silsesquioxane resin is represented by the following general formula (2):
[RSiO _3/2 ] _n (2)
[In Formula (2), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, and

n shows

8, 10, 12, or 14. ] The manufacturing method of the injection-molded article according to [9] or [10], characterized in that it is a cage-type silsesquioxane resin represented by

[12] R is the following general formula (3):

[In the formula (3), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. The method for producing an injection-molded article according to [10] or [11], wherein the organic functional group is represented by the formula:

[13] The method for producing an injection-molded article according to any one of [8] to [12], further comprising a plastic film cover layer on the surface of the hard coat layer side.

[14] The method for producing an injection-molded article according to any one of [8] to [13], wherein the thickness of the base material layer is in the range of 30 to 300 μm.

[15] Any one of [8] to [14], wherein the injection-molded hard coat film laminate is continuously fed into an injection mold from a state wound up in a roll state. A method for producing an injection-molded article according to item.

[16] Any one of [8] to [14], wherein the injection-molded hard coat film laminate is supplied into the injection mold one by one from a state of being cut into a sheet shape. A method for producing an injection-molded article according to 1.

In the present invention, by making a laminated structure of a base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate and a hard coat layer obtained by curing a predetermined photocurable resin composition, An effect that can be used for film insert molding while maintaining a high surface hardness is obtained. That is, the hard coat film laminate for injection molding of the present invention forms a hard coat layer from a photocurable resin composition containing a photocurable siliceous silsesquioxane resin. In addition, it is possible to impart high surface hardness to the surface of the injection molded product. In addition, since the hard coat layer is formed on the surface of the injection molded product through the base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, the hard coat layer has excellent adhesion. It is possible to prevent peeling.

Further, in the present invention, a hard coat film laminate for injection molding comprising a base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate and a hard coat layer is placed in an injection mold, In this state, by injecting polycarbonate resin, PMMA resin, or PET resin into the mold, resin molding is performed, and at the same time, the hard coat film laminate is integrated with the surface of the resin molded body, so that glass or metal is formed. It is possible to obtain an injection molded body that can be used as an alternative material. In particular, by forming a predetermined hard coat layer with a photocurable resin composition containing a photocurable siliceous silsesquioxane resin, it is possible to follow the mold while maintaining sufficient surface hardness. In addition, it is possible to impart high surface hardness to the surface of the injection molded product. In addition, since the hard coat layer is formed on the surface of the injection molded product through the base material layer containing one or more of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, the hard coat layer has excellent adhesion. While being able to prevent peeling, it is possible to integrate at the same time as the molding at the time of injection molding, and it is excellent in productivity.

FIG. 1 is a schematic cross-sectional view showing a hard coat film laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing the state of insert molding using the hard coat film laminate of the present invention. FIG. 3 is a schematic cross-sectional view showing an injection molded body obtained by insert molding. FIG. 4 is a schematic view showing an example of an injection molding machine used in the method for producing an injection molded body of the present invention. FIG. 5 shows the light transmittance of only the hard coat layer in the hard coat film laminate of the present invention. FIG. 6 shows the measurement results of the glass transition temperature of only the hard coat layer in the hard coat film laminate of the present invention.

Hereinafter, the present invention will be described in detail.
In FIG. 1, one Embodiment of the hard coat film laminated body 1 for injection molding of this invention is shown. The hard coat film laminate 1 includes a hard coat layer 2 on one side of a single layer of a single resin selected from the group consisting of polycarbonate, PMMA, and PET, or a base layer 4 composed of two or more layers. The cover layer 3 of the plastic film is formed by laminating and integrating. The resin for forming the base material layer is preferably a film-like resin, and preferably one resin film selected from the group consisting of polycarbonate, PMMA, and PET may be used alone as the base material layer. In addition, a plurality of layers in which two or more kinds of resin films are laminated may be used as the base material layer. Among these, a base material layer composed of a single layer of a polycarbonate film, a PMMA film, or a PET film, or a base material layer in which two polycarbonate films and a PMMA film are bonded together is more preferable.

