JP6844286B2 - Hard coat film for insert molding and resin molded products using this - Google Patents

Description

The present invention relates to a film used for a touch panel display used in an information panel of an automobile such as a car navigation system, a mobile phone, and a personal computer. In particular, the present invention relates to a hard coat film for insert molding in which fingerprints are inconspicuous and mold releasability during insert molding is good. Further, the present invention relates to a resin molded product using this.

In recent years, with the widespread use of car navigation systems and portable electronic devices, there are increasing opportunities for insert molded products to be used as covers for displays with touch panel functions. Insert molding is a method of integrally molding a hard-coated or printed film and a resin molding material with a mold (insert molding), and molding of highly-designed automobile parts and portable electronic device parts. Goods can be provided with high quality and high speed.
The hard coat layer used for insert molding is particularly required to have functions such as adhesion to a base material, moldability, and surface hardness. However, with the growing need for display applications with a touch panel function, fingerprints and the like are required. There is an increasing need for fingerprint resistance that suppresses deterioration of visibility due to the adhesion of sebum stains. For example, Patent Documents 1 and 2 provide fingerprint resistant films for insert molding that meet such demands. ing.

Insert molding is a molding method similar to in-mold molding in that it uses a decorative film and a resin injection molding process, but is technically far more advanced than in-mold molding. In in-mold molding, continuous transfer is possible by using an applicator film with good mold release, whereas in insert molding, an applicator film is used in order to further increase productivity. Instead, the thermoplastic resin for forming parts is injection-molded directly on the decorative film installed on the cavity (female mold), and the design parts, which are molded products, are taken out from the cavity. At that time, if there is a problem with the releasability of the film, a demolding defect called "cavity removal" occurs, and a serious situation occurs in which continuous line production is stopped. As the design of molded products increases, the cavity shape becomes complicated, while maintaining high productivity, which is an advantage of using a film, is required.
On the other hand, as the design of molded products of automobile parts and portable electronic device parts increases, the molded products are required to comply with design specifications having more complicated and various curved surfaces. Cracks are likely to occur on this curved surface portion, but if the flexibility of the hard coat film for insert molding is simply increased, cavities are likely to be removed this time.

As mentioned above, the contradictory mold release properties (cavities) without impairing the basic performance as a film for insert molding, such as high fingerprint visibility, low haze value after insert molding, and high pencil hardness. There is a demand for a hard coat film for insert molding that satisfies even higher required performances such as removability) and low cracking property in curved shape.

Japanese Unexamined Patent Publication No. 2014-226489 Japanese Unexamined Patent Publication No. 2016-049748

As described above, an object of the present invention is a film for insert molding, which suppresses a decrease in visibility due to fingerprints, has no cracks in a plaque shape, has a good haze after insert molding, and is a pencil. It is an object of the present invention to provide a fingerprint-resistant film for insert molding having sufficient hardness and good mold release property, and to provide a resin molded product using the same.

As a result of intensive research to solve the above problems, the present inventors have carried organic fine particles having a specific particle size in a polymer matrix having a specific solubility parameter and a glass transition temperature in a fingerprint resistant layer. The present invention has been completed by finding a finding to solve the above-mentioned problems by setting the surface unevenness roughness of the fingerprint-resistant layer within a specific range.
That is, the present invention is the following [1] to [3].
[1] A fingerprint-resistant layer is formed on one surface of a thermoplastic transparent base film.
The fingerprint-resistant layer has a film thickness of 0.5 to 3.0 μm.
A fingerprint-resistant film for insert molding in which the surface unevenness of the fingerprint-resistant layer is Ra (arithmetic mean roughness) of 0.04 to 0.20 μm.
The fingerprint-resistant layer contains the following components (A) to (D);
Polymer (A) with an SP value of 8 to 13 and a Tg of 65 to 100 ° C.
UV reactive (meth) acrylate Li Royle group-containing compound (B),
Organic fine particles (C) with an average particle diameter of 0.8 to 5.5 μm,
Photopolymerization initiator (D)
Mass ratio consists, and the polymer (A) and the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B) is 90: 10 to 60: A 40,
Polymer (A) and the ultraviolet-reactive (meth) per 100 parts by weight of accession Li Royle group-containing compound (B), 0.3 to 2.0 parts by mass of the organic fine particles (C), photopolymerization initiator ( A fingerprint-resistant film for insert molding, which is a cured product of a resin composition containing 1 to 10 parts by mass of D).
[2] The above-mentioned thermoplastic transparent base film has a two-layer structure of a polycarbonate layer and a polymethylmethacrylate layer, and the fingerprint-resistant layer is formed on the polymethylmethacrylate layer. The fingerprint-resistant film for insert molding according to [1].
[3] A resin molded product provided with the fingerprint-resistant film for insert molding according to the above [1] or [2] on its surface.

According to the present invention, deterioration of visibility due to fingerprints is suppressed, there are no cracks in the plaque shape, haze after insert molding is good, pencil hardness is sufficient, and mold release resistance is good for insert molding. A fingerprint film and a resin molded product using the same are provided.

FIG. 1 illustrates a method of calculating the glass transition temperature (Tg) by DSC measurement, and the glass transition temperature (Tg) in the present invention can be calculated from the change part of the heat generation curve with the increase in temperature. it can.

