JP6059684B2 - Manufacturing method of transfer molding - Google Patents

Description

  The present invention relates to a hard coat transfer sheet and a manufacturing method, and more particularly to a hard coat transfer sheet having fingerprint resistance.

  In recent years, functionality has been widely applied to hard coat transfer moldings. Among these, with the expansion of information devices equipped with touch panels such as smartphones, it has become a big issue to provide fingerprint resistance, that is, fingerprint wiping property.

  In general, as a method for imparting fingerprint resistance, there is a method of mixing an antifouling component into the hard coat layer, but there is a problem that obstructs adhesion with the anchor layer or adhesive layer to be recoated, or fingerprint after transfer molding Decrease in wiping performance and hard coat performance may occur.

  As another method, a method of coating the antifouling layer by spray coating or dipping coating after transfer molding is also conceivable, but the cost demerit due to an increase in the process becomes larger.

  Patent Document 1 discloses a technique in which a top coat layer is formed of a combination of a siloxane graft polymer in which an organosilica sol and a fluororesin or an acrylic resin and siloxane are combined as a technique for making fingerprints inconspicuous or easy to wipe off. ing.

  Patent Document 2 discloses that the topcoat layer is made of a specific fluorine-containing active energy ray-curable resin.

  Patent Document 3 and Patent Document 4 disclose a method of dispersing a filler so that fingerprints are not noticeable or easy to wipe off.

JP 2009-052019 JP International Publication No. 10/016452 JP 2008-273187 A JP 2008-296492 A

  However, the top coat layer is composed of a combination of a siloxane graft type polymer in which an organosilica sol and a fluororesin or an acrylic resin and siloxane are combined, or the top coat layer is composed of a specific fluorine-containing active energy ray-curable resin. However, the selectivity of the recoat layer is narrow and the performance as a hard coat layer is not satisfied.

  Further, as a method for imparting fingerprint resistance to the hard coat layer of the hard coat transfer sheet, there is a method of adding an antifouling component to the hard coat layer, and examples of the antifouling component include materials containing silicone or fluorine. However, when an antifouling component is added to the hard coat layer of the transfer sheet, the adhesion of the recoat layer is inhibited, and the fingerprint wiping performance and hardness physical properties after transfer molding cannot be obtained sufficiently.

  Although a method of adding an antifouling component to the release layer of the transfer sheet is also conceivable, it is difficult to transfer it to the entire surface of the hard coat layer, and sufficient anti-fingerprint performance cannot be obtained.

  Furthermore, although there is a method of coating the fingerprint-resistant layer by spraying or dipping after transfer molding, the merit of one process of the transfer sheet is impaired, and the cost demerit due to the increased process is larger.

  The present invention has been made in view of the above-mentioned problems of the prior art, and is to obtain a transfer molded article having excellent fingerprint resistance after transfer molding without impairing hard coat performance, that is, imparting fingerprint wiping properties. Objective.

The present invention comprises a release layer, and the hard coat layer, wherein formed between the release layer and the hard coat layer, Bei example a fingerprint layer of water-repellent and oleophilic, the fingerprint layer By adding an equivalent part of an isocyanate compound and a photopolymerization initiator to a fluorine-containing copolymer resin having a solvent-soluble hydroxyl value, and dispersing or dissolving it in a solvent, and applying or curing and crosslinking with heat and ionizing radiation. is formed, its thickness is less than 2μm above 0.01 [mu] m, and a water contact angle of the fingerprint layer surface after the transfer formation type supporting lifting body 70 ° or more and, in squalene contact angle less than 30 ° It is characterized by being transferred onto a support using a hard coat transfer sheet.

  According to the present invention, it is possible to obtain a transfer molded article imparted with excellent fingerprint resistance after transfer molding, that is, fingerprint wiping property, without impairing hard coat performance. In particular, it is possible to obtain a transfer molded product having excellent adhesion to the hard coat layer and excellent fingerprint wiping property.

It is sectional drawing of the hard coat transfer sheet in embodiment. It is sectional drawing of the hard-coat transfer sheet in other embodiment. 1 is an external view photograph of Example 1. FIG. FIG. 6 is an external view photograph of Comparative Example 1.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 shows a cross-sectional view of a heart coat transfer sheet in the present embodiment. The hard coat transfer sheet 1 is configured by sequentially laminating a base material 10, a release layer 12, a fingerprint resistant layer (or fingerprint wiping layer) 14, a hard coat layer 16, an anchor layer 18 and an adhesive layer 20. Hereinafter, each layer will be described.

