JP4790065B2 - Resin molded product using insert molding film - Google Patents

Description

  The present invention relates to various resin molded products such as operation units (keypad units) of devices such as touch panels, cellular phones, game machines, audio players, and notebook personal computers for home appliances, and in particular, resin molding materials and insert molding for surface protection. The present invention relates to a resin molded product integrated with a film for use.

  Conventionally, as a method of providing a pattern on the surface of various molded products made of resin or providing a surface protective layer, a film in which a printed layer or a surface protective layer is formed on a substrate when molding the molded product with a mold Is placed between the resin and the mold, the printing layer or surface protective layer is transferred to the surface of the molded product by molding, and then the substrate is peeled off, or the resin and the entire film are molded integrally with the mold There is a way.

Among the films used in these methods, a film that is integrated with a molded product without being peeled after molding is called an insert film or an insert molding film, as distinguished from a transfer film. As such an insert film, for example, a film is proposed in which a base film such as a polyester film is provided with a metal vapor deposition film or a printed layer and a hard coat layer serving as a surface protective layer is formed on the other. (Patent Document 1, Patent Document 2).
JP 2005-288720 A Japanese Patent Laying-Open No. 2005-305786

  In general, a hard coat layer used for the purpose of protecting the surface of a molded product is required to have scratch resistance, and for example, a hardness of 2H or more in pencil hardness and a load of 300 g or more in a steel wool test are required. For this reason, the hard coat layer is composed of a curable resin having excellent scratch resistance such as an electron beam curable resin and an ultraviolet curable resin. However, when a film having such a hard coat layer is used for insert molding, generally, the surface of the molded product is curved or has corners, so that the hard coat surface tends to crack during molding. .

  In order to solve this problem, it is conceivable to add a thermoplastic resin to the curable resin constituting the hard coat layer of the insert molding film to enhance flexibility. However, in that case, the hardness is lowered by increasing the flexibility, and cannot withstand the load of the steel wool test as described above.

  In addition, in a hard coat layer of a general hard coat film, the ionizing radiation curable resin composition has a dendrimer structure in order to prevent curing shrinkage and generation of cracks and whitening caused by the hard coat layer. Patent Document 3 proposes inclusion of an oligomer.

However, the hard coat film is not assumed to be used for insert molding, and the effect on the cured film when a pressure deformation is further applied to the cured film after curing cannot be predicted. Moreover, even if the hard coat film described in Patent Document 3 is used as it is for insert molding, it is not always possible to prevent the occurrence of cracks during pressure molding.
JP 2005-76005 A

  Accordingly, an object of the present invention is to provide a resin molded product having sufficient surface hardness, having no cracks during integral molding with an insert molding film, and having an excellent appearance.

  In order to solve the above problems, the present inventors have studied the monomer of the curable resin constituting the hard coat layer, and in particular, formed with an ionizing radiation curable resin composition containing a polyfunctional oligomer having a dendrimer structure. We have intensively studied the relationship between the cracks generated when external pressure is applied to the hard coat layer and the composition of the composition (and the thickness of the hard coat layer). As a result, when an insert molding film 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 was used, a force such as pressure deformation was applied. Even in this case, the present inventors have found that they have excellent crack prevention properties and can maintain excellent hard coat properties.

  That is, the resin molded product of the present invention is an insert having a hard coat layer formed from an ionizing radiation curable resin composition containing a polyfunctional oligomer having a dendrimer structure and having three or more (meth) acrylate functional groups. The molding film and the molding material are integrated by molding, and the hard coat layer is provided on the surface.

  The resin molded product of the present invention is characterized in that the polyfunctional oligomer having a dendrimer structure is contained in an amount of 10 to 160 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin composition excluding it.

  In the resin molded product of the present invention, the hard coat layer is an ionization containing a reactive monomer having a cyclo ring structure containing at least one element of carbon, nitrogen, oxygen and silicon in addition to a polyfunctional oligomer having a dendrimer structure. It is formed from a radiation curable resin composition.