In addition, the thickness of the base material layer is preferably in the range of 30 to 300 μm including the case of a single layer and the case of a plurality of layers. If it is smaller than 30 μm, the strength as a base material layer is insufficient and there is a risk of breakage. On the contrary, if it is larger than 300 μm, the followability to the mold shape is deteriorated at the time of injection molding. Further, for each resin of polycarbonate, PMMA, and PET used in the present invention, an ultraviolet absorber, a plasticizer, a pigment, or the like may be used as an additive. In the present invention, the entire thickness of the hard coat film laminate for injection molding is not particularly limited, and preferably has a suitable thickness range described for each layer.

In the present invention, the hard coat layer 2 preferably has a thickness of 20 μm or more by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin, and has a glass transition temperature. Is made of a transparent resin layer having a transmittance of not less than 230 ° C. and a transmittance of 90% or more at a wavelength of 550 nm.

Thus, the thickness of the preferred hard coat layer (transparent resin layer) is 20 μm or more, preferably in the range of 20 to 400 μm, and more preferably in the range of 50 to 80 μm. When the thickness is less than 20 μm, sufficient surface hardness cannot be obtained. On the other hand, when the thickness exceeds 400 μm, flexibility is impaired, and for example, it may be difficult to obtain a molded product having a curved surface. is there.

Assuming that the hard coat film laminate of the present invention is used for window glass of automobiles and aircraft, the surface becomes high temperature by direct sunlight. Further, when used as a housing for a personal computer or a portable electronic device, heat is generated inside the device. Therefore, the hard coat layer needs to have heat resistance to prevent deformation due to heat, and the resin forming the hard coat layer has a glass transition temperature of 230 ° C. or higher, preferably 250 ° C. or higher. In addition, the transmittance at a wavelength of 550 nm is preferably 90% or more in a liquid crystal display portion of a window glass of an automobile or an aircraft, a personal computer, or a portable electronic device.

Moreover, when forming such a suitable hard-coat layer, content of the said cage silsesquioxane resin in a photocurable resin composition is 3 mass% with respect to the mass of a photocurable resin composition. The amount is preferably in the above range, and more preferably in the range of 5 to 70% by mass. When the content is less than 3% by mass, the glass transition temperature of the transparent resin layer tends to be low in the hard coat film laminate for injection molding, and the heat resistance at the mold temperature at the time of injection molding may be insufficient. is there. On the other hand, when the content exceeds 70% by mass, the toughness of the hard coat layer is impaired, and there is a possibility that appearance defects such as cracks are generated on the surface by handling. Thus, by adjusting the content of the cage silsesquioxane resin, the glass transition temperature of the hard coat layer can be adjusted, for example, even when the content of the cage silsesquioxane resin is the same. The glass transition temperature of the transparent resin layer is appropriately adjusted by adjusting the content of the cage silsesquioxane resin, because it varies depending on the glass transition temperature of other resins used in combination with the cage silsesquioxane resin. Can be adjusted. Note that the upper limit of the glass transition temperature of the hard coat layer is about 450 ° C. in consideration of containing an organic substance.

The vertical silsesquioxane resin that forms a preferred hard coat layer in the present invention is a vertical silsesquioxane resin having photocurability. Examples of such cage-type silsesquioxane resins include the following general formula (1):
RSix ₃ (1)
The silicon compound represented by the formula is hydrolyzed in the presence of an organic polar solvent and a basic catalyst and partially condensed, and the resulting hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. Things. In the general formula (1), R represents an organic functional group having a (meth) acryloyl group or a vinyl group, and X represents a hydrolysis group such as an alkoxy group or an acetoxy group.

In the present invention, such a cage silsesquioxane resin is represented by the following general formula (2):
[RSiO _3/2 ] _n (2)
It is preferable that it is a cage-type silsesquioxane resin represented by these. In the general formula (2), R represents an organic functional group having a (meth) acryloyl group or a vinyl group, and n represents 8, 10, 12 or 14.

