TWI457242B - A resin molded product using a film for insert molding is used - Google Patents

Description

Resin molded article using a film for insert molding

The present invention relates to various resin molded articles such as a touch panel of a home appliance, a mobile phone, a game machine, a sound recorder, a notebook computer, and the like (keyboard portion), and more particularly to a resin molding material and surface protection. A resin molded article in which a film for molding is integrated is used.

Conventionally, in the case of performing a pattern on the surface of various molded articles composed of a resin or the like, or a method of providing a surface protective layer, there is a method of forming a printed layer or a surface on a substrate when the molded article is molded by a mold. The film of the protective layer is disposed between the resin and the mold, and the printing layer or the surface protective layer is transferred onto the surface of the molded object by molding, and then the method of peeling off the substrate; or the method of integrally molding the resin and the film by the mold .

Among the films used in these methods, a film which is not peeled off after molding and which is integrated with a molded article is distinguished from a transfer film, and is called an embedded film or a film for insert molding. In the case of such an embedded film, for example, a film of a base film such as a polyester film, a metal deposited film or a printed layer, and a film which can form a hard coat layer of a surface protective layer have been proposed (patent Document 1, Patent Document 2).

[Patent Document 1] JP-A-2005-288720 (Patent Document 2) JP-A-2005-305786

Generally, the hard coat layer used for the purpose of surface protection of a molded article is required to have scratch resistance. For example, the pencil hardness is 2H or more, and the steel wool test requires a hardness of 300 g or more. Therefore, the hard coat layer is composed of a hardenable resin excellent in scratch resistance such as an electron beam curable resin or an ultraviolet curable resin. However, when the film forming such a hard coat layer is used for insert molding, generally, the surface of the molded article is curved or angled, so that cracks are likely to occur on the hard coated surface during molding.

In addition, it is considered that the addition of a thermoplastic resin to the curable resin constituting the hard coat layer for the film for molding can improve the flexibility. However, at this time, by increasing the flexibility, the hardness is lowered and the load of the steel wool test as described above cannot be withstood.

Further, in the hard coat layer of a general hard coat film, in order to prevent hardening shrinkage upon formation of a hard coat layer and occurrence of cracking or whitening due to the occurrence thereof, the ionizing radiation-curable resin composition contains a branch An oligomer of a polymer structure has been proposed in Patent Document 3.

However, the above-mentioned hard coat film is not used for insert molding, and it is unpredictable that the hardened film is hardened and the influence of the hardened film is further suppressed. Moreover, even if the hard coat film described in Patent Document 3 is directly used for insert molding, it is not always possible to prevent occurrence of cracks during press molding.

[Patent Document 3] JP-A-2005-76005

Accordingly, it is an object of the present invention to provide a surface hardness having sufficient surface hardness and no cracking when molded into a film for insert molding. Excellent resin molded product.

In order to solve the above problems, the inventors of the present invention have studied the monomers relating to the hardening type resin constituting the hard coat layer, and have particularly studied the ionizing radiation hardening type by using a polyfunctional oligomer having a dendritic polymer structure. The hard coat layer formed of the resin composition, the relationship between the crack generated when external pressure is applied and the composition of the composition (or the thickness of the hard coat layer). As a result, it has been found that when a film for insert molding having a hard coat layer formed of an ionizing radiation-curable resin composition containing a polyfunctional oligomer having a dendrimer structure in a specific ratio is used, pressurization is applied. In the case of a force such as deformation, it is possible to maintain excellent hard coat resistance which is excellent in crack prevention resistance, and the inventors of the present invention have finally completed.

In other words, the resin molded article of the present invention is characterized in that the film for insert molding provided with a hard coat layer and a molding material are integrally molded by molding, and the hard coat layer is provided on the surface; A hard coat layer formed of an ionizing radiation-curable resin composition containing three or more (meth) acrylate functional groups and having a polyfunctional oligomer of a dendrimer structure.

Further, the resin molded article of the present invention is characterized in that the polyfunctional oligomer having the dendritic polymer structure is contained in an amount of 10 to 160 with respect to 100 parts by weight of the ionizing radiation curable resin composition. weight Share.