Hereinafter, the present invention will be described in more detail.
In the present specification, "○○ to XX" indicating a numerical range means "more than XX and less than XX" unless otherwise specified.
Further, in the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. The same applies to "(meth) acryloyl group" and "(meth) acrylic resin".
The fingerprint-resistant film for insert molding of the present invention has a fingerprint-resistant layer formed on one surface of a thermoplastic transparent base film, and the fingerprint-resistant layer comprises the following components (A) to (D). It is a cured product of the resin composition.
Polymer (A) having an SP value of 8 to 13 and a Tg of 65 to 100 ° C.
UV reactive (meth) acrylate Li Royle group-containing compound (B)
Organic fine particles (C) with an average particle diameter of 0.8 to 5.5 μm
Photopolymerization initiator (D)

≪Thermoplastic transparent base film≫
As the thermoplastic transparent base film, a film made of one or both of a polycarbonate resin and a polymethylmethacrylate resin can be used, and a film having a two-layer structure of a polycarbonate layer and a polymethylmethacrylate layer is particularly preferable. The film thickness of the thermoplastic transparent base film is usually 30 to 250 μm, preferably 125 to 200 μm. The refractive index of the thermoplastic transparent base film is preferably 1.49 to 1.59. A film made of a polyester resin such as PET is not preferable as the base film of the present invention because whitening or the like caused by cracks occurs when the base film is stretched during molding.

≪Fingerprint resistant layer≫
The thickness of the fingerprint-resistant layer is 0.5 to 3.0 μm. If it is less than 0.5 μm, the effect of suppressing the adhesion of fingerprints is reduced. If it is thicker than 3.0 μm, the stretchability is lowered during the insert molding process in which stress is applied, and cracks are likely to occur in the fingerprint resistant layer.
The Ra (arithmetic mean roughness) of the surface unevenness of the fingerprint-resistant layer is 0.04 to 0.20 μm. If it is lower than 0.04 μm, the mold releasability is lowered, and if it is higher than 0.20 μm, the haze after insert molding is bad.
The fingerprint-resistant layer is a cured product obtained by curing a resin composition for a fingerprint-resistant layer with ultraviolet rays or the like, and the composition thereof will be described below.

<Polymer (A)>
The polymer (A) used in the present invention has an SP value of 8 to 13, preferably 9 to 11. If the SP value is lower than 8, it becomes more noticeable when fingerprints are attached, and if it is higher than 13, the compatibility with other components in the paint of the fingerprint resistant layer deteriorates, so that a part of the fingerprint resistant layer is repelled on the transparent film. It is in a state of being in a state of being, and sufficient surface properties cannot be obtained.

The polymer (A) used in the present invention has a Tg of 65 to 100 ° C, preferably 70 to 90 ° C. If the Tg is lower than 65 ° C, it becomes too soft during the insert molding process and the mold releasability (cavity removal property) deteriorates, and if it is higher than 100 ° C, the stretchability decreases during the insert molding process where stress is applied. Therefore, cracks are likely to occur in the fingerprint-resistant layer, which is not preferable.

Examples of the polymer having an SP value of 8 to 13 and a Tg of 65 to 100 ° C. include a polyolefin structure, a polystyrene structure, a poly (meth) acrylic acid structure, a poly (meth) acrylic acid ester structure, a polysiloxane structure, and a polyester structure. Has at least one structure selected from the group consisting of a polyamide structure, a polyimide structure, a polyurethane structure, and a cellulose structure, and has a hydroxyl group (-OH), an ether group (-O-), and a carboxyl group (-COOH). ), Oxycarbonyl group (-OC (= O)-), siloxane bond (-SiO-), trialkoxysilyl group (-OR ₃ ) having 1 to 18 carbon atoms, fluoro group (-F), chloro group (-F) Examples thereof include polymers having a weight average molecular weight of 5000-500,000 having at least one functional group selected from the group consisting of -Cl), bromo group (-Br), and iodo group (-I). The SP value can be appropriately controlled by the content ratio of these structures and the like. The polymer may be a homopolymer, a block copolymer, a graft copolymer, or the like. For example, a block copolymer having a poly (meth) acrylic acid ester structure and a polysiloxane structure as units. , A graft copolymer or the like having a polyolefin structure as a main chain and a poly (meth) acrylic acid structure as a graft chain corresponds to the polymer. Further, the functional group in the polymer may be one that exists from the state of the monomer before polymerization, one that is formed by polymerization, or one that is introduced by modifying the polymer. As a method for modifying the polymer, a known method can be appropriately adopted. For example, a method in which the carboxylic acid anhydride structure in the polymer is reacted with an alcohol to esterify and the structure derived from the alcohol is introduced into the side chain of the polymer. (See the reaction formula below).

Specific materials for the polymer (A) include a carboxylic acid-modified unsaturated dicarboxylic acid grafted polyolefin, a silicone acrylic polymer, and a silicone acrylic block, in which an unsaturated dicarboxylic acid anhydride is grafted onto a polyolefin and modified by reacting with a carboxylic acid. Examples thereof include copolymers, styrene / methacrylic resins, organic acid vinyl ester resins, vinyl ether resins, polyamides (nylon 66), polyvinylidene chloride, polyvinyl alcohols, thermoplastic polyurethane resins, and thermoplastic resins such as cellulose derivatives.

<UV reactive (meth) acrylate Li Royle group-containing compound (B)>
UV reactive for use in the present invention (meth) acrylate Li Royle group-containing compound (B), (meth) has an acryloyl group to cure the fingerprint layer resin composition by exposure to UV radiation, resistant The fingerprint layer can be hardened. In addition, by including UV reactive (meth) acrylate Li Royle group containing compound (B), there is a tendency that weather resistance such as solvent corrosion resistance and moisture resistance are improved. UV reactive for use in the present invention (meth) acrylate Li Royle group-containing compound (B) is less than the weight-average molecular weight of 5,000 is not particularly limited as long as it is cured by ultraviolet rays are irradiated, known Can be used. SP values of UV reactive for use in the present invention (meth) acrylate Li Royle group-containing compound (B) is preferably 8-16, more preferably 8-13. When the SP value of the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B) is 8 to 13, it becomes easy to ensure the compatibility with the polymer (A).