Furthermore, in the present invention, the R is represented by the general formula (3):

It is preferable that it is an organic functional group represented by these. In the general formula (3), R ¹ represents a hydrogen atom or a methyl group. In the general formula (3), m represents an integer of 1 to 3.

Such a cage silsesquioxane resin has a reactive functional group composed of an organic functional group having a (meth) acryloyl group on all silicon atoms in the resin, and has a controlled molecular weight distribution and molecular structure. A cage silsesquioxane resin is preferred. Further, the molecular structure of such a cage silsesquioxane resin may not be a completely closed polyhedron, and may be a structure in which a part is cleaved, for example. Moreover, the average molecular weight of such cage-type silsesquioxane resin is not particularly limited, and such cage-type silsesquioxane resin may be an oligomer.

The photocurable resin composition referred to in the present invention is not particularly limited as long as it is a resin composition that can be cured by irradiation with active energy rays. Such a photocurable resin composition may contain other resins in addition to the cage silsesquioxane. The other resin that can be used by mixing with the cage silsesquioxane resin in this way is not particularly limited as long as the resin has compatibility and reactivity with the cage silsesquioxane resin. (Meth) acrylic acid, methyl (meth) acrylate, and the like are mentioned as the resin having a (meth) acrylic group, and it is not directly reactive with the cage silsesquioxane, but can be used in combination. , Epoxy resin, urethane resin, and silicone resin. Moreover, such a photocurable resin composition may further contain a filler-based additive as long as it does not inhibit photocurability. Specific examples of the filler-based additive include fine particle fillers such as silica, alumina and titanium oxide, glass fiber short fibers or long fibers, and plastic fibers such as styrene and polyester.

Moreover, such a photocurable resin composition usually further contains a photopolymerization initiator. Examples of such photopolymerization initiators include alkynephenone-based, acylphosphine oxide-based, and titanium cene-based photopolymerization initiators. Specific examples of such photopolymerization initiators include α-hydroxyalkylphenone, biacetylacetophenone, benzophenone, benzyl, benzoylisobutyl ether, benzyldimethyl ketal, (1-hydroxycyclohexyl) phenylketone, (1-hydroxy-1 -Methylethyl) phenyl ketone, (α-hydroxyisopropyl) (p-isopropylphenyl) ketone, diethylthioxanthone, ethyl anthraquinone, bis (diethylamino) benzophenone and the like.

In addition, as such a photocurable resin composition, what contains a well-known solvent as a diluent may be used for viscosity adjustment etc., but time is considered when the devolatilization removal process of a solvent is considered. Therefore, from the viewpoint that the production efficiency is reduced, and from the viewpoint that residual solvent exists in the cured film and leads to deterioration of the properties of the molded film, it is preferable to use a solvent having a content of 5% or less. It is more preferable to use those not containing.

Next, a method for producing the hard coat film laminate for injection molding of the present invention described above will be described. The hard coat film laminate for injection molding of the present invention is prepared, for example, when a polycarbonate film is used alone as a base material layer, and the photocurable resin composition is prepared on the surface of the polycarbonate film layer in advance. It can be manufactured by curing after forming the transparent resin layer.

The method for applying the photocurable resin composition in this way is not particularly limited, and a known method can be adopted as appropriate. As the coating device, a known coating device can be adopted. However, when a curing reaction is caused by using the coating head, gel-like deposits cause streaks and foreign matters. It is preferable not to hit. In addition, as a coating method, known methods such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion coating, spinner coating, etc. A coating method can be adopted.

In addition, as a method of curing after applying the photocurable resin composition, for example, an ultraviolet irradiation method in which ultraviolet rays are generated and irradiated on the photocurable resin composition after application to be photocured is adopted. Can do. Examples of the ultraviolet lamp used in such a method include a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a pulse type xenon lamp, a xenon / mercury mixed lamp, a low-pressure sterilization lamp, and an electrodeless lamp. Among these ultraviolet lamps, it is preferable to use a metal halide lamp or a high-pressure mercury lamp. Although irradiation conditions vary depending on the conditions of the respective lamp, irradiation exposure may be in the range of 20 ~ 10000mJ / cm ^2, it is preferably in the range of at 100 ~ 10000mJ / cm ^2. Further, from the viewpoint of effective use of light energy, it is preferable to attach an elliptical, parabolic, or diffusive reflector to the ultraviolet lamp, and a heat cut filter or the like may be attached as a cooling measure.