Further, the resin molded article of the present invention is characterized in that the hard coat layer contains at least one element containing carbon, nitrogen, oxygen and hydrazine in addition to the polyfunctional oligomer having a dendrimer structure. The ring structure is formed of an ionizing radiation-curable resin composition of a reactive monomer.

Further, the resin molded article of the present invention is characterized in that the hard coat layer contains a photopolymerizable prepolymer and/or a photopolymerizable monomer in addition to the polyfunctional oligomer having a dendritic polymer structure. The ionizing radiation hardening resin composition is formed.

The resin molded article of the present invention is preferably a polyfunctional oligomer (A) having a dendritic polymer structure, a reactive monomer (C) having a ring structure, a photopolymerizable prepolymer other than the same, and/or The ratio of the photopolymerizable monomer (B) is 20 to 200 parts by weight based on 100 parts by weight of (B), and the total of (A) and (C) is 100 parts by weight based on the total of (A) and (C). (C) is 10 to 90 parts by weight.

The resin molded article of the present invention, for example, a molding material is one selected from the group consisting of an acrylic resin and a polycarbonate resin.

Further, the resin molded article of the present invention is characterized in that at least one of a metal deposition layer, a printing layer and an adhesive layer is formed between the molding material and the hard coat layer.

The film for insert molding of the present invention is characterized in that the surface of at least one of the base film is provided with a hard coat layer formed of an ionizing radiation-curable resin composition; and the ionizing radiation hardening type The resin composition contains three or more (meth) acrylate functional groups and has branches A polyfunctional oligomer of a polymer structure.

Further, the film for insert molding of the present invention is characterized in that the polyfunctional oligomer having a dendritic polymer structure contains 10 to 160 parts by weight with respect to 100 parts by weight of the ionizing radiation-curable resin composition. Share.

Further, the film for insert molding of the present invention is characterized in that the ionizing radiation-curable resin composition contains carbon, nitrogen and oxygen in addition to a polyfunctional oligomer having a dendritic polymer structure. And a reactive monomer of a ring structure of at least one element of ruthenium.

Further, the film for insert molding of the present invention is characterized in that the ionizing radiation-curable resin composition has a photopolymerizable prepolymer and/or light in addition to a polyfunctional oligomer having a dendrimer structure. Polymerizable monomer.

The film for insert molding of the present invention is preferably a polyfunctional oligomer (A) having a dendritic polymer structure, a reactive monomer (C) having a ring structure, and a photopolymerizable prepolymer other than the above and/or Or the ratio of the photopolymerizable monomer (B) is 20 to 200 parts by weight in total of (A) and (C) with respect to 100 parts by weight of (B), and 100 parts by weight based on the total of (A) and (C). Parts (C) are 10 to 90 parts by weight.

Further, the film for insert molding of the present invention is characterized in that at least one of a metal deposition layer, a printing layer and an adhesive layer is formed on the other surface of the base film.

Further, the ionizing radiation-curable resin composition of the present invention is characterized by comprising: having three or more (meth) acrylate functional groups and having a polyfunctional oligomer (A) having a dendritic polymer structure, a reactive monomer (C) having a ring structure containing at least one element of carbon, nitrogen, oxygen and hydrazine, and a photopolymerizable prepolymer other than the same / or photopolymerizable monomer (B); the ratio of (A), (B) and (C) is 20 to 200 parts by weight based on 100 parts by weight of (B), (A) and (C), (C) is 10 to 90 parts by weight based on 100 parts by weight of the total of (A) and (C).

Further, the hard coat film of the present invention is formed of the above ionizing radiation curable resin composition.

[Effects of the Invention]

According to the present invention, the ionizing radiation-curable resin composition constituting the hard coat layer for insert molding film contains a polyfunctional oligomer having a dendrimer structure, and the steel wool test can obtain a load of 300 g or more. It is hard-coated and prevents cracking during molding. It is considered that the surface of the hard coat layer has a load which can withstand the load of the steel wool test, and the dendrite structure absorbs the pressure at the time of molding, so that cracking can be prevented.

Further, in addition to the polyfunctional oligomer having a dendritic polymer structure, the reactive monomer having a ring structure is contained, and the hard coat property is not impaired, and further high crack resistance during molding can be achieved. This ring structure is believed to absorb some of the pressure at the time of molding.