<Substrate 10>
As the base material 10, various materials can be applied depending on the use as long as they have heat resistance, mechanical strength, solvent resistance, and the like. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6, polyolefin resins such as polypropylene and polynorbornene, vinyl resins such as polyvinyl chloride, and cellulose films such as polymethyl methacrylate And imide resins such as polyimide. Preferably, in terms of heat resistance and mechanical strength, polyethylene terephthalate is most suitable for a film of a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. The thickness of the substrate 10 is usually about 15 μm to 100 μm, and preferably 25 to 50 μm from the viewpoint of transferability.

  The substrate 10 may be a copolymer resin containing these resins as a main component, a mixture (including an alloy), or a laminate including a plurality of layers. The substrate 10 may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength is preferable. The base material 10 is used as a film, sheet, or board formed of at least one layer of these resins. Prior to application, the substrate 10 is subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also referred to as an anchor coat, adhesion promoter, or easy adhesive) application treatment, pre-heat treatment, dust removal treatment. Alternatively, easy adhesion treatment such as vapor deposition or alkali treatment may be performed. Moreover, you may add additives, such as a filler, a coloring agent, a plasticizer, and an antistatic agent, as needed.

<Release layer 12>
As the release layer 12, there are usually a release resin, a resin containing a release agent, a curable resin that is cross-linked by ionizing radiation, etc. In this embodiment, a melamine resin is used. It is also possible to use a combination with a matting agent.

  The release layer 12 is formed by dispersing or dissolving the resin in a solvent, applying a known coating such as a roll coat or a gravure coat, drying, and baking at a temperature of about 140 ° C to 200 ° C. The thickness of the release layer 12 is usually about 0.01 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

<Anti-fingerprint layer (fingerprint wiping layer) 14>
The fingerprint-resistant layer 14 is crosslinked by using an isocyanate compound or a curing agent such as a photopolymerization initiator alone or in combination in order to obtain heat resistance during transfer molding, solvent resistance after transfer molding, and fingerprint wiping durability. The main component is a possible component.

  The water contact angle after transfer molding is 70 ° or more, preferably 80 ° or more, and the squalene contact angle is 30 ° or less, preferably 20 ° or less. Within this range, the resin system is not particularly limited, but specific examples thereof include a fluorine-containing copolymer resin having a solvent-soluble hydroxyl value and an ionizing radiation curable resin containing the same. It crosslinks by adding an isocyanate compound or a photoinitiator to these. You may mix 1-50 weight part of silica of 10 nm-5 micrometers as needed.

  Specific examples of the fluorine-containing copolymer resin having a hydroxyl value include a fluorinated olefin and an alkyl vinyl ether or alkyl vinyl ester for making a solvent soluble as disclosed in JP-A-6-271807, and a hydroxyl group. Examples thereof include a fluorine-containing copolymer composed of a compound having the above and optionally other monomers, or a radical polymerizable resin disclosed in JP-A-2009-249484. These are dry to the touch and are desirably oleophilic, thereby providing the recoatability and adhesion of the hard coat layer.

  The molecular weight of the fluorine-containing copolymer resin having a hydroxyl value is desirably 1000 or more and 200,000 or less in terms of polystyrene-reduced number average molecular weight by gel permeation chromatography, and has a hydroxyl value of 10 to 200 mgKOH / g. Things are desirable. As the isocyanate compound, known compounds can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3 , 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphth Aromatic diisocyanates such as len-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenation Examples thereof include alicyclic diisocyanates such as tolylene diisocyanate, hydrogenated xylene diisocyanate and hydrogenated diphenylmethane diisocyanate. Alternatively, in view of adhesion with the ionizing radiation curable resin to be recoated, those having a reactive double bond are desirable. In addition, these can be used 1 type or in mixture of 2 or more types.

  As the photopolymerization initiator, known ones can be used. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenylketone, 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl)- Examples include phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 4-methylbenzophenone. In addition, these can be used 1 type or in mixture of 2 or more types, You may use together a well-known hardening accelerator.

  In addition to the isocyanate compound and the photopolymerization initiator, a known curing agent can be used. For example, a compound having a thiol group at the terminal, a compound having a primary or secondary amine, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2, Azo initiators such as 2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanopentanoic acid), lauroyl peroxide, benzoyl peroxide, t-butyl peroxide Oxypivalate, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, acetyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, Disiisopropyl peroxycarbonate, t-butyl carbonate Mud peroxide, potassium persulfate and the like. In addition, these can be used 1 type or in mixture of 2 or more types, You may use together a well-known hardening accelerator.

