JP4968461B2 - HARD COAT FILM FOR INJECTION MOLDING AND METHOD FOR PRODUCING INJECTION MOLDING USING THE FILM - Google Patents

Description

  The present invention relates to a hard coat film for injection molding which can sufficiently cope with a molded shape having high stretchability and a corner.

  Conventionally, injection-molded articles of thermoplastic resins such as polycarbonate have been widely used as alternative materials such as glass and metal. However, thermoplastic resin injection-molded products generally have a surface hardness lower than that of glass or metal and are easily scratched. Therefore, a hard coat layer is often formed on the surface and used for use. .

For example, in Patent Document 1, an acrylic paint is applied to the surface of an injection molded body obtained by injection molding of polycarbonate with an injection molding machine and dried to form a primer layer, and then a silicone paint is further applied. It is described that a polycarbonate injection molded article having a hard coat layer on its surface is obtained by forming a hard coat layer by drying.
JP 2004-167946 A (paragraph 0027)

  However, the prior art described in Patent Document 1 has a problem of low productivity because it requires three steps of an injection molding step, a primer layer forming step, and a hard coat layer forming step.

  The present invention has been made in view of such a technical background, and can impart sufficient scratch resistance to the surface of an injection-molded body, and can be integrated simultaneously with the molding at the time of resin injection molding. It is an object of the present invention to provide a hard coat film for injection molding that is excellent in productivity and has high stretchability of the film during injection molding and can sufficiently cope with, for example, a cornered shape or a complicated shape. To do.

  In order to achieve the above object, the present invention provides the following means.

[1] a base material layer comprising a mixed resin composition containing a polycarbonate resin and a polyester resin;
A hard coat layer laminated and integrated on one side or both sides of the base material layer,
The hard coat layer is
A bifunctional urethane acrylate oligomer that is a reaction product of an isocyanate compound obtained by reacting a polyether polyol and an aromatic diisocyanate and an acrylate monomer having a hydroxyl group;
A polyfunctional oligomer;
One or more monomer components selected from the group consisting of polyfunctional monomers and monofunctional monomers;
A cured product of an ultraviolet curable resin composition containing a photopolymerization initiator,
The average functional group number in the compound group consisting of the polyfunctional oligomer and monomer component is 2.3 to 4.8,
The mass ratio of bifunctional urethane acrylate oligomer / (polyfunctional oligomer + monomer component) in the ultraviolet curable resin composition is in the range of 43/57 to 72/28,
A hard coat film for injection molding, wherein the mass ratio of polycarbonate resin / polyester resin in the base material layer is in the range of 38/62 to 92/8.

[2] The polyester resin constituting the base material layer is
Obtained by polycondensation of one or more dicarboxylic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and a glycol component containing 40 mol% or more of 1,4-cyclohexanedimethanol 2. A hard coat film for injection molding according to item 1 above, comprising the obtained polyester resin.

  [3] The hard-coating film for injection molding described in the preceding item 1 or 2 is placed in an injection mold without preforming, and the resin is molded by injecting the resin into the mold in this state. A method for producing an injection-molded article, wherein the hard coat film is integrated with a surface of a resin-molded article.

  [4] The method for producing an injection-molded article according to item 3, wherein a polycarbonate resin or a polymer alloy containing a polycarbonate resin is used as the resin to be injected into the mold.

  In the hard coating film for injection molding according to the invention of [1], the base material layer is excellent in heat resistance since it contains a polyester resin, and the base material layer is excellent in impact resistance because it contains a polycarbonate resin. The hard coat layer is composed of a cured product of an ultraviolet curable resin composition containing the specific bifunctional urethane acrylate oligomer, the polyfunctional oligomer, and the monomer component, and includes the polyfunctional oligomer and the monomer component. The average functional group number in the compound group is 2.3 to 4.8, and the mass ratio of bifunctional urethane acrylate oligomer / (polyfunctional oligomer + monomer component) in the ultraviolet curable resin composition is 43/57 to 72/28. Therefore, the surface of the injection-molded body can be given sufficient scratch resistance, and can be integrated simultaneously with the molding during the injection molding of the resin. When the film is highly stretchable, for example, it has a corner shape or a complicated shape. Is integrated into a good state the surface of the fat-shaped body. In addition, this hard coat layer does not bleed even when printed and has excellent printability.