[The best form for implementing the invention]

Hereinafter, an embodiment of the resin molded article of the present invention will be described.

The resin molded article of the present invention is a thin film for insert molding having a hard coat layer The film and the molding material are integrally formed by molding, and have a hard coat layer on the surface. The molding material may be any resin that can be injection molded, and for example, a thermoplastic resin such as an acrylic resin, a polycarbonate resin, an ABS resin, or an AS resin, or a thermosetting resin can be used.

The film for insert molding is basically composed of a base film and a hard coat layer which is a hard coat layer formed on the surface of the resin molded article of the present invention by molding.

The substrate film is preferably excellent in transparency, heat resistance, and mechanical strength, and specifically preferably, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. , polycarbonate, polyethylene, polypropylene, polystyrene, cellulose triacetate, acrylic acid, polyvinyl chloride, norbornene compounds, and the like. Especially for the viewpoint of good dimensional stability of heat, it is preferred to use a biaxially stretched polyester film.

The base film is excellent in adhesion between the hard coat layer and the metal vapor-deposited layer or the printed layer or the adhesive layer, and may be subjected to surface treatment such as easy adhesion treatment.

The thickness of the base film is not particularly limited, but is 20 μm to 200 μm, preferably about 50 μm to 150 μm, in consideration of handleability, mechanical strength, and the like.

Then, explain about the hard coat. The hard coat layer is formed of an ionizing radiation hardening type resin. In general, the ionizing radiation-curable resin is irradiated with ionizing radiation (ultraviolet rays or electron beams) to a photopolymerizable prepolymer and/or a photopolymerizable monomer having a reactive group such as an acrylonitrile group in the molecule, and is cross-linked and hardened. . The hard coat layer of the present invention is a photopolymerizable prepolymer having a dendrimer structure and having three or more (meth) acrylates. A multifunctional polyfunctional oligomer.

The dendrimer structure-based monomer is polymerized while being branched, and has a radially expanded shape, and the polyfunctional oligomer having a dendritic polymer structure is represented by the formula (1).

Wherein X is hydrogen, propylene sulfhydryl, or

Specifically, it has a functional group such as an amine group, a hydroxyl group, a carboxyl group, a phenyl group, an oxiranyl group, a vinyl group, or an propylene oxide group, and has a (meth) acrylate functional group at the terminal. In particular, it is preferable to contain an oxirane group and a (meth) acrylate at the terminal from the viewpoints of solubility in a solvent, handling property, and addition of other ionizing radiation-curable resin from the viewpoint of compatibility with a resin. Functional base.

The larger the number of (meth) acrylate functional groups and the molecular weight of the oligomer, the higher the hardness of the film (hard coat layer) formed by the ionizing radiation-curable resin composition, and the cracking is less likely to occur during molding. However, if the number of (meth) acrylate functional groups is too large, the crack resistance at the time of molding is lowered. Further, if the molecular weight of the oligomer is too large, the surface hardness of the hard coat layer is lowered. Therefore, the number of (meth) acrylate functional groups is preferably from 3 to 10, more preferably from 5 to 8. . Further, the molecular weight is preferably from 1,000 to 3,000, more preferably from 1,500 to 2,000.

The ionizing radiation-curable resin may contain a known photopolymerizable prepolymer and a photopolymerizable monomer in addition to the above polyfunctional oligomer. As the photopolymerizable prepolymer, a propylene-based prepolymer such as urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate or polyoxy acrylate can be used. . Further, as the photopolymerizable single system, a monofunctional acrylic monomer such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or butoxyethyl acrylate may be used. , 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxytrimethyl acetate neopentyl glycol diacrylate, etc. One or two or more kinds of polyfunctional acrylic monomers such as a bifunctional acrylic monomer, dipentaerythritol hexaacrylate, trimethylpropane triacrylate, and pentaerythritol triacrylate.

Further, in the case of a photopolymerizable monomer, a reactive monomer having a ring structure can be used. The ring system is composed of at least one element containing carbon, nitrogen, oxygen, and hydrazine, and is preferably a 5-membered ring or a 6-membered ring. In addition, it is not limited to the molecular weight, and it is not possible to provide three or more viewpoints from the viewpoint of preventing cracking of the edge portion due to pressurization at the time of molding and preventing deterioration of hard coatability. Base) acrylate functional group.