Moreover, it is preferable to attach a cooling device to the irradiated part of the ultraviolet lamp. By such a cooling device, it is possible to suppress thermal deformation of the hard coat film laminate for injection molding induced by heat generated from the ultraviolet lamp. As a cooling method of such a cooling device, a known method such as an air cooling method or a water cooling method can be employed.

In addition, when hardening a photocurable resin composition by an ultraviolet irradiation method in this way, since the ultraviolet curing reaction is a radical reaction, the reaction inhibition by oxygen is received. Therefore, from the viewpoint of suppressing reaction inhibition by oxygen in the curing reaction of the photocurable resin composition, it is preferable to cover the surface with a cover layer made of a transparent plastic film after applying the photocurable resin composition. In addition, by covering the surface of the photocurable resin composition with the cover layer in this manner, the oxygen concentration on the surface of the photocurable resin composition is preferably 1% or less, and preferably 0.1% or less. preferable. In order to reduce the oxygen concentration in this way, it is preferable to employ a transparent plastic film having no voids on the surface and low oxygen permeability. Examples of such film materials include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene phthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, and vinyl fluoride. Plastics such as resin, polyamide, polyarylate, cellophane, polyethersulfone and norbornene resin. These plastics can be used alone or in combination of two or more. Since such a plastic film must be able to be peeled off from the cured photocurable resin composition (hard coat layer), the surface of the plastic film is subjected to easy peeling treatment such as silicon coating or fluorine coating. It is preferable to use what is.

Next, a method for manufacturing the injection molded body 8 according to the present invention will be described. First, the hard coat layer 2 and the plastic film are formed on one surface of a single layer of a single resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer 4 composed of two or more types. The hard coat film laminate in which the cover layer 3 is laminated and integrated is placed in an injection mold. For example, as shown in FIG. 2 (a), the hard coat film laminate 1 is arranged in a flat shape in the cavity of the first injection mold 5. At this time, the cover layer 3 of the plastic film of the hard coat film laminate 1 is disposed so as to contact the cavity wall surface of the first injection mold 5.

Thereafter, as shown in FIG. 2B, the second injection mold 6 is overlaid on the first injection mold 5 and closed, and in this state, the cavities in the

molds

5 and 6 are inserted through the injection gate. A thermoplastic resin is injected into the container. At this time, injection molding of a thermoplastic resin is performed to form a resin molded body, and at the same time, the hard coat film laminate is integrally formed on the surface of the resin molded body. Thereafter, the plastic film cover layer 3 on the surface of FIG. 3 is peeled off to obtain an injection molded body 8 having a hard coat portion on the surface.

FIG. 4 is a schematic view showing the entire injection molding machine equipped with a mechanism for continuously supplying the hard coat film laminate 1. Here, the second injection molding 6 in FIG. 2 is arranged on the fixed side platen 11, the first injection mold 5 is arranged on the movable side platen 9, and harder than the film loading machine 13 along the movable side platen 9. After the coated film laminate 1 is supplied to the first injection mold 5 and the movable platen 9 is moved, the first injection mold 5 is overlapped with the second injection mold 6 and closed, and then from the nozzle 12. The injection molded body 8 is obtained by injecting the thermoplastic resin. Then, the hard coat film laminated body 1 for obtaining the next injection molding body can be supplied by operating a film loading machine. The film loading machine only needs to have a mechanism for continuously unwinding from the supply side, and does not necessarily have a mechanism for winding.

As the resin for injection molding, that is, as the thermoplastic resin constituting the resin molding 7, the base material layer (base material layer containing at least one of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate) 4 The resin is not particularly limited as long as it is a thermoplastic resin that can be melted and integrated with each other, and is preferably a polycarbonate resin, a PMMA resin, or a PET resin.