  In addition, since the mass ratio of polycarbonate resin / polyester resin in the base material layer is in the range of 38/62 to 92/8, sufficient heat resistance and impact resistance can be ensured, and this hard coat film can be used during injection molding. For example, it can be stretched (stretched) sufficiently corresponding to a molded shape with a corner or a complicated molded shape, and a hard coat film can be integrated in a better state on the surface of an injection molded body. it can.

  In the invention of [2], the polyester resin constituting the base layer is composed of one or two or more dicarboxylic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and 1,4-cyclohexanedimethanol. Since it consists of a polyester resin obtained by polycondensation with a glycol component containing at least mol%, there is an advantage that sufficient transparency can be secured.

  According to the invention of [3] (method for producing an injection-molded article), for example, a hard coat film having sufficient scratch resistance can be injected into a resin even in a cornered shape or a complicated shape. Since it can be integrated into a good state at the same time as molding, an injection molded article excellent in scratch resistance can be produced with high production efficiency.

  In the invention of [4], a polycarbonate resin or a polymer alloy containing a polycarbonate resin is used as the resin to be injected into the mold, so that the injection strength (adhesion strength by melting) between the resin molded body and the hard coat film is further increased. A molded body can be produced.

  FIG. 1 shows an embodiment of a hard coat film (1) for injection molding according to the present invention. The hard coat film (1) is formed by laminating and integrating a hard coat layer (3) on one surface of a base material layer (2) made of a mixed resin composition containing a polycarbonate resin and a polyester resin.

In the present invention, the hard coat layer (3) is composed of a cured product of an ultraviolet curable resin composition containing the following four essential components (A), (B), (C), and (D).
(A) Bifunctional urethane acrylate oligomer (B) polyfunctional oligomer (C) polyfunctional monomer which is a reaction product of an isocyanate compound obtained by reacting polyether polyol and aromatic diisocyanate and an acrylate monomer having a hydroxyl group And one or more monomer components (D) photopolymerization initiator selected from the group consisting of monofunctional monomers.

  The polyether polyol that is a raw material of the bifunctional urethane acrylate oligomer (component A) is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, and ethylene oxide-propylene oxide random copolymer. Among them, those having a number average molecular weight (Mn) of 400 or more are preferably used.

  The aromatic diisocyanate that is a raw material of the bifunctional urethane acrylate oligomer (component A) mainly plays a role of developing scratch resistance. In addition, with linear aliphatic diisocyanate, the expression of scratch resistance is insufficient and cannot be used. Although it does not specifically limit as said aromatic diisocyanate, For example, tolylene diisocyanate, xylene diisocyanate, a methylene diphenyl diisocyanate etc. are mentioned.

  The acrylate monomer having a hydroxyl group, which is a raw material of the bifunctional urethane acrylate oligomer (component A), is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate , 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate and the like.

  The number average molecular weight of the bifunctional urethane acrylate oligomer (component A) is preferably 700 to 5,000.

  Although it does not specifically limit as said polyfunctional oligomer (component B), For example, a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer etc. are mentioned. However, the component B includes the component A (a bifunctional urethane acrylate oligomer which is a reaction product of an isocyanate compound obtained by reacting a polyether polyol and an aromatic diisocyanate and an acrylate monomer having a hydroxyl group). Make it not exist.

  Although it does not specifically limit as a urethane acrylate oligomer as said component B, For example, the reaction product of the isocyanate compound obtained by making a polyol and diisocyanate react, and the acrylate monomer which has a hydroxyl group etc. are mentioned. Although it does not specifically limit as said polyol, For example, polyester polyol, polyether polyol, polycarbonate diol etc. are mentioned.

  The epoxy acrylate oligomer as component B is not particularly limited. For example, an oligomer obtained by an esterification reaction of an oxirane ring of a bisphenol type epoxy resin and acrylic acid, an oxirane ring of an novolak epoxy resin and an acrylic resin. Examples include oligomers obtained by an esterification reaction with an acid.

  The polyester acrylate oligomer as component B is not particularly limited. For example, the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol is esterified with acrylic acid. And polyester acrylate oligomers obtained by esterifying a hydroxyl group at the terminal of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with acrylic acid.

  Among them, as the component B, it is preferable to use a urethane acrylate oligomer. In this case, sufficient hardness can be secured as the hard coat layer (3) and sufficient scratch resistance can be secured. Furthermore, as the urethane acrylate oligomer as component B, it is particularly preferable to use a monomer having a functionality of 6 or more. In this case, the urethane acrylate oligomer is generated when the hard coat layer (3) is crosslinked while ensuring sufficient scratch resistance. It is possible to reduce the curing shrinkage that is easy to make than the urethane acrylate oligomer having 5 or less functional groups.