Specific examples of the ring structure include cycloolefins such as cyclopentene and cyclohexene, tetrahydrofuran, 1,3-dioxane, ε-caprolactone, ε-caprolactam, decane cyclopentene, and cyclodecane. Isoborn based and the like. The monomer having such a ring structure may, for example, be ε-caprolactone-modified tris-(2-propenyloxyethyl)trimeric isocyanate or ε-caprolactam-modified tris-(2-hydroxyethyl). Trimeric isocyanate, Dimethylol tricyclodecane di(meth)acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-propenyl oxyethyl hexahydrophthalic acid, and the like.

The ratio of the polyfunctional oligomer (A) having the above-described dendrimer structure, the photopolymerizable prepolymer/photopolymerizable monomer (B), and the reactive monomer (C) having a ring structure, considering hard The thickness of the coating or the required hardness or the material of the molded article is appropriately selected. Specifically, when the molding resin is formed by (A) and (B), the polyfunctional oligomer (A) is 160 parts by weight based on 100 parts by weight of the photopolymerizable prepolymer/photopolymerizable monomer (B). The amount by weight or less is preferably 100 parts by weight or less, more preferably 70 parts by weight or less. In addition, the amount of the photopolymerizable prepolymer/photopolymerizable monomer (B) is 10 parts by weight or more, preferably 20 parts by weight or more, and more preferably 30 parts by weight or more. When the content of the polyfunctional oligomer (A) to the (B) 100 parts by weight is 10 parts by weight or more, the ruthenium prevents cracking at the edge portion when it is pressurized at the time of molding. Further, by being 160 parts by weight or less, the hard coat property can be maintained.

Further, when the molding resin is formed of (A), (B), and (C), the polyfunctional oligomer (A) and the reactive monomer (C) having a ring structure are combined. The photopolymerizable prepolymer/photopolymerizable monomer (B) is 20 parts by weight to 200 parts by weight, preferably 30 to 160 parts by weight, more preferably 40 to 140 parts by weight. The ratio of (A) to (C) varies depending on the thickness of the hard coat layer, etc., so it cannot be generalized, but the thickness of the hard coat layer is from 0.5 μm to 10 μm, more preferably from 2 μm to 5 μm. (C) is 10 to 90% by weight, preferably 15 to 60% by weight, more preferably based on the total of (A) and (C). 20~40% by weight. When the content of (C) is 10% by weight or more, cracking is less likely to occur at the edge portion when the crucible is pressurized at the time of molding. Further, by being 90% by weight or less, ruthenium can be prevented from being lowered in hard coatability.

In the ultraviolet curing of the ionizing radiation-curable resin, an additive such as a photopolymerization initiator or a photopolymerization accelerator is preferably used in addition to the photopolymerizable prepolymer and the photopolymerizable monomer described above.

The photopolymerization initiator may, for example, be acetophenone, benzophenone, michelone, benzoin, benzylmethyl ketal, benzhydryl benzoate or α-mercapto oxime ester, Thiol ketones. The photopolymerization accelerator can reduce the polymerization barrier caused by the air during curing, and accelerates the curing rate, and examples thereof include p-dimethylamino benzoic acid isoamyl ester and p-dimethylamino benzoic acid ethyl ester.

Further, in addition to the above-described ionizing radiation curing resin, a resin such as a thermoplastic resin or a thermosetting resin may be added as a binder component in addition to the range of functions of the present invention. Specifically, a resin such as an acrylic resin, a polyester, a polystyrene, a polyvinyl acetate, a polyurethane, or a cellulose acetate may be added as long as it is about 30% by weight or less of the resin constituting the hard coat layer.

Further, the hard coat layer may contain a matting agent for imparting an antiglare function, or an additive such as a colorant, an antistatic agent, or a UV absorber.

The thickness of the hard coat layer is from 0.5 μm to 10 μm, preferably from about 1 μm to about 5 μm. When the ionizing radiation-curable resin composition contains no reactive monomer (C) and contains only the polyfunctional oligomer (A), cracking can be prevented by setting the thickness to 5 μm or less. Ionizing radiation hardening resin composition When the polyfunctional oligomer (A) and the reactive monomer (C) are contained, cracking can be prevented by setting the thickness to 10 μm or less.