In the resin molded product of the present invention, the hard coat layer is formed from an ionizing radiation curable resin composition containing a photopolymerizable prepolymer and / or a photopolymerizable monomer in addition to a polyfunctional oligomer having a dendrimer structure. It is characterized by that.
Molded resin product of the present invention, preferably, a polyfunctional Oh oligomer having a dendrimer structure (A), the reactive monomer (C) having a cyclo ring structure, photopolymerizable prepolymers and / or photopolymerization otherwise The ratio of the monomer (B) to 100 parts by weight of (B) is such that the total of (A) and (C) is 20 to 200 parts by weight, and the total of (A) and (C) is 100 parts by weight. On the other hand, (C) is 10 to 90 parts by weight.

  In the resin molded product of the present invention, for example, the molding material is one selected from an acrylic resin and a polycarbonate resin.

  The resin molded product of the present invention is characterized in that at least one layer including a metal vapor 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 an ionizing radiation curable resin composition containing a polyfunctional oligomer having a dendrimer structure having three or more (meth) acrylate functional groups on at least one surface of a base film. It is characterized by comprising a formed hard coat layer.

  The insert molding film of the present invention is characterized in that the polyfunctional oligomer having a dendrimer structure is contained in an amount of 10 to 160 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin composition excluding it.

  The film for insert molding of the present invention is a reaction in which the ionizing radiation curable resin composition has a cyclo ring structure containing at least one element of carbon, nitrogen, oxygen and silicon in addition to a polyfunctional oligomer having a dendrimer structure. It is characterized by containing a sex monomer.

The film for insert molding of the present invention is characterized in that the ionizing radiation curable resin composition contains a photopolymerizable prepolymer and / or a photopolymerizable monomer in addition to a polyfunctional oligomer having a dendrimer structure.
Film for insert molding of the present invention, preferably, a polyfunctional Oh oligomer having a dendrimer structure (A), a reactive monomer having a cyclo ring structure (C), other photopolymerizable prepolymers and / or optical The ratio of the polymerizable monomer (B) is 20 to 200 parts by weight of the total of (A) and (C) with respect to 100 parts by weight of (B), and the total of 100 parts by weight of (A) and (C). On the other hand, (C) is 10 to 90 parts by weight.

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

The ionizing radiation curable resin compositions of the present invention has three or more the (meth) acrylate functional group, and polyfunctional Oh oligomer having a dendrimer structure (A), carbon, nitrogen, oxygen and silicon least a A reactive monomer (C) having a cyclo ring structure containing two elements and another photopolymerizable prepolymer and / or photopolymerizable monomer (B), and (A), (B) and (C) The ratio of (A) and (C) is 20 to 200 parts by weight with respect to 100 parts by weight of (B), and (C) is 100 parts by weight of (A) and (C). An ionizing radiation curable resin composition characterized by being 10 to 90 parts by weight.
The hard coat film of the present invention is a hard coat film formed from the ionizing radiation curable resin composition.

  According to the present invention, when the ionizing radiation curable resin composition constituting the hard coat layer of the insert molding film contains a polyfunctional oligomer having a dendrimer structure, a hard coat property with a load of 300 g or more is obtained in a steel wool test. And the generation of cracks during molding can be prevented. This is presumably because the hard coat layer surface absorbs the pressure at the time of molding by the dendrimer structure while having a hardness that can withstand the load of the steel wool test, so that the generation of cracks is prevented.

The other polyfunctional oligomer having a dendrimer structure, by containing Cecil reactive monomer having a cyclo ring structure, without compromising the hardcoded preparative can achieve higher during molding crack preventing properties. This is presumably because the cyclo ring structure absorbs pressure during molding to some extent.

Hereinafter, embodiments of the resin molded product of the present invention will be described.
The resin molded product of the present invention is an integral product of a film for insert molding provided with a hard coat layer and a molding material, and has a hard coat layer on the surface. The molding material may be any resin that can be injection-molded. For example, thermoplastic resins such as acrylic resins, polycarbonate resins, ABS resins, and AS resins, and thermosetting resins are used.

  The insert molding film basically comprises a base film and a hard coat layer, and this hard coat layer becomes a hard coat layer formed on the surface of the resin molded product of the present invention by molding.