  The production method of the polyester polyol which is an example of the raw material of the urethane acrylate oligomer as the component B is not particularly limited. For example, a method of polycondensation of diol and dicarboxylic acid or dicarboxylic acid chloride, esterification of diol or dicarboxylic acid Then, a known production method such as a method of transesterification can be employed. Examples of the dicarboxylic acid include, but are not limited to, adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, and phthalic acid. Further, the diol is not particularly limited, but for example, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene. Examples include glycol and tetrapropylene glycol.

  The polyether polyol which is an example of the raw material of the urethane acrylate oligomer as the component B is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide random copolymer and the like. Among these, those having a number average molecular weight (Mn) of less than 600 are preferably used. A number average molecular weight (Mn) of 600 or more is not preferable because the scratch resistance is lowered.

  The polycarbonate diol which is an example of the raw material of the urethane acrylate oligomer as the component B is not particularly limited. For example, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, polyoxyethylene glycol and the like may be mentioned, and two or more of these may be used in combination.

  The diisocyanate that is an example of the raw material of the urethane acrylate oligomer as the component B is not particularly limited. Is mentioned.

  The acrylate monomer having a hydroxyl group, which is an example of the raw material of the urethane acrylate oligomer as the component B, is not particularly limited. For example, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, 2- Examples include hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and polyethylene glycol monoacrylate.

  The number average molecular weight of the polyfunctional oligomer (component B) is preferably 600 to 5,000.

  The monofunctional monomer as the component C is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, Examples include acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl formamide, and isobornyl acrylate.

  The polyfunctional monomer as the component C is not particularly limited. For example, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diester Examples include pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, and polyethylene glycol diacrylate. Among them, a bifunctional acrylate monomer having a cyclic structure is suitable as the polyfunctional monomer, and when this is used, the base layer (2) of the hard coat layer (3) is maintained while maintaining sufficient scratch resistance. ) Can be sufficiently improved. The bifunctional acrylate monomer having a cyclic structure is not particularly limited. For example, ethoxylated bisphenol A diacrylate, ethoxylated hydrogenated bisphenol A diacrylate, ethoxylated cyclohexanedimethanol diacrylate, tricyclodecanedi. Examples include methanol diacrylate.

  In addition, as a component C, a monofunctional monomer may be used independently, a polyfunctional monomer may be used independently, or a polyfunctional monomer and a monofunctional monomer may be used together.

  The photopolymerization initiator (component D) is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzoin alkyl ethers, benzophenone, and benzoylbenzoic acid. Aromatic ketones, alpha-dicarbonyls such as benzyl, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane-1- ON, 2- Acetophenones such as til-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,4- Thioxanthones such as dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, alpha-acyloximes such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, p-dimethyl And amines such as ethyl aminobenzoate and isoamyl p-dimethylaminobenzoate. Of these, acetophenones such as 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one and aromatic ketones such as benzophenone are particularly suitable.

  The average number of functional groups in the compound group consisting of the polyfunctional oligomer (component B) and the monomer component (component C) needs to be in the range of 2.3 to 4.8. When the average functional group number is less than 2.3, sufficient scratch resistance cannot be ensured, and when the average functional group number exceeds 4.8, the stretchability of the hard coat film (1) is lowered. The “average number of functional groups” means the average number of functional groups averaged by weight (number of weight average functional groups).

  Moreover, the mass ratio of (component A) / (component B + component C) in the ultraviolet curable resin composition needs to be set in a range of 43/57 to 72/28. That is, the mass ratio of bifunctional urethane acrylate oligomer / (polyfunctional oligomer + monomer component) needs to be set in the range of 43/57 to 72/28. Sufficient stretchability is not obtained when the blending ratio of the bifunctional urethane acrylate oligomer (component A) is smaller than the above lower limit, and sufficient scratch resistance is obtained when the blending ratio of the bifunctional urethane acrylate oligomer (component A) is larger than the above upper limit. Can not be secured. Among them, the mass ratio of bifunctional urethane acrylate oligomer / (polyfunctional oligomer + monomer component) is preferably set in the range of 45/55 to 70/30.