The hard coat layer is a polyfunctional oligomer, a photopolymerizable prepolymer, a photopolymerizable monomer (including a reactive monomer), a photopolymerization initiator added as needed, a photopolymerization accelerator, and the like. The coating liquid adjusted by mixing the additive with the diluent solvent is a known coating method such as a bar coater, a die coater, a knife coater, a spin coater, a roll coater, a gravure coater, A flow coater, a spray coater, or screen printing is applied to a base film, and an electron beam or an ultraviolet ray is irradiated to form an ionizing radiation-curable resin composition. The hard coat layer is a layer having a high hardness and a high crack resistance which has a three-dimensional mesh structure by irradiation with an electron beam or ultraviolet rays. It is considered that when pressure (bending force or tensile force) from the outside is applied, the pressure is absorbed by the dendrimer structure in the molecule, so that cracks are prevented from occurring on the surface of the layer.

The basic structure of the film for insert molding is the base film and the hard coat layer, but further, a surface of the base film opposite to the surface on which the hard coat layer is provided may be provided with a printed layer for attaching the molded article or Metal vapor deposition layer. An example of the structure of a typical film for insert molding is shown in Fig. 1 .

The insert molding film 10 shown in the figure is formed on the surface of one of the base films 11 to form the hard coat layer 12, and on the other surface, the decorative layer composed of the metal deposited layer 13 or the printed layer 14 is sequentially formed and The structure of the adhesive layer 15. For example, after the metal deposition layer 13 is formed on the base film 11, the portion of the metal deposition layer 13 is removed by etching, and the base film 11 from which the metal deposition layer 13 is removed is printed, or on the substrate film. 11 is formed by a known printing method, a screen method, a gravure method, an inkjet method, or the like. After the characters or patterns are formed, a metal vapor-deposited layer 13 or the like is formed thereon. The printed layer 14 may be omitted, and the metal deposited layer 13 may be formed directly on the base film 11, or only the printed layer 14 may be free of the metal deposited layer 13. When the printing layer 14 is provided, a receiving layer for receiving printing ink may be provided on the surface of the base film 11 on which the printing layer 14 is provided.

The metal deposition layer 13 may be a metal such as aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, or zinc, or an alloy or compound thereof, such as a vacuum by a known method. The vapor deposition method, the sputtering method, the ion plating method, and the like are formed by vapor deposition.

The adhesive layer 15 is a layer provided to increase the adhesion between the molded material and the metal vapor-deposited layer 13, and a polyurethane, a polyacryl, a polyester, or an epoxy can be suitably used depending on the material of the molded article. Adhesives such as polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, and cellulose.

Next, an example of a method for producing a resin molded article using the film for insert molding of the present invention will be described.

First, the above-mentioned film for insert molding is placed so that the hard coat layer is formed outside when the resin molded article is formed, and the film is formed into a desired shape by press working. Then, the formed film for insert molding is placed in a molding die, heated between the dies, and flows into a resin in a flowing state. The resin is cured and integrated with the film for insert molding to obtain a resin molded article of the present invention. The molding conditions (temperature, mold clamping pressure, time) are appropriately selected depending on the shape of the resin (molding material) or the molded product. Generally, the mold clamping pressure is calculated from the projected area of the molded product × the resin pressure in the mold. In one example, the injection molding resin is ABS resin, and when the molded product size (L×W×H) is 60×80×2 (mm ³ ), the mold clamping pressure is 60 t, the mold temperature is 60° C., the resin temperature is 250° C., and the injection speed is high. 60mm / sec.

In the resin molded article of the present invention, a film having a hard coat layer excellent in crack resistance is used as a film for insert molding, so that cracking does not occur during press forming of the film for insert molding and molding at the time of molding, and the appearance is excellent. And excellent scratch resistance.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples. In the present embodiment, "parts" and "%" are based on weight unless otherwise indicated.

[Example 1]

For the base film, a coating liquid for a hard coat layer of the following formulation is applied by a bar coating method on the surface of one of polyester films (COSMOSHINE A4300: Tokibo Co., Ltd.) having a thickness of 125 μm. After drying, ultraviolet rays (irradiation amount: 400 mJ/cm ² ) were irradiated with a high pressure mercury lamp to form a hard coat layer. The thickness of the hard coat layer was made different, and a film for insert molding having a thickness of the hard coat layer of 3 μm and 4 μm was produced.