  The anti-fingerprint layer 14 is formed by dispersing or dissolving the resin in a solvent, applying it with a known coating such as a roll coat, gravure coat, comma coat, knife coat, die coat, etc., and drying it with heat or ionizing radiation. Semi-cured or fully crosslinked. The thickness of the anti-fingerprint layer 14 is 0.01 μm to less than 2 μm, preferably 0.1 μm to 1 μm or less.

<Hard coat layer 16>
The hard coat layer 16 contains an ionizing radiation curable resin as a main component. Specific examples of the ionizing radiation curable resin include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate Isophorone diisocyanate urethane prepolymer, reactive acrylic polymer, It is possible to use a refractory polyurethanes, and the like. These can be used alone or in combination of two or more. If necessary, an acrylic resin, a polyester resin, a vinyl resin, an imide resin, a photopolymerization initiator, a surfactant, silica, wax, a metal oxide, or the like is added. Specific examples of the ionizing radiation curable resin containing a urethane (meth) acrylate oligomer include a photocurable resin disclosed in JP-A-2001-329031.

  The hard coat layer 16 is formed by dispersing or dissolving the above mixture in a solvent, applying a known coating such as roll coat, gravure coat, comma coat, knife coat, die coat, etc., and drying, heat, or ionizing radiation. Semi-cured with or with ionizing radiation. In the case of semi-curing, it is sufficiently cured by ionizing radiation after transfer molding. The thickness of the hard coat layer 16 is about 1 μm to 20 μm, preferably about 3 μm to 10 μm.

<Anchor layer 18>
The anchor layer 18 is mainly composed of urethane resins such as acrylic urethane, polyester urethane, and epoxy urethane, particularly curable urethane resins such as two-component cured urethane resins and thermosetting urethane resins, melamine resins, and nitrocellulose resins. Etc. These may be used alone or in combination of two or more.

  The above mixture is dispersed or dissolved in a solvent, applied with a known coating such as roll coat, gravure coat, comma coat, knife coat, die coat, and dried. The thickness of the anchor layer 18 is about 0.1 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

<Adhesive layer 20>
For the adhesive layer 20, a known heat-sensitive adhesive that melts or softens when heated to exhibit an adhesive effect can be applied. Specifically, a vinyl chloride resin, a vinyl acetate resin, and a vinyl chloride vinyl acetate copolymer resin. , Acrylic resins, polyester resins and the like. Moreover, micro silica etc. are included as needed. These may be used alone or in combination of two or more.

  The above mixture is dispersed or dissolved in a solvent, applied with a known coating such as roll coat, gravure coat, comma coat, knife coat, die coat, and dried. The thickness of the adhesive layer 20 is about 0.1 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

  Using the hard coat transfer sheet 1 as described above, thermal transfer or in-mold molding is performed on the support 22 shown in FIG. After the release layer 12 is peeled off, the cross-linked fingerprint-resistant layer 14 is exposed on the entire outermost surface, whereby stable fingerprint resistance, that is, fingerprint wiping property can be obtained. The support 22 is made of acrylic resin (PMMA), polystyrene resin (PS), acrylonitrile / butadiene / styrene copolymer resin (ABS), modified polyphenylene ether resin (modified PPE), polycarbonate resin (PC). ), An amorphous resin such as PC / ABS is preferably used.

  FIG. 2 shows a cross-sectional view of a hard coat transfer sheet in another embodiment. The difference from FIG. 1 is that another layer 19 is laminated between the anchor layer 18 and the adhesive layer 20. The other layer 19 is dispersed or dissolved in a solvent, applied with a known coating such as a roll coat, a gravure coat, a comma coat, a knife coat, or a die coat and dried, or after drying, reacted with an aging treatment or ionizing radiation. . Alternatively, a metal thin film layer processed by a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like is also included.

  Hereinafter, examples and comparative examples will be described. In the following Examples, Examples (Example 1, Example 3, Example 5 and the like) in which no photopolymerization initiator is added as an anti-fingerprint layer component are positioned as reference examples in this embodiment.

[ Reference Example 1]
To 100 parts by weight of solvent-soluble fluororesin ZX-214-A (Fuji Kasei Kogyo Co., Ltd.), an equivalent part of isocyanate and EXF-CR3 curing agent (Daiichi Seika Kogyo Co., Ltd.) is added, and this is added with methyl ethyl ketone. Dilution adjustment was performed so that the total solid content was 15% by weight to obtain a fingerprint-resistant layer component.