  In addition, you may mix | blend various additives, such as antioxidant, a light stabilizer, a ultraviolet absorber, and an antistatic agent, with the ultraviolet curable resin composition which comprises the said hard-coat layer (3).

  In this invention, the said base material layer (2) consists of a mixed resin composition containing polycarbonate resin and polyester resin.

  Although it does not specifically limit as a polycarbonate resin which comprises the said base material layer (2), For example, the polycarbonate resin etc. which were manufactured by the well-known method of making an aromatic dihydroxy compound and a carbonate precursor react are mentioned. . Specifically, for example, a polycarbonate resin produced by an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound and phosgene are reacted in a sodium hydroxide aqueous solution in the presence of methylene chloride, an aromatic dihydroxy compound and a carbonic acid diester (for example, A polycarbonate resin produced by a transesterification method (melting method) in which diphenyl carbonate) is reacted, a polycarbonate resin produced by a solid phase polymerization of a crystallized carbonate prepolymer obtained by the phosgene method or the melting method, etc. Can be mentioned.

  As a polyester resin which comprises the said base material layer (2), 40 mol% of 1 type, or 2 or more types of dicarboxylic acid components chosen from the group which consists of terephthalic acid and a terephthalic acid derivative, and 1, 4- cyclohexane dimethanol It is preferable to use a polyester resin obtained by polycondensation with the glycol component contained above. When the proportion of 1,4-cyclohexanedimethanol in the entire glycol component is less than 40 mol%, the transparency of the film (1) cannot be obtained. Especially, it is especially preferable that the ratio of 1, 4- cyclohexane dimethanol to the whole glycol component is 50 mol% or more. 1,4-Cyclohexanedimethanol has two types of isomers, cis type and trans type, either of which may be used.

  Although it does not specifically limit as a glycol component (except 1, 4- cyclohexane dimethanol) used as the raw material of the polyester resin which comprises the said base material layer (2), For example, ethylene glycol, propylene glycol, etc. are mentioned. It is done. Among these, ethylene glycol is particularly preferably used because it has a good balance of physical properties, is widely produced industrially and is inexpensive. Of course, as the glycol component, 100 mol% of 1,4-cyclohexanedimethanol may be used (a structure composed of only 1,4-cyclohexanedimethanol may be used).

  In addition, the dicarboxylic acid component that is a raw material of the polyester resin constituting the base material layer (2) is not particularly limited, and examples thereof include dimethyl terephthalate and diethyl terephthalate. Among these, dimethyl terephthalate is preferably used.

  The mass ratio of polycarbonate resin / polyester resin in the base material layer (2) needs to be set in the range of 38/62 to 92/8. When the blending ratio of the polycarbonate resin is smaller than the above lower limit, sufficient heat resistance cannot be obtained, and when the blending ratio of the polycarbonate resin is larger than the above upper limit, sufficient stretchability cannot be obtained and a hard coat film (1 ) Cannot be integrated in good condition. Especially, it is preferable that the mass ratio of polycarbonate resin / polyester resin in the base material layer (2) is set in a range of 40/60 to 90/10.

  The mixed resin composition constituting the substrate layer (2) includes various additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a fluorescent brightener, a transesterification agent, and an antistatic agent. May be blended.

  Although the thickness of the hard coat film (1) of the present invention is not particularly limited, it is preferably 80 μm or more from the viewpoint of workability during injection molding, and 1 mm or less from the viewpoint of ensuring good stretchability during injection molding. Is preferred. Especially, it is especially preferable that the thickness of the hard coat film (1) is 0.1 to 0.3 mm.

  In the embodiment shown in FIG. 1, a configuration in which the hard coat layer (3) is laminated and integrated on one side of the base material layer (2) made of the mixed resin composition containing the polycarbonate resin and the polyester resin is adopted. The configuration is not particularly limited to such a configuration, and a configuration in which the hard coat layer (3) is laminated and integrated on both surfaces of the base material layer (2) may be adopted.

  Next, the manufacturing method of the hard coat film (1) of this invention is demonstrated. First, the base film (base material layer) (2) which consists of the said structure is prepared. For example, the base film (2) is obtained by extruding a mixed resin composition containing a polycarbonate resin and a polyester resin.

  Thereafter, the ultraviolet curable resin composition is applied to one or both surfaces of the substrate film (substrate layer) (2), and then the resin composition is cured by irradiating with ultraviolet rays to hard coat layer (3 ) To form a hard coat film (1).