<Formulation of Coating Liquid for Hard Coating Layer of Example 1>

[Example 2]

In the coating liquid for a hard coat layer of Example 1, the dendrimer structure polyfunctional oligomer A1 was changed to a dendrimer structure polyfunctional oligomer A2 (NK ester A-HBR 5: Xinzhongcun Chemical Co., Ltd. Other than the industrial company, in the same manner as in the first embodiment, two types of insert molding films having different thicknesses of the hard coat layer were produced.

[Example 3]

In the coating liquid for a hard coat layer of Example 1, the dendrimer structure polyfunctional oligomer A1 was changed to 12 parts, and the photopolymerizable prepolymer/photopolymerizable monomer was changed to 8 parts. In the same manner as in Example 1, two types of insert molding films having different thicknesses of the hard coat layer were produced.

[Example 4]

In the coating liquid for a hard coat layer of Example 1, the dendrimer structure polyfunctional oligomer A1 was changed to 4 parts, and the photopolymerizable prepolymer/photopolymerizable monomer was changed to 16 parts. The rest are the same as in the first embodiment. In the method, two types of insert molding films having different thicknesses of the hard coat layer were produced.

[Example 5]

The film for insert molding was produced in the same manner as in Example 1 except that the coating liquid for a hard coat layer of Example 1 was changed to the coating liquid for a hard coat layer of the following formulation. The thickness of the hard coat layer was made different, and three types of insert molding films having a thickness of 3 μm, 4 μm, and 5 μm of the hard coat layer were produced.

<Formulation of Coating Liquid for Hard Coating Layer of Example 5>

[Example 6]

In the coating liquid for a hard coat layer of Example 5, the dendrimer structure polyfunctional oligomer A1 was changed to 9 parts, and the ring structure reactive monomer was changed to 2 parts, and the photopolymerizable prepolymer/light was changed. The polymerizable monomer was changed to 9 parts. In the same manner as in Example 5, three types of insert molding films having different thicknesses of the hard coat layer were produced.

[Example 7]

In the coating liquid for a hard coat layer of Example 5, the dendrimer structure polyfunctional oligomer A1 was changed to 2 parts, and the ring structure reactive monomer was changed to 9 parts, and the photopolymerizable prepolymer/light was used. In the same manner as in Example 5 except that the polymerizable monomer was changed to 9 parts, three types of insert molding films having different thicknesses of the hard coat layer were produced.

[Comparative Example 1]

In the coating liquid for a hard coat layer of Example 1, the dendrimer structure polyfunctional oligomer A1 was not added, and the photopolymerizable prepolymer/photopolymerizable monomer was changed to 20 parts. In the same manner as in the first embodiment, two types of insert molding films having different thicknesses of the hard coat layer were produced.

[Comparative Example 2]

In the same manner as in Example 1, except that the coating liquid for a hard coat layer of Example 1 was changed to the coating liquid for a hard coat layer of the following formulation, two types of embedding in which the thickness of the hard coat layer was different were produced. Film for molding.

<Recipe of coating liquid for hard coat layer of Comparative Example 2>

The materials and ratios used in the examples and comparative examples are summarized in Table 1. The numerical values in the table are expressed by the ratio (parts by weight) to 100 parts by weight of (B).

With respect to the films for insert molding obtained in the examples and the comparative examples, the hard coat properties and the crack resistance were evaluated. The results are shown in Table 2.

(1) Evaluation of hard coatability

After the surface of the hard coat layer was rubbed 10 times with a load of 300 g and steel wool # 0000, the presence or absence of the flaw on the surface was visually evaluated. The number of unscared persons in the assessment department was "◎", the number of people who had not been scratched was "○", and the one who was obviously scratched was "X".

(2) Evaluation of crack resistance

According to the bending resistance (cylinder mandrel method) (JIS K 5600-5-1: 1999), the iron for the insert having a diameter of about 5 mm was obtained by embedding the film for the insert molding obtained in the examples and the comparative examples. The outer side was folded and wound up to visually evaluate whether or not the hard coat layer of the wound portion was cracked. In the evaluation system, it is not possible to confirm that the cracker is "◎", and the almost unrecognizable person is "○", and some of the confirmable persons are "△", and it is apparent that the person who is confirmed is "X".