As the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B), monofunctional (meth) acrylate represented by the following formula (B-1) or (B-2), the following formula (B-3) ~ Examples thereof include a bifunctional (meth) acrylate represented by any one of (B-5) and a polyfunctional (meth) acrylate represented by the following formula (B-6) or (B-7).
(In formulas (B-1) to (B-7), R ¹ independently has a hydrogen atom or a methyl group, and R ² and R ⁴ have a hydroxyl group (-OH) and an ether group (-O-). A hydrocarbon group having 1 to 20 carbon atoms which may contain at least one functional group selected from the group consisting of a carboxyl group (-COOH) and an oxycarbonyl group (-OC (= O)-). , R ³ , R ⁶ and R ⁸ are carbon atoms which may each independently contain at least one functional group selected from the group consisting of a hydroxyl group (-OH) and an ether group (-O-). The divalent hydrocarbon groups of numbers 1 to 20, R ⁵ and R ⁷ are hydroxyl groups (-OH), ether groups (-O-), carboxyl groups (-COOH), and oxycarbonyl groups (-OC (=). A divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one functional group selected from the group consisting of O)-), and m is an independently integer of 1 to 30. , N represents an integer of 3 to 10 and Z represents an n-valent group consisting of a carbon atom and at least one atom selected from the group consisting of hydrogen atom, oxygen atom and nitrogen atom.)
The "hydrocarbon group" may have a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (carbon-carbon double bond, carbon-carbon triple bond), respectively, and is a saturated hydrocarbon group. , Unsaturated hydrocarbon group, aromatic hydrocarbon group and the like.
R ¹ is preferably a hydrogen atom, R ² and R ⁴ are preferably hydrocarbon groups having 1 to 10 carbon atoms, and R ³ , R ⁶ and R ⁸ are hydrocarbon groups having 3 to 12 carbon atoms. It is preferred, as ^{R 5} and ^{R 7} include preferably a hydrocarbon group having 2 to 12 carbon atoms.

Examples of the monofunctional (meth) acrylate represented by the formula (B-1) or (B-2) include ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol # 400 acrylate (m = 9), and methoxypolyethylene glycol # 550. Acrylate (m = 13), Phenoxypolyethylene glycol acrylate (m = 2), 2-acryloyloxyethyl succinate, isostearyl acrylate, 2-methacryloyloxyethylphthalic acid, methoxypolyethylene glycol # 400 methacrylate (m = 9), Examples thereof include methoxypolyethylene glycol # 1000 methacrylate (m = 23), phenoxyethylene glycol methacrylate, stearyl methacrylate, 2-methacryloyloxyethyl succinate and the like.

Examples of the bifunctional (meth) acrylate represented by any of the formulas (B-3) to (B-5) include 2-hydroxy-3-acryloyloxypropyl methacrylate and polyethylene glycol # 200 diacrylate (m = 4). ), Polyethylene Glycol # 400 Diacrylate (m = 9), Polyethylene Glycol # 600 Diacrylate (m = 14), Polyethylene Glycol # 1000 Diacrylate (m = 23), Propoxyized Eethoxyated Bisphenol A Diacrylate (m Total =) 12), ethoxylated bisphenol A diacrylate, 9,9- [4- (2-acryloyloxyethoxy) phenyl] fluorene, tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexane Didiol diacrylate, 1,9-nonane diol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, neopentyl glycol Dimethacrylate and the like can be mentioned.

Examples of the polyfunctional (meth) acrylate represented by the formula (B-6) or (B-7) include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, and dipenta. Elythritol hexaacrylate, pentaerythritol triacrylate, tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, as "Shikou UV-7600B" manufactured by Nippon Synthetic Chemical Co., Ltd. Examples include available hexafunctional urethane acrylates. Of these, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and hexafunctional urethane acrylate available as "Shikou UV-7600B" manufactured by Nippon Synthetic Chemical Co., Ltd. can be applied because it is easy to maintain high hardness. preferable.

The mass ratio of the polymer (A) and the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B) is 90: 10 to 60: A 40, preferably 80: 30: 20 to 70. The polymer (A), becomes insufficient hardness of the mass ratio is too small fingerprint layer of UV reactive (meth) acrylate Li Royle group-containing compound (B), pencil hardness (Evaluation Method: JIS-K5600- 5-4) does not exceed 2H. On the other hand, if it is too large, the stretchability is lowered during the insert molding process in which stress is applied, and cracks are likely to occur in the fingerprint resistant layer, which is not preferable.

<Organic fine particles (C)>
Examples of the organic fine particles (C) used in the present invention include (meth) acrylic resin, polyamide resin, polyamideimide resin, thermoplastic resin such as polyacetal resin, crosslinked polyolefin resin, crosslinked (meth) acrylic resin, and crosslinked polystyrene. Examples thereof include based resins, crosslinked thermoplastic resins such as crosslinked polyurethane resins, and particles formed of thermocurable resins such as epoxy resins. These organic particles can be used alone or in combination of two or more. Among these organic particles, thermoplastic resin particles such as polyamide particles and crosslinked thermoplastic resin particles such as crosslinked poly (meth) acrylic acid ester particles, crosslinked polystyrene particles, and crosslinked polyurethane particles are widely used.