  The adjusted product is uniformly applied and dried by a bar coating method to a melamine-treated PET film having a thickness of 38 μm as the base material 10 so as to have a dry film thickness of 0.5 μm, and then 24 hours in a low humidity dryer at 40 ° C. Aging was performed to obtain an anti-fingerprint layer 14. Thereafter, the hard coat layer 16, the anchor layer 18 and the adhesive layer 20 were laminated in this order to obtain the transfer sheet 1.

The hard coat layer 16 is made by applying and drying Seika Beam EXF-RT01 (manufactured by Dainichi Seika Kogyo Co., Ltd.) uniformly by the bar coat method so that the dry film thickness is 5 μm, and then using an 80 W / cm high-pressure mercury lamp to obtain an integrated light amount of 35 mJ Semi-cured at / cm ² .

  The anchor layer 18 is prepared by adding an equivalent part of EXF-CR3 curing agent (manufactured by Dainichi Seika Kogyo) to 100 parts by weight of EXF-CAMV (manufactured by Dainichi Seika Kogyo), so that the dry film thickness becomes 1.2 μm After uniformly coating and drying by a coating method, aging was performed for 48 hours with a dryer at 40 ° C.

  For the adhesive layer 20, EXF-HS1 medium (manufactured by Dainichi Seika Kogyo Co., Ltd.) was uniformly applied and dried by a bar coating method so that the dry film thickness was 1.5 μm.

The transfer sheet 1 is thermocompression bonded to a 1 mm thick transparent acrylic plate (Comoglass P (transparent), manufactured by Kuraray Co., Ltd.) by two passes at 240 ° C. with a heat roll, and after peeling off the melamine PET, 80 W / cm. Was cured with an integrated light quantity of 1200 mJ / cm ² with a high-pressure mercury lamp to obtain a transfer molded product.

[Example 1 ]
Solvent-soluble fluororesin, ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) with 100 parts by weight, isocyanate, EXF-CR3 curing agent (Daiichi Seika Kogyo Co., Ltd.) equivalent part, Irgacure 184 (BASF Japan) Was added with 1 part in terms of solid content, and this was diluted with methyl ethyl ketone so that the total solid content was 15% by weight, whereby a component of the anti-fingerprint layer 14 was obtained. The production of the transfer sheet and the production of the transfer molded product were the same as in Reference Example 1.

[ Reference Example 2 ]
Equivalent part of isocyanate and EXF-CR3 curing agent (manufactured by Dainichi Seika Kogyo Co., Ltd.) is added to 100 parts by weight of solvent-soluble fluororesin, Fantent FTX-220S (manufactured by Neos Co., Ltd.) Dilution adjustment was performed so that the content was 15% by weight, and a component of the anti-fingerprint layer 14 was obtained. The production of the transfer sheet and the production of the transfer molded product were the same as in Reference Example 1.

[Example 2 ]
The component resin of the anti-fingerprint layer of Reference Example 1 is added to Seika Beam EXF-RT01 so as to be 10 parts by weight (in terms of solid content), and an equivalent part of isocyanate and EXF-CR3 curing agent (manufactured by Dainichi Seika Kogyo) is added. This was diluted with methyl ethyl ketone so that the total solid content was 15% by weight, and the component of the anti-fingerprint layer 14 was obtained. The production of the transfer sheet and the production of the transfer molded product were the same as in Reference Example 1.

[Comparative Example 1]
A transfer sheet was prepared without providing the fingerprint-resistant layer 14, and a transfer molded product was obtained in the same manner as in Reference Example 1.

[Comparative Example 2]
The component resin of the anti-fingerprint layer 14 of Reference Example 1 was added to Seika Beam EXF-RT01 so as to be 5 parts by weight (in terms of solid content), and the component of the hard coat layer 16 was obtained. As in Comparative Example 1, a transfer sheet was prepared without providing the anti-fingerprint layer 14, and a transfer molded product was obtained in the same manner as in Reference Example 1.

[Comparative Example 3]
The component resin of the anti-fingerprint layer 14 of Reference Example 1 was added to Seika Beam EXF-RT01 so as to be 10 parts by weight (in terms of solid content), and the component of the hard coat layer 16 was obtained. As in Comparative Example 1, a transfer sheet was prepared without providing the anti-fingerprint layer 14, and a transfer molded product was obtained in the same manner as in Reference Example 1.

[Comparative Example 4]
The component resin of the anti-fingerprint layer 14 of Reference Example 1 was added to Seika Beam EXF-RT01 so as to be 50 parts by weight (in terms of solid content), and the component of the hard coat layer 16 was obtained. As in Comparative Example 1, a transfer sheet was prepared without providing the anti-fingerprint layer 14, and a transfer molded product was obtained in the same manner as in Reference Example 1.