Obviously, from Table 2, polyfunctional structures were constructed using specific dendrimers. Any of the films for insert molding of the examples 1 to 7 in which the oligomer is a monomer constituting the resin of the hard coat layer is excellent in hard coat property and crack resistance.

In Examples 1 to 4, a dendrimer was used to construct a polyfunctional oligomer (A) and a photopolymerizable prepolymer/monomer (B) as a resin for a hard coat layer. In the two-component system, it is understood that the ratio of (A) to 100 parts by weight of the component (B) is from 25 to 150 parts by weight, and good hard coatability and crack resistance can be obtained. In particular, in the film for insert molding of Examples 1 and 2 in which the ratio of (A) was 67 parts by weight, both the hard coat property and the crack resistance were excellent.

Examples 5 to 7 use a dendrimer structure to form a polyfunctional oligomer (A), a ring structure reactive monomer (C), and a photopolymerizable prepolymer/monomer (B) as a resin for a hard coat layer. By adding a ring structure reactive monomer (C), the crack resistance is improved. Generally, if the thickness of the hard coat layer is increased, the hardness is increased, and cracking is liable to occur. However, in the three-component system, even if the thickness is increased, excellent crack resistance can be obtained.

In the film for insert molding having the hard coat layer of the components of the fifth to seventh embodiments, the total amount of the polyfunctional oligomer (A) and the ring-structure-reactive monomer (C) with respect to the dendrimer structure was found. The ratio of the ring-forming reactive monomer (C) in the range of 18% by weight to 82% by weight can provide excellent hard coat properties and crack resistance. In particular, in Example 5, in which the ratio of the ring-constitutive reactive monomer (C) was 30% by weight, the film for insert molding having a thickness of 5 μm showed that it was superior to Example 6 of the same thickness (the ratio of C was 18% by weight). The crack-resistant, 3 μm thick film for insert molding showed a hard coatability superior to that of Example 7 (the ratio of C was 82% by weight) of the same thickness.

Further, the film for insert molding of Comparative Example 1 which does not use a dendrimer structure polyfunctional oligomer is excellent in hard coat properties, but the crack resistance is inferior to the examples.

The polyfunctional oligomer was not used as the dendrimer, and the film for insert molding of Comparative Example 2 using a thermoplastic resin was excellent in crack resistance, but the hard coat property was inferior to that of the examples.

Then, the film for insert molding having a thickness of 3 μm of the hard coat layer obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was incorporated in the injection molding so that the hard coat layer was formed outside when the resin molded product was formed. After molding into a three-dimensional shape by vacuum molding using a mold (a mold for covering a mobile phone, size: about 50 mm × 100 mm), the molten acrylic resin is filled in a mold, the mold is cooled, and the film for insertion molding is taken out. Hardened acrylic resin molded article. With respect to these resin molded articles, the edge portions (curved surfaces and corner portions) of the surface of the resin molded article were visually observed. Moreover, the hard coatability of the surface of the resin molded article was evaluated in the same manner as the film for insert molding described above.

When the resin molded article of the film for insert molding of Examples 1 to 7 was used, no cracking occurred or whitening occurred at the edge portion, and the hard coat property was similarly obtained as well as the film for insert molding described above.

Further, in the resin molded article using the film for insert molding of Comparative Example 1, good results were obtained with respect to the hard coat property, but occurrence of cracking or whitening was confirmed at the edge portion.

When the resin molded article of the film for insert molding of Comparative Example 2 was used, no cracking occurred or whitening occurred at the edge portion, and the hard coat system was inferior to the implementation. The resin molded articles of Examples 1 to 7.

(industrial use possibility)

According to the present invention, it is possible to provide a molded article using a film for insert molding, which is free from cracking or whitening during molding, and has excellent scratch resistance on the surface, and there is no between the molding material and the film for insert molding even after passage of time. Stripped molded product.

10‧‧‧Insert molding film

11‧‧‧Substrate film

12‧‧‧hard coating

13‧‧‧Metal evaporation

14‧‧‧Printing layer

15‧‧‧Adhesive layer

Fig. 1 is a view showing an example of a structure of a film for insert molding which is applicable to the present invention.