The average particle size of the organic fine particles (C) used in the present invention is 0.8 to 5.5 μm, preferably 3.0 to 5.5 μm. When the average particle size is less than 0.8 μm, the unevenness on the surface of the fingerprint-resistant layer becomes small and the mold releasability becomes insufficient. On the other hand, if it exceeds 5.5 μm, the unevenness on the surface of the fingerprint-resistant layer becomes large, causing whitening and impairing transparency, which is not preferable.

The average particle size in the present invention is a value calculated from the obtained particle number distribution obtained by measuring by the Coulter counter method and converting the measured distribution into the particle number distribution. The Coulter counter method is a particle size measuring method using electric resistance, and is a method of measuring an average particle size by measuring a change in electric resistance between two electrodes that occurs when a particle passes through a pore. ..

The refractive index of the organic fine particles (C) used in the present invention is preferably 1.46 to 1.60, more preferably 1.48 to 1.53. When the refractive index of the organic fine particles (C) is 1.48 to 1.53, it becomes easy to maintain good haze after insert molding.

The organic fine particles (C) used in the present invention are 0.3 to 2.0 parts by mass, preferably 0.5 to 1.0 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). contains. When the content of the organic fine particles is less than 0.3 parts by mass, the functions of the organic fine particles cannot be fully exerted, and the mold releasability cannot be obtained. On the other hand, if it is more than 2.0 parts by mass, the haze value after insert molding becomes too high, and when the fingerprint-resistant film is placed on the display surface, whitening or the like occurs and scintillation (face glare) occurs. Image sharpness is reduced.

<Photopolymerization initiator (D)>
The photopolymerization initiator used in the present invention is further added to the above components (A) to (C) to form a resin composition, which is cured by active energy rays such as ultraviolet rays (UV) to form a coating film. .. The photopolymerization initiator is not particularly limited as long as it initiates polymerization by irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpherinopropane-1. -On, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one and other acetphenone-based polymerization initiators, benzophenone, 2,2-dimethoxy 1,2 Benzophenone-based polymerization initiators such as −diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3', 4,4' Examples thereof include benzophenone-based polymerization initiators such as -tetra (t-butylperoxycarbonyl) benzophenone, and thioxanthone-based polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone.

The addition amount of the photopolymerization initiator (D), so that the total 100 parts by mass of the polymer (A) and the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B), the 1 to 10 parts by weight To. If it is less than 1 part by mass, curing does not proceed sufficiently, sufficient hardness cannot be secured, and if it exceeds 10 parts by mass, the adhesion may be lowered.

[SP value: Solubility parameter]
The SP value is a solubility parameter and is a measure of solubility. The larger the SP value, the higher the polarity, and conversely, the smaller the value, the lower the polarity. Generally, the difference in SP value of the two components is regarded as a measure of compatibility, and the larger the difference, the more difficult it is for the two components to mix.

The SP value of the polymer in the present invention is determined by the voiced sound mark method [References: Suh, Clarke, J. et al. Polym. Sci, .A-1, 5, 1671-1681 (1967)]. Specifically, the polymer is dissolved in a good solvent having a known SP value, and a poor solvent having a higher SP value than the good solvent in which the polymer is dissolved and a poor solvent having a lower SP value than the good solvent in which the polymer is dissolved are used. The SP value of the polymer can be determined by turbidity titration with. The SP value δ of the polymer is given by the following equation.
V _mL = V ₁ V ₂ / (φ ₁ V ₂ + φ ₂ V ₁ )
V ₁ : Molecular content of the poor solvent at the point where turbidity begins to occur in a poor solvent with an SP value lower than the good solvent in which the polymer is dissolved (turbidity point) V ₂ : Poor solvent with an SP value lower than the good solvent in which the polymer is dissolved Molecular volume of a good solvent at the point where turbidity begins to occur (turbidity point) φ ₁ : Body integration rate of the poor solvent at the point where turbidity begins to occur at a poor solvent with an SP value lower than that of the good solvent in which the polymer is dissolved (turbidity point) φ _{2 : Body integration} rate of the good solvent at the point (turbidity point) where turbidity began to occur in a poor solvent with an SP value lower than that of the good solvent in which the polymer was dissolved V mh = V ₃ V ₄ / (φ ₃ V ₄ + φ ₄ V ₃ )
V ₃ : Molecular content of the poor solvent at the point where turbidity began to occur in the poor solvent with a higher SP value than the good solvent in which the polymer was dissolved (turbidity point) V ₄ : Poor solvent with a higher SP value than the good solvent in which the polymer was dissolved Molecular volume of good solvent at the point where turbidity begins to occur (turbidity point) φ ₃ : Body integration rate of the poor solvent at the point where turbidity begins to occur with a poor solvent with a higher SP value than the good solvent in which the polymer is dissolved (turbidity point) φ _{4 : Body integration} rate of the good solvent at the point (turbidity point) where turbidity begins to occur in a poor solvent with a higher SP value than the good solvent in which the polymer is dissolved φ mh = φ ₃ δ ₃ + φ ₄ δ ₄
δ ₃ : SP value of the poor solvent, which is a higher SP value than the good solvent in which the polymer is dissolved δ ₄ : SP value of the good solvent whose turbidity is measured in the poor solvent, which has a higher SP value than the good solvent in which the polymer is dissolved.