  As the base film, those having excellent transparency, heat resistance and mechanical strength are preferable. Specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose. Acryl, polyvinyl chloride, norbornene compounds and the like. In particular, it is preferable to use a biaxially stretched polyester film from the viewpoint of good dimensional stability due to heat.

The base film may be subjected to a surface treatment such as an easy adhesion treatment in order to improve the adhesion between the hard coat layer and the metal deposition layer or the printed layer or the adhesive layer.
Although the thickness of a base film is not specifically limited, When handling property, mechanical strength, etc. are considered, it is 20 micrometers-200 micrometers, Preferably it is about 50 micrometers-150 micrometers.

  Next, the hard coat layer will be described. The hard coat layer is formed from an ionizing radiation curable resin. Generally, an ionizing radiation curable resin is obtained by irradiating a photopolymerizable prepolymer and / or a photopolymerizable monomer having a reactive group such as an acroyl group in the molecule with ionizing radiation (ultraviolet rays or electron beams) and crosslinking and curing. It is done. The hard coat layer of the present invention uses a polyfunctional oligomer having a dendrimer structure and having three or more (meth) acrylate functional groups as a photopolymerizable prepolymer.

The dendrimer structure means a shape in which monomers are polymerized while branching and spread radially, and a polyfunctional oligomer having a dendrimer structure is represented by the general formula (1).

  Specifically, it has a functional group such as an amino group, a hydroxyl group, a carboxyl group, a phenyl group, an ethylene oxide group, a vinyl group, or a propylene oxide group, and has a (meth) acrylate functional group at the terminal. In particular, from the viewpoint of solubility in a solvent, handling properties, and compatibility with other ionizing radiation curable resins, it contains an ethylene oxide group and a (meth) acrylate functional group at the end. What has is preferable.

  The greater 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 cracks are less likely to occur during molding. However, if the number of (meth) acrylate functional groups is too large, the crack resistance during molding is reduced. On the other hand, if the molecular weight of the oligomer is too large, the surface hardness of the hard coat layer decreases. Therefore, the number of (meth) acrylate functional groups is preferably 3 to 10, more preferably 5 to 8. Moreover, molecular weight becomes like this. Preferably it is 1000-3000, More preferably, it is 1500-2000.

  The ionizing radiation curable resin can contain a known photopolymerizable prepolymer and a photopolymerizable monomer in addition to the polyfunctional oligomer described above. As the photopolymerizable prepolymer, acrylic prepolymers such as urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, and silicone acrylate can be used. Examples of the photopolymerizable monomer include monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and butoxyethyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, One kind of bifunctional acrylic monomer such as diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, etc., polyfunctional acrylic monomer such as dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol triacrylate, etc. Or two or more can be used.

Furthermore, a reactive monomer having a cyclo ring structure can be used as the photopolymerizable monomer. The cyclo ring is composed of one containing at least one element of carbon, nitrogen, oxygen, and silicon, and is preferably a 5-membered ring or a 6-membered ring. In addition, since it varies depending on the molecular weight, it cannot be generally stated, but from the viewpoint of preventing cracking of the edge due to pressurization during molding and preventing deterioration of hard coat properties, three or more (meth) acrylates. It is preferable that it has a functional group.
Specific examples of the cyclo ring structure include cycloolefins such as cyclopentene and cyclohexene, tetrahydrofuran, 1,3-dioxane, ε-caprolactone, ε-caprolactam, silacyclopentene, cyclodecane, isobornyl and the like. As monomers having such a cyclo ring structure, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2-hydroxyethyl) isocyanurate, dimethylol tricyclodecanedi (meta ) Acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-acryloyloxyethyl hexahydrophthalic acid and the like.