The injection molding resin may contain various additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and a plasticizer inhibitor.

As the shape of the injection mold, a planar mold and a mold having a curvature can be used. A mold having a curvature is preferably set so that the elongation is 0.1% to 10%, the length to the end, and the amount of sagging.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. Note that “part” means “part by mass” unless otherwise specified.

Example 1
The following structural formula (4)

25 parts of silsesquioxane, 65 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “light acrylate DCP— A ") 10 parts and 2.5 parts of hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, trade name" IRGACURE 184 ") are stirred and mixed uniformly, and then defoamed to obtain a liquid photocurable resin composition. Got.

Next, a polycarbonate film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy”) obtained by surface-treating the obtained liquid photocurable resin composition with a silane coupling agent (trade name “KBE-903”, manufactured by Shin-Etsu Chemical Co., Ltd.) in advance. C000 ") so that the thickness after curing was 0.05 mm. Then, a transparent cover film (material: polyethylene terephthalate, light transmittance of 90% or more at a wavelength of 550 nm) is pressure-bonded to a photocurable resin to form a cover layer, and then ultraviolet rays are emitted from a metal halide lamp at 6400 mJ / cm ^2. The hard coating layer is cured by irradiating with an irradiation exposure amount of 1 to 3, whereby a hard layer for injection molding having a three-layer structure of a base material layer 4-hard coat layer 2-cover layer 3 made of polycarbonate resin as shown in FIG. Coated film laminate 1 was obtained.

Next, as shown in FIG. 2A, a part of the cover layer 3 remains on the cavity wall surface of the first injection mold while the hard coat film laminate 1 is kept flat in the first injection mold 5. After placing in a contact manner, the second injection mold was overlaid on the first injection mold, and in this state, it was dried in advance at 120 ° C. for 24 hours from the injection gate into the cavity in the mold. By injecting a polycarbonate resin (trade name “Taflon 1900” manufactured by Idemitsu Co., Ltd.) under the conditions of a resin temperature of 280 ° C., a mold temperature of 80 ° C., a set injection pressure of 1700 kg / cm ² , and an injection time of 3 seconds, FIG. An injection molded body 8 having a hard coat portion made of the hard coat film laminate 1 on the surface of a resin molded body 7 made of a polycarbonate resin having a thickness of 3 mm as shown in FIG.

The surface hardness and strength of the injection molded body 8 provided with the hard coat portion obtained as described above were evaluated as follows. The results are shown in Table 1.

<Surface hardness evaluation method>
The molded body provided with the hard coat portion was subjected to scratch hardness (pencil method) according to JIS K5600-5-4. A steel wool test was also conducted. The steel wool test was performed using an eraser testing machine (manufactured by Honko Seisakusho Co., Ltd.) using steel wool # 0000, and the steel wool was reciprocated with a load of 500 g.

<Strength evaluation method>
A bending test was performed on a molded body having a hard coat portion. As a test method, a test piece of 120 mm × 30 mm is placed on a base having an opening at the center (opening: 80 mm × 50 mm), and from the upper side, a push core tip R: SR5, speed: 5 mm / cm, indentation The bending stress when pressed down to a depth of 40 mm and the surface state of the hard coat layer were observed.