[Tg: glass transition temperature]
The glass transition temperature (Tg) indicates the external glass transition start temperature measured by DSC (Differential Scanning Calorimetry) described in JIS K7121-1987. As shown in FIG. 1, the extra glass transition start temperature is the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the curve gradient of the stepwise change portion of the glass transition is maximized. The temperature at the intersection (see Figure 1).

[Formation of fingerprint resistant layer]
First, the fingerprint-resistant layer resin composition is applied onto one surface of the thermoplastic transparent base film, and then dried or irradiated with ultraviolet rays to be cured to withstand the resistance on the thermoplastic transparent base film. A fingerprint layer is formed. As a result, a fingerprint-resistant film for insert molding can be obtained.

The method for applying the above-mentioned resin composition for fingerprint-resistant layer is not particularly limited, and commonly used application methods such as roll coating method, spin coating method, dip coating method, spray coating method, bar coating method, and knife coating method are used. , A die coating method, an inkjet method, a gravure coating method, or any other known method is adopted. At the time of coating, in order to improve the adhesion, the surface of the thermoplastic transparent base film can be pretreated in advance by a corona discharge treatment or the like.

Further, from the viewpoint of coatability, it is preferable that each resin composition is diluted with a solvent and coated. The solvent is not particularly limited as long as it is a known solvent conventionally used for the coating liquid for forming each layer, and for example, an alcohol-based solvent, a ketone-based solvent, or an ester-based solvent can be selected in a timely manner.

When irradiating the coating film with ultraviolet rays, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radiation source of a radioactive element or the like is used as the ultraviolet ray source. In this case, the irradiation amount of ultraviolet rays is preferably ^{50 to 5000 mJ / cm 2} as the integrated light amount of ultraviolet rays at a wavelength of 365 nm. When the irradiation amount is within this range, the coating film is not sufficiently cured and the polymer of the component (A) is not colored, and the coating film can be suitably cured.

[Resin molded product using fingerprint resistant film for insert molding]
The fingerprint-resistant film for insert molding is integrated with the surface of the molded product at the same time as molding the resin by insert molding. By holding the fingerprint-resistant film for insert molding in the cavity inside the injection molding mold and injecting the molten resin into the mold, the fingerprint-resistant film for insert molding is integrated on the surface, and the surface is fingerprint-resistant. A resin molded product having a layer can be obtained.

In insert molding for obtaining the resin molded product of the present invention, the temperature of the mold is appropriately set in consideration of other molding conditions, but in most cases, it is maintained at about 100 ° C. The reason why the temperature of the mold is kept at about 100 ° C is that if the temperature of the mold exceeds 100 ° C and becomes high, the antiglare film on the surface will be wrinkled or distorted due to the thermal history of the molded product. This is because On the other hand, if the temperature of the mold is significantly lower than 100 ° C., the resin temperature drops too much during the molding process, and it becomes difficult to form the desired shape.

The fingerprint-resistant film of the present invention and a resin molded product using the same are liquid crystal displays in electronic image devices such as televisions, video cameras, word processors, car navigation systems, car navigation system cover lens personal computers, mobile phones, automobile information panels, and touch panels. , Plasma display, organic EL (electroluminescence) display, inorganic EL display, FED (field emission display) and other various displays.

Hereinafter, the embodiment will be described in more detail with reference to Production Examples, Examples and Comparative Examples.
First, the following raw materials were prepared in order to prepare a resin composition used for forming the fingerprint-resistant layer.

<Preparation of polymer (A)>
Polymers A1 to A4, which are polymers (A) used in the present invention, were prepared as follows.
1. 1. Preparation of propionyl-modified unsaturated dicarboxylic acid (anhydrous) grafted polyolefin (A1) High molecular weight polyolefin (copolymer of propylene and 1-butene: "Toughmer XR110T" manufactured by Mitsui Kagaku Co., Ltd.) with a stirrer and thermometer A low-molecular-weight polyolefin (a1) was obtained by heat reduction by placing it in a prepared reaction vessel, heating it to 360 ° C. to melt it, and heating it under a nitrogen stream for 100 minutes.

Next, 160 parts by mass of the low molecular weight polyolefin (a1) was placed in a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, heated to 180 ° C. under a nitrogen stream to melt, and then maleic anhydride 25. 20 parts by mass and 20 parts by mass of 1-dodecene were added and mixed uniformly. Next, a solution prepared by dissolving 1 part by mass of dicumyl peroxide in 20 parts by mass of xylene prepared in advance was added dropwise over 2 hours while maintaining 180 ° C., and after the addition, the mixture was further stirred at 180 ° C. for 2 hours to obtain maleic anhydride. An acid grafting reaction was carried out. Then, xylene and 1-dodecene were distilled off under reduced pressure to obtain a maleic anhydride grafted polyolefin (a2).

Next, 450 parts by mass of the maleic anhydride-grafted polyolefin (a2) is placed in a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, and the temperature is raised to 105 ° C. under a nitrogen stream to maintain the temperature. 300 parts by mass of toluene was gradually added dropwise with stirring. Next, 135 parts by mass of hydroxyl group-containing propionate [CH ₃ CH ₂ COO (CH ₂ ) ₂ OCO (CH ₂ ) ₅ OH] was added, reacted at the same temperature for 3 hours with stirring, cooled, and hydroxyl group-containing propionyl. A modified maleic anhydride grafted polyolefin (A1) was obtained. This resin had a weight average molecular weight of 12,100, an SP value of 10.9, and a Tg: 80 ° C.