  The ratio of the polyfunctional oligomer (A) having the above-mentioned dendrimer structure, the photopolymerizable prepolymer / photopolymerizable monomer (B), and the reactive monomer (C) having a cyclo ring structure depends on the thickness of the hard coat layer and the requirements. Is appropriately selected in consideration of the hardness to be used and the material of the molded product. Specifically, when the molding resin is formed of (A) and (B), the polyfunctional oligomer (A) is 160 parts by weight with respect to 100 parts by weight of the photopolymerizable prepolymer / photopolymerizable monomer (B). The amount is preferably 100 parts by weight or less, more preferably 70 parts by weight or less. Further, it is 10 parts by weight or more, preferably 20 parts by weight or more, and more preferably 30 parts by weight or more with respect to 100 parts by weight of the photopolymerizable prepolymer / photopolymerizable monomer (B). (B) By making content of polyfunctional oligomer (A) with respect to 100 weight part into 10 weight part or more, when it pressurizes at the time of shaping | molding, it can prevent that an edge part produces a crack. Moreover, hard coat property can be maintained by setting it as 160 weight part or less.

  When the molding resin is formed of (A), (B) and (C), the total of the polyfunctional oligomer (A) and the reactive monomer (C) having a cyclo ring structure is a photopolymerizable prepolymer / The amount is 20 to 200 parts by weight, preferably 30 to 160 parts by weight, and more preferably 40 to 140 parts by weight with respect to 100 parts by weight of the photopolymerizable monomer (B). Although the ratio of (A) and (C) varies depending on the thickness of the hard coat layer and the like, it cannot be generally stated. For example, the hard coat layer has a thickness of 0.5 μm to 10 μm, preferably in the range of 2 μm to 5 μm. , (C) is 10 to 90% by weight, preferably 15 to 60% by weight, more preferably 20 to 40% by weight, based on the total of (A) and (C). By setting the content of (C) to 10% by weight or more, it is possible to make cracks less likely to occur at the edge portion when pressed during molding. Moreover, it can prevent that hard-coat property falls by setting it as 90 weight% or less.

  In the case of ultraviolet curing, the ionizing radiation curable resin preferably uses additives such as a photopolymerization initiator and a photopolymerization accelerator in addition to the above-described photopolymerizable prepolymer and photopolymerizable monomer.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthone and the like. The photopolymerization accelerator is one that can reduce polymerization damage due to air during curing and increase the curing speed, and examples thereof include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. .

Furthermore, as long as the function of the present invention is not impaired, other resins such as a thermoplastic resin and a thermosetting resin may be added as the binder component in addition to the ionizing radiation curable resin. Specifically, a resin such as an acrylic resin, polyester, polystyrene, polyvinyl acetate, polyurethane, and cellulose acetate can be added as long as it is about 30% by weight or less of the resin constituting the hard coat layer.
The hard coat layer may contain additives such as a matting agent for imparting an antiglare function, a colorant, an antistatic agent, and a UV absorber.

  The thickness of the hard coat layer is about 0.5 μm to 10 μm, preferably about 1 μm to 5 μm. When the ionizing radiation curable resin composition does not contain the reactive monomer (C) and contains only the polyfunctional oligomer (A), the occurrence of cracks can be prevented by setting the thickness to 5 μm or less. When the ionizing radiation curable resin composition contains the polyfunctional oligomer (A) and the reactive monomer (C), the occurrence of cracks can be prevented by setting the thickness to 10 μm or less.

  The hard coat layer is composed of the above-mentioned polyfunctional oligomer, photopolymerizable prepolymer, photopolymerizable monomer (including reactive monomer), and a photopolymerization initiator, photopolymerization accelerator, and other additives that are added as necessary. Apply the coating solution prepared by mixing with a dilution solvent to a base film by a known coating method, for example, bar coater, die coater, blade coater, spin coater, roll coater, gravure coater, flow coater, spray, screen printing. The ionizing radiation curable resin composition is cured by irradiating an electron beam or ultraviolet rays. The hard coat layer is a layer having a three-dimensional network structure with high hardness and excellent crack resistance when irradiated with an electron beam or ultraviolet rays. This is considered to prevent the generation of cracks on the surface of the layer because the pressure is absorbed by the dendrimer structure in the molecule when an external pressure (bending force or tensile force) is applied.