(Example 2)
The liquid photocurable resin composition was applied so that the thickness after curing was 0.025 mm, and after obtaining an injection molded body 8 provided with a hard coat portion in the same manner as in Example 1, Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
The polycarbonate film side of the polycarbonate PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy C001”) in which the polycarbonate film and the PMMA film are bonded together is previously a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-903”). Surface treatment with. An injection-molded article provided with the above-mentioned liquid photocurable resin composition on the surface-treated polycarbonate film side so that the thickness after curing is 0.07 mm, and having a hard coat portion in the same manner as in Example 1. After obtaining 8, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
The above liquid photocurable resin composition was applied so that the thickness after curing was 0.015 mm, and after obtaining an injection-molded body 8 having a hard coat portion by the same method as in Example 1, it was carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
As a comparative example, the product name Iupilon sheet MR58 (thickness: 0.65 mm) manufactured by Mitsubishi Gas Chemical Co., Ltd., which had an acrylic hard coat applied to the surface of a polycarbonate sheet, was attached and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
The liquid photocurable resin composition described above was applied to a PMMA film (manufactured by Sumitomo Chemical Co., Ltd., trade name “Technoloy S001G”) which was previously surface-treated with a silane coupling agent (trade name “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.). It applied so that the thickness after hardening might be set to 0.1 mm, and the hard coat film laminated body 1 for injection molding was obtained by the method similar to Example 1. FIG. Thereafter, the injection resin was changed to PMMA resin (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumipex HT55X”) in the same manner as in Example 1, resin temperature 250 ° C., mold temperature 80 ° C., set injection pressure 129 MPa, injection time 6 seconds. The injection molded body 8 provided with the hard coat portion made of the hard coat film laminate 1 on the surface of the resin molded body 7 made of 1.6 mm thick PMMA resin as shown in FIG. It was. Table 1 shows the results of evaluation in the same manner as in Example 1.

(Example 5)
15 parts of silsesquioxane represented by the above structural formula (4), 55 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product) 30 parts of the name “light acrylate DCP-A”) and 2.5 parts of hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name “IRGACURE 184”) are stirred and mixed uniformly, and then defoamed and liquidized. A photocurable resin composition was obtained.

The above liquid photocurable resin composition was applied so that the thickness after curing was 0.050 mm, and an injection-molded body 8 provided with a hard coat portion was obtained in the same manner as in Example 1. Table 1 shows the results of evaluation in the same manner as in Example 1.

(Example 6)
70 parts of silsesquioxane represented by the structural formula (4), 20 parts of dipentaerythritol (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product) 10 parts of the name “light acrylate DCP-A”) and 2.5 parts of hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, trade name “IRGACURE 184”) are uniformly stirred and mixed, and then defoamed to form a liquid. A photocurable resin composition was obtained.

(Reference example)
The liquid photocurable resin composition used in Example 1 above was applied on PET for the base layer so that the thickness after curing was 0.050 mm, and another cover layer PET was then applied thereon. After pressure-bonding to the coated photocurable resin, the hard coat layer was cured by irradiating ultraviolet rays with an ultra-high pressure mercury lamp at an irradiation exposure amount of 6400 mJ / cm ² . After curing, the PET for the base layer and the cover layer were peeled off to obtain a film having only the hard coat layer.

<Light transmittance measurement>
The light transmittance of only the hard coat layer was measured with a spectrophotometer (manufactured by Hitachi, Ltd., Spectrophotometer U-4000), and the transmittance at 550 nm was 91.7%. The results are shown in FIG.

<Dynamic viscoelasticity measurement>
The glass transition temperature of only the hard coat layer was measured with a dynamic viscoelasticity measuring device (DVE-V4 Rheospectr manufactured by UBM Co., Ltd.). The results are as shown in FIG. 6, and the glass transition temperature represented by tan δ was not observed in the measurement up to 230 ° C. Here, E ′ represents the storage elastic modulus, E ″ represents the loss elastic modulus, and tan δ = E ″ / E ′.

Moreover, although the light transmittance and the dynamic annual elasticity measurement were similarly performed about the photocurable resin composition used in Example 5 and Example 6, both were 90% or more of transmittance, up to 230 ° C. No glass transition temperature was observed in the measurement.