  In addition, the said manufacturing method is only what showed a suitable example, and the hard coat film (1) of this invention is not specifically limited to what was manufactured with such a manufacturing method.

  Next, the manufacturing method of the injection molded body (10) according to the present invention will be described. First, the hard coat film (1) of the present invention according to the above configuration is placed in an injection mold without preforming. For example, as shown in FIG. 2 (a), the hard coat film (1) is placed in a flat shape in the cavity of the first injection mold (21) without being preformed. At this time, it arrange | positions so that the hard-coat layer (3) of a hard-coat film (1) may contact | abut to the cavity wall surface of a 1st injection mold (21).

  Thereafter, as shown in FIG. 2 (b), the second injection mold (22) is overlaid on the first injection mold (21) and closed, and in this state, the injection gate (23) is interposed. The thermoplastic resin is injected into the cavities in the molds (21) and (22). At this time, injection molding of a thermoplastic resin is performed to form a resin molded body (11), and at the same time, the hard coat film (1) is integrally formed on the surface of the resin molded body (11). The In this way, an injection molded body (10) having a hard coat portion made of the hard coat film (1) on the surface as shown in FIG. 3 is obtained.

  As the resin for injection molding, that is, as the thermoplastic resin constituting the resin molded body (11), the base layer (base layer made of a mixed resin composition containing a polycarbonate resin and a polyester resin) (2 If it is a thermoplastic resin which can be melted and integrated with a transparent resin, it is not particularly limited, and examples thereof include a polycarbonate resin and a polymer alloy containing a polycarbonate resin. Although it does not specifically limit as a polymer alloy containing the said polycarbonate resin, For example, the polymer alloy etc. which consist of a polycarbonate resin and an acrylonitrile butadiene styrene copolymer (ABS resin) etc. are mentioned.

  The injection molding resin includes an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a plasticizer, a stabilizer, a release agent, an antistatic agent, a colorant, a flame retardant, glass fiber, carbon fiber, You may mix | blend various additives, such as a drip inhibitor.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Raw materials>
(Constituent material of base material layer)
Polycarbonate resin: "Iupilon H-3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Polyester resin: “PCTG5445” manufactured by Eastman Chemical Co., Ltd.
(Constituent material of hard coat layer)
Bifunctional urethane acrylate oligomer: 150 parts by mass of hydrogenated tolylene diisocyanate and number average molecular weight (Mn) 600 in a 1 L four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser Of polyoxypropylene diol was charged and reacted at 80 ° C. for 5 hours in a nitrogen atmosphere, and then cooled to 40 ° C. Next, 150 parts by mass of 2-hydroxyethyl acrylate was added and reacted at 80 ° C. for 4 hours in an air atmosphere. The bifunctional urethane acrylate oligomer having a number average molecular weight of 1200, the polyfunctional oligomer X, and the aliphatic system having a number average molecular weight of 1000 were obtained. Hexafunctional urethane acrylate ("EB1290" manufactured by Daicel UCB)
Multifunctional oligomer Y ... Bifunctional bisphenol A epoxy acrylate ("EB3700" manufactured by Daicel UCB)
Polyfunctional oligomer Z: Aliphatic 15-functional urethane acrylate having a number average molecular weight of 2300 ("U-15HA" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Multifunctional monomer V ... 6-functional pentaerythritol hexaacrylate ("PET-K" manufactured by Daicel UCB)
Multifunctional monomer W ... Bifunctional ethoxylated bisphenol A diacrylate ("A-BPE-4" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Monofunctional monomer U ... N-vinylformamide (Arakawa Chemical Industries "Beam Set 770")
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.).

<Examples 1-5 , Comparative Examples 1-7>
A mixed resin composition obtained by mixing a polycarbonate resin (Iupilon H-3000) and a polyester resin (PCTG5445) at a blending ratio shown in Tables 1 and 2 was used using a 50 mm diameter single screw extruder (L / D = 28). A base layer film (2) having a thickness of 0.3 mm was obtained by extrusion molding.

  On the other hand, after mixing component A, component B, and component C at the blending ratios shown in Tables 1 and 2, diluted with isopropyl alcohol so that the total amount of components A, B, and C is 20% by mass, A paint for forming a hard coat layer was obtained. At this time, a photopolymerization initiator (Irgacure 184) is dissolved in isopropyl alcohol in advance, and the photopolymerization initiator is in a ratio of 4 parts by mass with respect to 100 parts by mass of the solid content (component A, component B and component C). Thus, a photopolymerization initiator was added as a part of isopropyl alcohol.