  The basic structure of the film for insert molding is the base film and the hard coat layer described above, but the molded product is decorated on the surface of the base film opposite to the surface on which the hard coat layer is provided. A printing layer or a metal vapor deposition layer may be provided. FIG. 1 shows an example of the structure of a typical insert molding film.

  In the illustrated insert molding film 10, a hard coat layer 12 is formed on one surface of a substrate film 11, and a decorative layer composed of a metal vapor-deposited layer 13 and a printed layer 14 and an adhesive layer 15 are disposed in this order on the other surface. It has a formed structure. For example, after the metal vapor deposition layer 13 is formed on the base film 11, the decorative layer is removed by etching a part of the metal vapor deposition layer 13, and printing is performed on the base film 11 from which the metal vapor deposition layer 13 has been removed. Or after forming a desired character or pattern on the substrate film 11 by a known printing method, silk screen method, gravure method, ink jet method or the like, and then forming a metal vapor deposition layer 13 thereon. Form. There is a case where the printing layer 14 is omitted and the metal vapor deposition layer 13 is formed directly on the base film 11, or there is a case where only the printing layer 14 does not have the metal vapor deposition layer 13. When providing the printing layer 14, you may provide the receiving layer for receiving printing ink in the surface in which the printing layer 14 of the base film 11 is provided.

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

  The adhesive layer 15 is a layer provided to enhance the adhesion between the molded product material and the metal vapor deposition layer 13, and is polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate based on the molded product material. , Vinyl chloride / vinyl acetate copolymer, and cellulose-based adhesives can be used as appropriate.

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

First, the insert molding film described above is placed and pressed so that the hard coat layer is on the outside when a resin molded product is formed, and is molded into a desired shape. Next, the molded film for insert molding is placed in a molding die, and a resin that is heated and fluidized between the die is poured. The resin is cured and integrated with the film for insert molding to obtain the resin molded product of the present invention. The molding conditions (temperature, mold clamping pressure, time) are appropriately selected according to the resin (molding material), the shape of the molded product, and the like. In general, the mold clamping pressure is calculated by molding product projection area × in-mold resin pressure. As an example, when the resin to be injection-molded is ABS resin and 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., and the resin temperature is 250 ° C. The injection speed is 60 mm / second.

  Since the resin molded product of the present invention uses a film with a hard coat layer having excellent crack resistance as an insert molding film, cracks are generated during press molding of the insert molding film and molding with a mold. It has excellent aesthetics and scratch resistance.

  Hereinafter, the present invention will be described in more detail based on examples. In this example, “parts” and “%” are based on weight unless otherwise specified.

[Example 1]
After applying and drying a hard coat layer coating solution of the following formulation on one side of a 125 μm thick polyester film (Cosmo Shine A4300: Toyobo Co., Ltd.) as a base film, irradiate it with ultraviolet light with a high-pressure mercury lamp. (Irradiation amount 400 mJ / cm ² ), and a hard coat layer was formed. Two types of insert molding films having a hard coat layer thickness of 3 μm and 4 μm were prepared by varying the thickness of the hard coat layer.

<Prescription of coating liquid for hard coat layer of Example 1>
Dendrimer structure polyfunctional oligomer A1 8 parts (solid content 100%) (Miramer SP1114: MIWON)
・ Photopolymerizable prepolymer / photopolymerizable monomer 12 parts (100% solid content) (Beamset 575: Arakawa Chemical Industries)
・ Photopolymerization initiator 0.6 parts (Irgacure 651: Ciba Specialty Chemicals)
・ 45 parts of propylene glycol monomethyl ether

[Example 2]
In the same manner as in Example 1 except that the dendrimer structure polyfunctional oligomer A1 was changed to a dendrimer structure polyfunctional oligomer A2 (NK ester A-HBR5: Shin-Nakamura Chemical Co., Ltd.) in the coating liquid for hard coat layer of Example 1. Thus, two types of insert molding films having different hard coat layer thicknesses were produced.

[Example 3]
Except for changing the dendrimer structure polyfunctional oligomer A1 to 12 parts and the photopolymerizable prepolymer / photopolymerizable monomer to 8 parts in the coating liquid for hard coat layer of Example 1, Two types of insert molding films having different hard coat layer thicknesses were produced.