2. Preparation of Silicone Acrylic Block Copolymer (A2) VPS-1001N (azo group-containing polysiloxane compound, manufactured by Wako Pure Chemical Industries, Ltd., polysiloxane chain molecular weight 10,000, solid content 50%) 243.9 parts by mass Was mixed with a mixture consisting of 144.0 parts by mass of cyclohexane methacrylate, 43.7 parts by mass of styrene, 52.3 parts by mass of hydroxylethyl methacrylate and 343.3 parts by mass of butyl acetate. This mixed solution was placed in 270.0 parts by mass of butyl acetate heated to 120 ° C. under a nitrogen atmosphere in a 1000 mL reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel over 3 hours, etc. It was added dropwise at a rapid rate, and then mixed at 120 ° C. for 30 minutes for reaction. A solution of 15.0 parts by mass of butyl acetate containing 0.60 parts by mass of tertiary butyl peroxy-2-ethylhexanoate was added dropwise over 30 minutes at a constant velocity, and then mixed at 120 ° C. for 1 hour for reaction. A silicone acrylic block copolymer having a number average molecular weight of 34,000 and a weight average molecular weight of 125,000 was obtained. This resin had an SP value of 10.8 and a Tg of 69 ° C.

3. 3. Preparation of Silicone Acrylic Polymer (A3) 40 parts by mass of γ-methacryloxypropyltrimethoxysilane and 20 parts by mass of butyl acetate are placed in a reactor and refluxed while heating and stirring. A solution of 40 parts by mass of butyl acetate by mass of azobisisobutyronitrile was added dropwise to this over 2 hours while maintaining the reflux state, and reflux was continued for another 1 hour after the completion of the addition. The obtained resin liquid had a non-volatile content of 41%, and the Tg of the resin was 90 ° C. Weight average molecular weight 110,000, SP value: 8.5.

4. Styrene / methacrylic resin (A4)
Styrene / methacrylic resin: "BR-50" manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 65,000, SP value: 9.2, Tg: 100 ° C.
Polymers A'5 and A'6 other than the polymer (A) used in the present invention were prepared as follows.

5. Styrene / methacrylic resin (A'5)
Polymethylmethacrylate: "M-4003" manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 1,000,000, SP value: 9.0, Tg: 105 ° C.

6. Preparation of Fluorine-Containing Compound (A'6) 104 parts by mass of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) in a four-necked flask And 11 parts by mass of an 8% by mass perfluorohexane solution of bis (2,2,3,3,4,5,5,6,6,7,7-dodecafluoroheptanoid) peroxide was added. Then, after replacing the hollow portion with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream to obtain a highly viscous solid. The obtained solid was dissolved in diethyl ether, poured into perfluorohexane, separated, and vacuum dried to obtain a colorless and transparent polymer.
When this polymer was ^{analyzed by 19} F-NMR (nuclear magnetic resonance spectrum), ¹ H-NMR, and IR (infrared absorption spectrum), it was a fluorine-containing polymer having a hydroxyl group at the end of the side chain composed of the structural unit of the allyl ether. It was. The weight average molecular weight was 118,000.
5 parts by mass of the obtained fluorine-containing allyl ether polymer having a hydroxyl group, 43 parts by mass of methyl ethyl ketone (MEK), and 1 part by mass of pyridine were placed in a four-necked flask and ice-cooled to 5 ° C. or lower. Then, 1 part by mass of α-fluoroacrylic acid fluoride dissolved in 9 parts by mass of MEK was added dropwise over 10 minutes while stirring under a nitrogen stream. As a result, a fluorine-containing compound (A'6) having a polymerizable double bond was obtained. This resin had an SP value of 7.5 and a Tg of 102 ° C.

<UV reactive (meth) acrylate Li Royle group-containing compound (B)>
UV reactive for use in the present invention (meth) acrylate Li Royle group-containing compound (B) was prepared as follows.
DPHA: Dipentaerythritol hexaacrylate, "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd., molecular weight: 578, SP value: 12.1
A-TMM-3LM-N: Pentaerythritol triacrylate, "A-TMM-3LM-N" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 298, SP value: 12.7

<Organic fine particles (C)>
The organic fine particles (C) used in the present invention were prepared as follows.
XX-27V: Fine particles of styrene-acrylic copolymer, "XX-27V" manufactured by Sekisui Plastics Co., Ltd., average particle diameter 3.0 μm, refractive index 1.50
MX-80H3wT: Cross-linked polymethyl methacrylate resin fine particles, "Chemisnow MX-80H3wT" manufactured by Soken Kagaku Co., Ltd., average particle diameter 0.8 μm, refractive index 1.49
SSX1055QXE: Crosslinked acrylic-styrene copolymer resin particles, "SSX1055QXE" manufactured by Sekisui Plastics Co., Ltd., average particle diameter 5.5 μm, refractive index 1.51
SSX-108: Acrylic particles, "SSX-108" manufactured by Sekisui Plastics Co., Ltd., average particle diameter 8.0 μm, refractive index 1.49
MX-40T: Cross-linked acrylic particles, "MX-40T" manufactured by Soken Kagaku Co., Ltd., average particle diameter 0.4 μm, refractive index 1.49

<Photopolymerization initiator (D)>
I-184: 1-Hydroxycyclohexane-1-ylphenylketone, "I-184" manufactured by Ciba Specialty Chemicals Co., Ltd.