1: Hard coat film laminate 2 for injection molding 2: Hard coat layer 3: Cover layer 4: Base material layer 5: First injection mold 6: Second injection mold 7: Resin molded body 8: Injection molded body 9: Movable side platen 10: Tie bar 11: Fixed side platen 12: Nozzle 13: Film loading machine

Claims

A single layer of one type of resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more types of layers, and laminated and integrated on one side of the base layer A hard coat film laminate for injection molding comprising a hard coat layer, wherein the hard coat layer is obtained by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin. A hard coat film laminate for injection molding, characterized in that the thickness is 20 μm or more, the transmittance at a wavelength of 550 nm is 90% or more, and the glass transition temperature is 230 ° C. or more.
The cage silsesquioxane resin has the following general formula (1):
RSix 3 (1)
[In Formula (1), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group. In the presence of an organic polar solvent and a basic catalyst, the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The hard coat film laminate for injection molding according to claim 1, which is obtained.
The cage silsesquioxane resin has the following general formula (2):
[RSiO 3/2 ] n (2)
[In Formula (2), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, and n shows 8, 10, 12, or 14. The hard coat film laminate for injection molding according to claim 1, wherein the laminate is a cage silsesquioxane resin represented by the formula:
R is the following general formula (3):

[In the formula (3), R 1 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. The hard coat film laminate for injection molding according to claim 2 or 3, wherein the organic functional group is represented by the formula:
The hard coat film laminate for injection molding according to any one of claims 1 to 4, further comprising a plastic film cover layer on the surface of the hard coat layer side.
The hard coat film laminate for injection molding according to any one of claims 1 to 5, wherein the thickness of the base material layer is in the range of 30 to 300 µm.
For injection molding in which a single layer of a single resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate or a base layer composed of two or more layers and a hard coat layer are laminated and integrated. A method for producing a hard coat film laminate, wherein a photocurable resin composition containing a photocurable silsesquioxane resin is applied to one side of a base material layer and cured to obtain a thickness Of a hard coat film laminate for injection molding, characterized in that a hard coat layer having a glass transition temperature of 230 ° C. or higher is formed at a transmittance of 90% or higher at a wavelength of 550 nm. Production method.
A single layer of one type of resin selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a base layer composed of two or more types of layers, and laminated and integrated on one side of the base layer A resin by placing a hard coat film laminate for injection molding provided with a hard coat layer in an injection mold and injecting any of polycarbonate, polymethyl methacrylate, or polyethylene terephthalate into the mold in that state A method for producing an injection-molded product, wherein the hard coat film laminate is integrated with the surface of the resin molded product at the same time as the molding is performed.
The hard coat layer is formed by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin, having a thickness of 20 μm or more, and having a transmittance of 90% or more at a wavelength of 550 nm. And the glass transition temperature is 230 degreeC or more, The manufacturing method of the injection molded object of Claim 8 characterized by the above-mentioned.
The cage silsesquioxane resin has the following general formula (1):
RSix 3 (1)
[In Formula (1), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, X shows the hydrolysis group chosen from an alkoxy group or an acetoxy group. In the presence of an organic polar solvent and a basic catalyst, the silicon compound is hydrolyzed and partially condensed, and the obtained hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The method for producing an injection-molded article according to claim 9, which is obtained.
The cage silsesquioxane resin has the following general formula (2):
[RSiO 3/2 ] n (2)
[In Formula (2), R shows the organic functional group or vinyl group which has a (meth) acryloyl group, and n shows 8, 10, 12, or 14. The method for producing an injection-molded article according to claim 9 or 10, wherein the resin is a cage-type silsesquioxane resin represented by the formula:
R is the following general formula (3):

[In the formula (3), R 1 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. The method for producing an injection-molded article according to claim 10 or 11, wherein the organic functional group is represented by the formula:
The method for producing an injection-molded article according to any one of claims 8 to 12, further comprising a plastic film cover layer on the surface of the hard coat layer side.
The method for producing an injection-molded article according to any one of claims 8 to 13, wherein the thickness of the base material layer is in the range of 30 to 300 µm.
The injection according to any one of claims 8 to 14, wherein the injection-molded hard coat film laminate is continuously supplied into the injection mold from a state of being wound in a roll state. Manufacturing method of a molded object.
The injection molding according to any one of claims 8 to 14, wherein the injection-molded hard coat film laminate is supplied into the injection mold one by one from a state of being cut into a sheet shape. Body manufacturing method.