[Example 4]
Except for changing the dendrimer structure polyfunctional oligomer A1 to 4 parts and the photopolymerizable prepolymer / photopolymerizable monomer to 16 parts in the coating liquid for hard coat layer of Example 1, Two types of insert molding films having different hard coat layer thicknesses were produced.

[Example 5]
An insert molding film was produced in the same manner as in Example 1 except that the hard coat layer coating solution of Example 1 was changed to a hard coat layer coating solution having the following formulation. By varying the thickness of the hard coat layer, three types of insert molding films having a hard coat layer thickness of 3 μm, 4 μm and 5 μm were obtained.

<Prescription of coating liquid for hard coat layer of Example 5>
・ 7 parts of dendrimer structure polyfunctional oligomer A1 (100% solid content) (Miramer SP1114: MIWON)
・ Cyclocyclic structure reactive monomer 3 parts (ε-caprolactone modified tris-
(2-hydroxyethyl) isocyanurate)
(Solid content 100%) (SR368: Sartomer)
-Photopolymerizable prepolymer / photopolymerizable monomer 10 parts (solid content 100%) (Beamset 575: Arakawa Chemical Industries)
・ Photopolymerization initiator 0.6 parts (Irgacure 651: Ciba Specialty Chemicals)
・ 45 parts of propylene glycol monomethyl ether

[Example 6]
In the coating liquid for hard coat layer of Example 5, except that the dendrimer structure polyfunctional oligomer A1 was changed to 9 parts, the cyclocyclic structure reactive monomer was changed to 2 parts, and the photopolymerizable prepolymer / photopolymerizable monomer was changed to 9 parts. In the same manner as in Example 5, three types of insert molding films having different hard coat layer thicknesses were produced.

[Example 7]
In the coating liquid for hard coat layer of Example 5, except that the dendrimer polyfunctional oligomer A1 was changed to 2 parts, the cyclocyclic structure reactive monomer was changed to 9 parts, and the photopolymerizable prepolymer / photopolymerizable monomer was changed to 9 parts. In the same manner as in Example 5, three types of insert molding films having different hard coat layer thicknesses were produced.

[Comparative Example 1]
In the coating liquid for 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 Example 1, Two types of insert molding films having different hard coat layer thicknesses were produced.

[Comparative Example 2]
Two types of insert molding films with different hard coat layer thicknesses were prepared in the same manner as in Example 1 except that the hard coat layer coating liquid of Example 1 was changed to the hard coat layer coating liquid of the following formulation. did.

<Prescription of coating liquid for hard coat layer of Comparative Example 2>
・ 20 parts of thermoplastic acrylic resin (solid content 40%) (Acridic A195: Dainippon Ink and Chemicals)
・ Photopolymerizable prepolymer / photopolymerizable monomer 12 parts (100% solid content) (Beamset 575: Arakawa Chemical Industries)
・ Photopolymerization initiator 0.4 parts (Irgacure 651: Ciba Specialty Chemicals)
・ 33 parts of propylene glycol monomethyl ether

Table 1 summarizes the materials and ratios used in the examples and comparative examples. The numerical value in the table | surface was shown by the ratio (weight part) with respect to (B) 100 weight part.

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

(1) Evaluation of hard coat properties The surface of the hard coat layer was rubbed 10 times with steel wool # 0000 under a load of 300 g, and then the presence or absence of scratches on the surface was visually evaluated. The evaluation was "◎" for those that were not scratched, "○" for those that were hardly scratched, and "X" for those that were clearly scratched.

(2) Evaluation of crack resistance Films for insert molding obtained in Examples and Comparative Examples on an iron bar having a diameter of about 5 mm based on flex resistance (cylindrical mandrel method) (JIS K5600-5-1: 1999) Each of these was folded and wound so that the hard coat layer was on the outside, and it was visually evaluated whether or not cracks occurred in the hard coat layer of the wound portion. In the evaluation, “◎” indicates that no crack was confirmed, “◯” indicates that it was hardly confirmed, “Δ” indicates that it was slightly confirmed, and “×” indicates that it was clearly confirmed.