<Solvent>
Methyl isobutyl ketone / isopropyl alcohol = 50/50

(Production Examples 1 to 10, Comparative Production Examples 1 to 9)
Next, the above raw materials were used as the resin composition for the fingerprint resistant layer, and each raw material was mixed with the compositions shown in Tables 1 and 2. Further, 25 parts by mass of the mixture and 75 parts by mass of the solvent were mixed to prepare a coating liquid for a fingerprint resistant layer. Regarding the names of each material, some of the above abbreviations were used in the table.

[Manufacturing of fingerprint resistant film for insert molding]
The fingerprint-resistant films for insert molding of Examples 1 to 12 and Comparative Examples 1 to 13 in which the fingerprint-resistant layer was formed on one surface of the thermoplastic transparent base film shown in Tables 3 and 4 were produced.

<Thermoplastic transparent base film>
In each Example and Comparative Example, the following was used as the thermoplastic transparent base film.
Polycarbonate film (PC): "C000" manufactured by Sumitomo Chemical Co., Ltd. 188 μm,
Polymethylmethacrylate film (PMMA): "S014G" manufactured by Sumitomo Chemical Co., Ltd. 188 μm,
Film (PC / PMMA) consisting of a two-layer structure consisting of a polycarbonate layer and a polymethylmethacrylate layer: "C001" manufactured by Sumitomo Chemical Co., Ltd. 200 μm

(Making a fingerprint resistant film)
(Example 1)
The fingerprint-resistant layer coating solution (Production Example 1) was applied onto the polymethylmethacrylate film (PMMA) with a roll coater, and dried at 80 ° C. for 2 minutes. Then, it was irradiated with ultraviolet rays by a 120 W high-pressure mercury lamp [manufactured by Nippon Battery Co., Ltd.] (integrated light intensity 400 mJ / cm ² ) and cured to prepare a fingerprint-resistant layer. The thickness of the fingerprint-resistant layer was 1.0 μm. The arithmetic mean roughness Ra, which is the surface unevenness of the fingerprint-resistant layer, was 0.08.

(Example 2)
The fingerprint-resistant layer coating liquid (Production Example 1) was applied onto the polycarbonate film (PC) with a roll coater, and dried at 80 ° C. for 2 minutes. Then, it was irradiated with ultraviolet rays by a 120 W high-pressure mercury lamp [manufactured by Nippon Battery Co., Ltd.] (integrated light intensity 400 mJ / cm ² ) and cured to prepare a fingerprint-resistant layer. The thickness of the fingerprint-resistant layer was 0.5 μm. The arithmetic mean roughness Ra was 0.04.

(Example 3)
The fingerprint-resistant layer coating solution (Production Example 1) was applied onto the polymethylmethacrylate film (PMMA) with a roll coater, and dried at 80 ° C. for 2 minutes. Then, it was irradiated with ultraviolet rays by a 120 W high-pressure mercury lamp [manufactured by Nippon Battery Co., Ltd.] (integrated light intensity 400 mJ / cm ² ) and cured to prepare a fingerprint-resistant layer. The thickness of the fingerprint-resistant layer was 3.0 μm. The arithmetic mean roughness Ra was 0.19.

(Example 4)
The fingerprint-resistant layer coating liquid (Production Example 2) was applied on a film (PC / PMMA) having a two-layer structure of the polycarbonate layer and the polymethylmethacrylate layer with a roll coater, and dried at 80 ° C. for 2 minutes. .. Then, it was irradiated with ultraviolet rays by a 120 W high-pressure mercury lamp [manufactured by Nippon Battery Co., Ltd.] (integrated light intensity 400 mJ / cm ² ) and cured to prepare a fingerprint-resistant layer. The thickness of the fingerprint-resistant layer was 1.0 μm. The arithmetic mean roughness Ra was 0.08.

(Examples 5 to 12)
A fingerprint-resistant layer was prepared by curing in the same manner as in Example 4 except that the coating liquid for the fingerprint-resistant layer was changed to Production Examples 3 to 10. The arithmetic mean roughness Ra is as shown in Table 3.

(Comparative Examples 1 and 2)
The fingerprint-resistant layer was prepared by curing in the same manner as in Example 4 except that the coating liquid for the fingerprint-resistant layer was changed to Production Example 1 and the thickness of the fingerprint-resistant layer was changed to 0.4 μm and 3.2 μm, respectively. The arithmetic mean roughness Ra is as shown in Table 4.

(Comparative Example 3)
A fingerprint-resistant layer was prepared by curing in the same manner as in Example 6 except that the thickness of each of the fingerprint-resistant layers was changed to 0.6 μm. The arithmetic mean roughness Ra is as shown in Table 4.

(Comparative Example 4)
A fingerprint-resistant layer was prepared by curing in the same manner as in Example 7 except that the thickness of each of the fingerprint-resistant layers was changed to 1.2 μm. The arithmetic mean roughness Ra is as shown in Table 4.

(Comparative Examples 5 to 13)
A fingerprint-resistant layer was prepared by curing in the same manner as in Example 4 except that the coating liquid for the fingerprint-resistant layer was changed to Comparative Production Examples 1 to 9. The arithmetic mean roughness Ra is as shown in Table 4.

Regarding the obtained fingerprint-resistant film for insert molding, the haze after insert molding, Ra, fingerprint visibility, pencil hardness, the presence or absence of cracks in the curved shape of the molded product, and the mold releasability (mold removal property) are determined by the following methods. Measured in.

(1) Haze value A haze value (%) as an optical characteristic was measured using a haze meter [NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.].

(2) Arithmetic mean roughness Ra
Arithmetic mean roughness Ra in accordance with JIS B0601-1994 under the conditions of scanning range 4 mm and scanning speed 0.2 mm / s using a surface roughness measuring instrument [manufactured by Kosaka Laboratory Co., Ltd., model name Surfcorder SE500]. (Μm) was measured.