10‧‧‧Insert molding film

11‧‧‧Substrate film

12‧‧‧hard coating

13‧‧‧Metal evaporation

14‧‧‧Printing layer

15‧‧‧Adhesive layer

Claims (13)

A resin molded article obtained by integrating a film for insert molding having a hard coat layer and a molding material by molding, and having the hard coat layer on a surface thereof; the hard coat layer having three or more layers a hard coat layer formed of an ionizing radiation-curable resin composition of a polyfunctional oligomer having a acrylate functional group and having a dendrimer structure, the aforementioned polyfunctional oligomer having a dendrimer structure The system is contained in an amount of 10 to 160 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin composition. The resin molded article of claim 1, wherein the hard coat layer contains at least one of carbon, nitrogen, oxygen, and hydrazine in addition to the polyfunctional oligomer having the dendrimer structure. The ionizing radiation-curable resin composition of the reactive monomer of the ring structure of the element is formed. The resin molded article of claim 1 or 2, wherein the hard coat layer further comprises a photopolymerizable prepolymer and/or photopolymerization in addition to the polyfunctional oligomer having a dendritic polymer structure. An ionizing radiation hardening type resin composition of a monomer. The resin molded article of claim 3, wherein the polyfunctional oligomer (A) having a dendritic polymer structure, the reactive monomer (C) having a ring structure, and photopolymerizable pre-polymerization thereof The ratio of the polymer and/or the photopolymerizable monomer (B) is 20 to 200 parts by weight based on 100 parts by weight of (B), and the total of (A) and (C) is relative to (A) and (C). The total amount is 100 parts by weight, and (C) is 10 to 90 parts by weight. For example, the resin molded article of claim 1 or 2, wherein The molding material is one selected from the group consisting of an acrylic resin and a polycarbonate resin. A resin molded article according to claim 1 or 2, wherein at least one of a metal deposition layer, a printing layer and an adhesive layer is formed between the molding material and the hard coat layer. A film for insert molding, which is formed on a surface of at least one of the base film and has a hard coat layer formed of an ionizing radiation-curable resin composition; and the ionizing radiation-curable resin composition system a polyfunctional oligomer having a dendrimer structure having three or more (meth) acrylate functional groups, the aforementioned polyfunctional oligomer having a dendrimer structure, with respect to the ionization except for the same 100 parts by weight of the radiation curable resin composition is contained in an amount of 10 to 160 parts by weight. The film for insert molding according to claim 7, wherein the ionizing radiation-curable resin composition contains carbon and nitrogen in addition to the polyfunctional oligomer having a dendrimer structure. A reactive monomer of a ring structure of at least one element of oxygen and hydrazine. The film for insert molding according to claim 7 or 8, wherein the ionizing radiation-curable resin composition contains a photopolymerizable pre-except in addition to the polyfunctional oligomer having a dendrimer structure. Polymer and/or photopolymerizable monomer. The film for insert molding according to claim 9, wherein the polyfunctional oligomer (A) having a dendritic polymer structure, the reactive monomer having a ring structure (C), and other photopolymerizable properties thereof The ratio of the prepolymer and/or the photopolymerizable monomer (B) is 20 to 200 parts by weight based on 100 parts by weight of (B), and the total of (A) and (C) is relative to (A) and (C) are 100 parts by weight in total, and (C) is 10 to 90 parts by weight. The film for insert molding according to claim 7 or 8, wherein at least one of a metal deposition layer, a printing layer and an adhesive layer is formed on the other surface of the substrate film. An ionizing radiation-curable resin composition comprising: a polyfunctional oligomer (A) having three or more (meth) acrylate functional groups and having a dendrimer structure, having carbon, a reactive monomer (C) having a ring structure of at least one element of nitrogen, oxygen and hydrazine, a photopolymerizable prepolymer other than the other, and/or a photopolymerizable monomer (B); (A), (B) and The ratio of (C) is 20 to 200 parts by weight based on 100 parts by weight of (B), and the total amount of (A) and (C) is 100 parts by weight, and (C) is (C). 10 to 90 parts by weight. A hard coat film formed of the ionizing radiation curable resin composition of claim 12 of the patent application.