The coating material for forming the hard coat layer was applied to one side of the substrate layer film (2) using a metal bar coater, and then heated and dried at 60 ° C. for 10 minutes in a hot air circulating oven. In Example 5 and Comparative Example 7, it was applied to both surfaces of the film (2). Thereafter, a hard coat layer (3) having a thickness of 10 μm is formed by irradiating the coating film with ultraviolet rays using a 160 W / cm high-pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.). A coated film (1) was obtained. In Example 5 and Comparative Example 7, hard coat layers (3) are formed on both surfaces of the film (2). The ultraviolet irradiation was performed under the conditions of a mercury lamp and film (2) distance of 15 cm and a conveyor speed of 1.5 m / min.

Next, as shown in FIG. 2 (a), a portion of the hard coat layer (3) remains flat without the hard coat film (1) being preformed in the first injection mold (21). After being arranged so as to abut against the cavity wall surface of the one injection mold (21), the second injection mold (22) is superimposed on the first injection mold (21), and the injection is performed in this state. Polycarbonate resin (“Iupilon H-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) previously dried at 120 ° C. for 24 hours from the gate (23) into the cavities in the molds (21) and (22) has a resin temperature of 300 ° C. a mold temperature of 90 ° C., set injection pressure 100 kg / cm ^2, by injection under the conditions of an injection time of 1 second, the surface of the resin molded body (11) made of a polycarbonate resin as shown in FIG. 3 Ha It was obtained injection molded article having a hard coating portion made of coated film (1) to (10).

  The hard coat film (1) obtained as described above was evaluated for scratch resistance, transparency, heat resistance and stretchability based on the following evaluation methods. These evaluation results are shown in Tables 1 and 2.

<Scratch resistance evaluation method>
After performing a Taber abrasion test (wear wheel: CS-10F, load: 500 g, rotation speed: 100 rotations) in accordance with ASTM D1044 for the hard coat film, the haze ratio H ₂ (% ) To determine the amount of change (change value) with the haze ratio H ₁ (%) of the hard coat film before the wear test,
Change in haze ratio before and after wear test (%) = H ₂ −H ₁
The scratch resistance was evaluated from the amount of change according to the following criteria.
“◎”: Excellent scratch resistance (change in haze ratio is less than 5%)
“◯”: Excellent scratch resistance (change in haze ratio is 5% or more and less than 7%)
“△”: Scratch resistance is slightly insufficient for practical use (change in haze ratio is 7% or more and less than 10%)
“×”: Scratch resistance is practically insufficient (change value of haze ratio is 10% or more).

<Transparency evaluation method>
The hard coat layer (3) of the hard coat film (1) was visually observed and evaluated according to the following criteria.
“◎”… The surface of the hard coat layer coating is smooth and transparent from any angle. “○”… The surface of the hard coat layer coating is smooth and the transparency is slightly impaired when viewed from an extremely oblique angle. Although there is a practically no problem level, “△”: Hard coat layer coating surface is not smooth and appears to be cloudy when viewed from an angle “×”: Hard coat layer coating layer The surface is rough, and it looks cloudy when viewed from the front as well as diagonally.

<Heat resistance evaluation method>
The deflection temperature under load of the hard coat film (1) was measured according to JIS K7191-1996 and evaluated according to the following criteria. In JIS K7191, the minimum thickness of the test piece is defined as 3 mm. Therefore, only in this heat resistance evaluation, a hard coat film manufactured using the base layer film (2) having a thickness of 3.0 mm is used. Using.
“◯”: The deflection temperature under load is 90 ° C. or higher. “X”: The deflection temperature under load is less than 90 ° C.

<Elongation evaluation method>
The hard coat layer (3) of the hard coat film (1) on the surface of the injection molded body (10) was visually observed and evaluated according to the following criteria.
“○”: good reproducibility of molds in all parts of the hard coat layer, no wrinkles or cracks even at corners, “×”: no cracks or cracks in the hard coat layer, resin Those in which poor adhesion and floating phenomenon of the hard coat film (1) to the molded body (11) are observed, or those in which the mold reproducibility is not good at the corners.

As is apparent from the table, the hard coat films (1) of Examples 1 to 5 of the present invention were excellent in scratch resistance, transparency, stretchability and heat resistance.