(3) Fingerprint Visibility A fingerprint was adhered to the fingerprint-resistant layer, and the visibility was visually evaluated in the following four stages.
⊚: Fingerprints are not visible at all, ○: Fingerprints are slightly visible, Δ: Fingerprints are slightly visible, ×: Fingerprints are visible.
○ The above is the pass range that can be put to practical use.

(4) Pencil hardness The load was 750 gf and evaluated in accordance with JIS K 5600.
2H or more is the pass range that can be put into practical use.

(5) Presence or absence of cracks in the curved surface shape of the molded product A resin molded product is produced by insert molding using a fingerprint resistant film for insert molding under the following molding conditions, and the curved surface portion of the molded product is visually confirmed. Then, the presence or absence of cracks such as cracks was confirmed.
○: No cracks such as cracks, ×: Cracks such as cracks

(6) Die release property (cavity removal property)
When a resin molded product is manufactured by insert molding using a fingerprint-resistant film for insert molding under the following molding conditions and the molded product is removed from the mold, the presence or absence of poor mold releasability from the mold and the mold The mold releasability was evaluated by visually confirming that no wrinkles, blisters, peeling, etc. were generated on the surface layer in contact with the surface layer and that there was no problem in appearance.
◯: Good releasability from the mold and good appearance without wrinkles, blisters, peeling, etc. ×: Poor releasability from the mold, or wrinkles, blisters, peeling, etc. occur Poor appearance Tables 3 and 4 show the evaluation results of the fingerprint-resistant film for insert molding based on the above evaluation method.

From the results shown in Table 3, in Examples 1 to 12, the fingerprints are inconspicuous because they have good mold release property (mold removal resistance) and excellent fingerprint visibility. Further, the pencil hardness has achieved 2H.

On the other hand, from the results shown in Table 4, in Comparative Example 1, the film thickness of the fingerprint-resistant layer is thin and the mold release property is poor. In Comparative Example 3, the arithmetic mean roughness Ra was low and the mold release property was poor.
In Comparative Example 2, the fingerprint-resistant layer is too thick, so that the haze after insert molding is poor. In Comparative Example 4, not only the arithmetic mean roughness Ra was high and the haze after insert molding was poor, but also cracks were generated in the curved surface shape.
In Comparative Example 5, since the composition amount of the component (A) was less than the lower limit, cracks were generated in the curved surface shape, and the fingerprint visibility was also poor.
In Comparative Example 6, since the composition amount of the component (A) exceeded the upper limit, the pencil hardness was poor.
In Comparative Example 7, since the Tg of the component (A) exceeded the upper limit, a crack was generated in the curved surface shape.
In Comparative Example 8, since the polymer in which the SP value of the component (A) is below the lower limit is used, cracks occur in the curved surface shape, and the fingerprint visibility is also poor.
In Comparative Example 9, since the composition amount of the organic fine particles (C) is larger than the upper limit, the arithmetic mean roughness Ra is high and the haze after insert molding is poor.
In Comparative Example 10, since the composition amount of the organic fine particles (C) is less than the lower limit, the mold release property is poor.
In Comparative Example 11, since the particle size of the organic fine particles (C) is larger than the upper limit, the haze after insert molding is poor.
In Comparative Example 12, since the particle size of the organic fine particles (C) is smaller than the lower limit, the mold release property is poor.
In Comparative Example 13, since the organic fine particles (C) are not contained, the mold release property is poor.

The fingerprint-resistant film of the present invention and a resin molded product using the same can be used for liquid crystal displays in electronic image devices such as televisions, video cameras, word processors, car navigation systems, car navigation system cover lenses, personal computers, mobile phones, automobile information panels, and touch panels. It can be applied to various displays such as displays, plasma displays, organic EL (electroluminescence) displays, inorganic EL displays, and FEDs (field emission displays).

Claims (3)

A fingerprint-resistant layer is formed on one side of the thermoplastic transparent base film.
The fingerprint-resistant layer has a film thickness of 0.5 to 3.0 μm.
A fingerprint-resistant film for insert molding in which the surface unevenness of the fingerprint-resistant layer is Ra (arithmetic mean roughness) of 0.04 to 0.20 μm.
The fingerprint-resistant layer contains the following components (A) to (D);
Polymer (A) with an SP value of 8 to 13 and a Tg of 65 to 100 ° C.
UV reactive (meth) acrylate Li Royle group-containing compound (B),
Organic fine particles (C) with an average particle diameter of 0.8 to 5.5 μm,
Photopolymerization initiator (D)
Mass ratio consists, and the polymer (A) and the ultraviolet-reactive (meth) acrylate Li Royle group-containing compound (B) is 90: 10 to 60: A 40,
Polymer (A) and the ultraviolet-reactive (meth) per 100 parts by weight of accession Li Royle group-containing compound (B), 0.3 to 2.0 parts by mass of the organic fine particles (C), photopolymerization initiator ( A fingerprint-resistant film for insert molding, which is a cured product of a resin composition containing 1 to 10 parts by mass of D). The first aspect of the present invention, wherein the thermoplastic transparent base film has a two-layer structure of a polycarbonate layer and a polymethylmethacrylate layer, and the fingerprint-resistant layer is formed on the polymethylmethacrylate layer. Fingerprint resistant film for insert molding. A resin molded product having the fingerprint-resistant film for insert molding according to claim 1 or 2 on its surface.