  As is apparent from Table 2, the insert molding films of Examples 1 to 7 using specific dendrimer structure polyfunctional oligomers as the monomer of the resin constituting the hard coat layer are both hard coat and crack resistant. It was excellent.

  In Examples 1 to 4, a dendrimer structure polyfunctional oligomer (A) and a photopolymerizable prepolymer / monomer (B) are used as the resin for the hard coat layer. In this two-component system, it was found that good hard coat properties and crack resistance were obtained when the ratio of (A) to 100 parts by weight of component (B) was in the range of 25 to 150 parts by weight. In particular, in the insert molding films of Examples 1 and 2 in which the proportion of (A) was 67 parts by weight, excellent results were obtained in both hard coat properties and crack resistance.

  In Examples 5 to 7, a dendrimer structure polyfunctional oligomer (A), a cyclocyclic structure reactive monomer (C), and a photopolymerizable prepolymer / monomer (B) were used as resins for the hard coat layer. The crack resistance was improved by adding the ring structure reactive monomer (C). Generally, as the thickness of the hard coat layer increases, the hardness increases and cracks are likely to occur. However, in the three-component system, excellent crack resistance was obtained even when the thickness was increased.

  In the film for insert molding having the three-component hard coat layer of Examples 5 to 7, the cycloreactive monomer (C) relative to the total of the dendrimer polyfunctional oligomer (A) and the cycloreactive monomer (C) ) In the range of 18 wt% to 82 wt%, it was found that excellent hard coat properties and crack resistance were obtained. In particular, in Example 5 in which the proportion of the cyclic structure reactive monomer (C) is 30% by weight, the insert molding film having a thickness of 5 μm is superior to Example 6 (the proportion of C is 18% by weight) having the same thickness. The film for insert molding having a thickness of 3 μm showed a hard coat property superior to that of Example 7 (the ratio of C was 82% by weight).

  On the other hand, the film for insert molding of Comparative Example 1 that did not use the dendrimer-structured polyfunctional oligomer was excellent in hard coat properties but was inferior to the examples in terms of crack resistance.

  Moreover, the film for insert molding of Comparative Example 2 using a thermoplastic resin without using a dendrimer structure polyfunctional oligomer was excellent in crack resistance but inferior to Examples in terms of hard coat properties. It was.

  Next, when the film for insert molding with a thickness of 3 μm of the hard coat layer obtained in Examples 1 to 7 and Comparative Examples 1 and 2 is made into a resin molded product, it is for injection molding so that the hard coat layer is on the outside. It is assembled into a mold (mold for a mobile phone cover case, size: approx. 50 mm x 100 mm), molded into a three-dimensional shape by vacuum molding, then filled with molten acrylic resin, and the mold is cooled. Then, an acrylic resin molded product cured integrally with the insert molding film was taken out. About these resin molded products, the edge part (curved surface and corner | angular part) of the resin molded product surface was observed visually. Moreover, the same evaluation as the above-mentioned film for insert molding was performed about the hard coat property of the surface of these resin molded products.

  For the resin molded products using the insert molding films of Examples 1 to 7, the edge portion is free from cracking and whitening, and the same good results as the above-described insert molding film are obtained for the hard coat properties. It was.

  Moreover, about the resin molded product using the film for insert molding of the comparative example 1, although the favorable result was obtained about hard-coat property, generation | occurrence | production of the crack and whitening were confirmed in the edge part.

  As for the resin molded product using the film for insert molding of Comparative Example 2, the edge portion was neither cracked nor whitened, but the hard coat property was inferior to the resin molded products of Examples 1-7. became.

  According to the present invention, it is a molded product using an insert molding film, has no cracking or whitening during molding, has excellent surface scratch resistance, and has a molding material and insert molding film over time. A molded product that does not peel off between the two is provided.

The figure which shows an example of the structure of the film for insert molding to which this invention is applied

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Film for insert molding, 11 ... Base film, 12 ... Hard-coat layer, 13 ... Metal vapor deposition layer, 14 ... Printed layer, 15 ... Adhesive layer.