  On the other hand, in Comparative Examples 1 and 7 in which the polycarbonate resin content in the base material layer is smaller than the lower limit of the specified range of the present invention, sufficient heat resistance cannot be obtained, and the polycarbonate resin content in the base material layer is in accordance with the prescription of the present invention. In Comparative Example 2, which is larger than the upper limit of the range, sufficient stretchability cannot be obtained. In Comparative Example 3 in which the content ratio of the bifunctional urethane acrylate oligomer in the hard coat layer is smaller than the lower limit of the specified range of the present invention, sufficient stretchability is not obtained, and the content ratio of the bifunctional urethane acrylate oligomer in the hard coat layer is In Comparative Example 4, which is larger than the upper limit of the specified range of the present invention, sufficient scratch resistance cannot be obtained. Further, in Comparative Example 5 where the average number of functional groups in (Component B + Component C) is smaller than the lower limit of the specified range of the present invention, sufficient scratch resistance cannot be obtained, and the same average functional group number is larger than the upper limit of the specified range of the present invention. In Comparative Example 6, sufficient stretchability cannot be obtained.

  The injection-molded article produced by the production method according to the present invention is used as, for example, an automobile meter panel, an automobile console panel, a mobile phone casing or keypad, various membrane switch covers, and the like. It is not limited to.

It is an expanded sectional view showing one embodiment of the hard coat film for injection molding concerning this invention. It is explanatory drawing of the manufacturing method of the injection molding body which concerns on this invention, Comprising: (a) is the state arrange | positioned in an injection mold, without pre-molding a hard-coat film, (b) is in the closed mold | type. The state immediately after injecting resin is shown, respectively. It is sectional drawing of the obtained injection molded object.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Hard coat film for injection molding 2 ... Base material layer 3 ... Hard coat layer 10 ... Injection molded object 11 ... Resin molded object 21 ... 1st injection mold 22 ... 2nd injection mold

Claims (8)

A base material layer comprising a mixed resin composition containing a polycarbonate resin and a polyester resin;
A hard coat layer laminated and integrated on one side or both sides of the base material layer,
The hard coat layer is
A bifunctional urethane acrylate oligomer that is a reaction product of an isocyanate compound obtained by reacting a polyether polyol and an aromatic diisocyanate and an acrylate monomer having a hydroxyl group;
A polyfunctional oligomer comprising a polyfunctional urethane acrylate oligomer (not including the above bifunctional urethane acrylate oligomer) and a polyfunctional epoxy acrylate oligomer ;
One or more monomer components selected from the group consisting of polyfunctional monomers and monofunctional monomers;
A cured product of an ultraviolet curable resin composition containing a photopolymerization initiator,
The average functional group number in the compound group consisting of the polyfunctional oligomer and monomer component is 2.3 to 4.8,
The mass ratio of bifunctional urethane acrylate oligomer / (polyfunctional oligomer + monomer component) in the ultraviolet curable resin composition is in the range of 43/57 to 72/28,
A hard coat film for injection molding, wherein the mass ratio of polycarbonate resin / polyester resin in the base material layer is in the range of 38/62 to 92/8. The hard coat film for injection molding according to claim 1, wherein the bifunctional urethane acrylate oligomer has a number average molecular weight of 700 to 5,000. The hard coat film for injection molding according to claim 1 or 2, wherein the polyfunctional urethane acrylate oligomer has a number average molecular weight of 600 to 5,000. The hard coat film for injection molding according to any one of claims 1 to 3, wherein the polyfunctional urethane acrylate oligomer is a hexa-functional or higher urethane acrylate oligomer. The polyester resin constituting the base material layer is
Obtained by polycondensation of one or more dicarboxylic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and a glycol component containing 40 mol% or more of 1,4-cyclohexanedimethanol The hard coat film for injection molding according to any one of claims 1 to 4, comprising the obtained polyester resin. The injection-molded hard coat film according to any one of claims 1 to 5 is placed in an injection mold without preforming, and the resin is molded by injecting the resin into the mold in this state. At the same time, the method for producing an injection-molded article, wherein the hard coat film is integrated on the surface of the resin-molded article. The method for producing an injection-molded article according to claim 6 , wherein a polycarbonate resin or a polymer alloy containing a polycarbonate resin is used as the resin to be injected into the mold. An injection-molded article comprising a hard-coated portion comprising the hard-coated film for injection molding according to any one of claims 1 to 7 on the surface of a resin molded article.

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