Claims (15)

  An insert molding film having a hard coat layer formed from an ionizing radiation curable resin composition containing a polyfunctional oligomer having a (meth) acrylate functional group and having a dendrimer structure, and a molding material A resin molded product which is integrated by molding and has the hard coat layer on the surface.   2. The resin molded product according to claim 1, wherein the polyfunctional oligomer having a dendrimer structure is contained in an amount of 10 to 160 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin composition excluding the polyfunctional oligomer. Resin molded product. The resin molded product according to claim 1 or 2,
The hard coat layer comprises an ionizing radiation curable resin composition containing a reactive monomer having a cyclo ring structure containing at least one element of carbon, nitrogen, oxygen and silicon, in addition to the polyfunctional oligomer having the dendrimer structure. A resin molded product characterized by being formed. The resin molded product according to any one of claims 1 to 3,
The hard coat layer is formed from an ionizing radiation curable resin composition containing a photopolymerizable prepolymer and / or a photopolymerizable monomer in addition to the polyfunctional oligomer having the dendrimer structure. Goods. The resin molded product according to claim 4,
Polyfunctional Oh oligomer (A) having the dendrimer structure, the ratio of the reactive monomer having the cyclo ring structure (C), and other photopolymerizable prepolymers and / or a photopolymerizable monomer (B) The total of (A) and (C) is 20 to 200 parts by weight with respect to 100 parts by weight of (B), and (C) is 10 to 90 with respect to the total of 100 parts by weight of (A) and (C). A resin molded product characterized by being a part by weight. The resin molded product according to any one of claims 1 to 5,
A resin molded product in which the molding material is one selected from acrylic resin and polycarbonate resin. The resin molded product according to any one of claims 1 to 6,
At least one layer including a metal vapor-deposited layer, a printed layer, and an adhesive layer is formed between the molding material and the hard coat layer.   A hard coat layer formed from an ionizing radiation curable resin composition containing a polyfunctional oligomer having a dendrimer structure and having three or more (meth) acrylate functional groups on at least one surface of a base film The film for insert molding characterized by becoming. The film for insert molding according to claim 8,
The polyfunctional oligomer having a dendrimer structure 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 excluding the polyfunctional oligomer. The film for insert molding according to claim 8 or 9,
The ionizing radiation curable resin composition contains a reactive monomer having a cyclo ring structure containing at least one element of carbon, nitrogen, oxygen and silicon in addition to the polyfunctional oligomer having the dendrimer structure. Insert molding film. The insert molding film according to any one of claims 8 to 10,
The ionizing radiation curable resin composition contains a photopolymerizable prepolymer and / or a photopolymerizable monomer in addition to the polyfunctional oligomer having the dendrimer structure. The insert molding film according to claim 11,
Polyfunctional Oh oligomer (A) having the dendrimer structure, the ratio of the reactive monomer having the cyclo ring structure (C), and other photopolymerizable prepolymers and / or a photopolymerizable monomer (B) The total of (A) and (C) is 20 to 200 parts by weight with respect to 100 parts by weight of (B), and (C) is 10 to 90 with respect to the total of 100 parts by weight of (A) and (C). An insert molding film characterized by being a weight part. The film for insert molding according to any one of claims 8 to 12,
At least one layer containing a metal vapor deposition layer, a printing layer, and an adhesive layer is formed on the other surface of the base film. Having three or more (meth) acrylate functional groups, a polyfunctional Oh oligomer having a dendrimer structure (A), carbon, nitrogen, reactive monomer having a cyclo ring structure containing at least one element of oxygen and silicon ( C) and other photopolymerizable prepolymer and / or photopolymerizable monomer (B), and the ratio of (A), (B) and (C) is (B) 100 parts by weight, The total of (A) and (C) is 20 to 200 parts by weight, and (C) is 10 to 90 parts by weight with respect to 100 parts by weight of (A) and (C) in total. Radiation curable resin composition.   A hard coat film formed from the ionizing radiation curable resin composition according to claim 14.

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