[Comparative Example 5]
The dry film thickness of the anti-fingerprint layer 14 of Reference Example 1 was 2.4 μm to obtain a transfer molded product.

[Comparative Example 6]
To 100 parts by weight of solvent-soluble fluororesin, Lumiflon LF-100 (Asahi Glass Co., Ltd.), an equivalent part of isocyanate and EXF-CR3 curing agent (manufactured by Dainichi Seika Kogyo Co., Ltd.) is added. Was adjusted to 15% by weight to obtain a component of the finger-proof layer 14. The production of the transfer sheet and the production of the transfer molded product were the same as in Reference Example 1.

  The evaluation method is as follows.

(1) Appearance Evaluation Regarding the appearance of the transfer molded product, defects such as smoothness, crushed skin, and whitening were visually confirmed.

(2) Evaluation of fingerprint resistance, that is, fingerprint wiping property After actually attaching the fingerprint to the surface of the transfer molded product, it was rubbed 5 times with gauze and evaluated how much the fingerprint could be wiped off visually. The evaluation criteria were as follows.
○: No fingerprint mark is left. (Can be wiped off completely)
Δ: Some fingerprint marks remain. (Another 5 strokes can be wiped off completely)
X: Fingerprints grow and cannot be wiped off at all.

(3) Contact angle measurement Water and squalene contact angles at a room temperature of 25 ° C on the surface of the transfer molded product were measured.

(4) Steel Wool Resistance The degree of scratching when the transfer molded product surface was reciprocated 10 times with steel wool (Bonster # 0000) at 300 g / cm ² load was visually evaluated. The evaluation criteria were as follows.
○: No scratch.
Δ: Slightly more scratches than standard.
X: Obviously many scratches.

(5) Pencil hardness Based on JIS K5600, the surface of the transfer molded product was subjected to a scratch test at a load of 750 g / cm ² using a Mitsubishi uni pencil.

(6) Adhesiveness The surface of the transfer molded product was evaluated by a cross cut method (100/100) using a cellophane tape having a width of 24 mm (manufactured by Nichiban Co., Ltd.).

<Evaluation results>
The evaluation results are shown in Table 1.

As shown in Table 1, it can be seen that the molded products of the examples are generally easy to wipe off fingerprints and maintain the physical properties of hardness. As for the fingerprint wiping property, a squalene contact angle of 20 ° or less was a more desirable result. FIG. 3 shows an appearance photograph of Reference Example 1. FIG. 4 shows an external appearance photograph of Comparative Example 1. In FIG. 3, the fingerprint is wiped cleanly, whereas in FIG. 4, the fingerprint is stretched and not wiped off.

  As shown in Comparative Examples 2 to 4, as the component resin of the anti-fingerprint layer 14 is mixed, even if the contact angle is an ideal value, the whitening of the appearance due to a decrease in compatibility is conspicuous, and the steel wool resistance And adhesion decreased.

  As shown in Comparative Example 5, when the thickness of the anti-fingerprint layer 14 was thick, the adhesion and hardness properties were lowered. From this, it can be said that the upper limit of the dry film thickness is preferably less than 2 μm. The lower limit of the film thickness is preferably 0.01 μm or more because it is necessary to exhibit a function as an anti-fingerprint layer. Accordingly, the range of film thickness is preferably 0.01 μm or more and less than 2 μm.

  As shown in Comparative Example 6, when an oil-repellent material was used as a component of the anti-fingerprint layer 14, adhesion by recoating was not obtained at all.

  From the above results, the method of laminating the anti-fingerprint layer 14 between the release layer 12 and the hard coat layer 16 in the present embodiment is a fingerprint rather than the method of adding a fingerprint wiping component to the hard coat layer 16. It is clear that the wiping component is oriented over the entire transfer surface, has excellent fingerprint wiping performance, has a low squalene contact angle, and does not interfere with recoat adhesion when thin film coating is applied. Moreover, since it is a single-layer thin film coating, the appearance is good and the hardness properties can be maintained.

  Note that the anti-fingerprint layer 14 is preferably qualitatively water-repellent and lipophilic. Since most fingerprints are composed of moisture, wiping of fingerprints can be facilitated by water repellency. In addition, the lipophilicity makes the fingerprint inconspicuous, and the adhesion with the hard coat layer 16 can be secured. Regarding the water contact angle and squalene contact angle of fingerprint resistance 14, the water contact angle is 70 ° or more, preferably 75 ° or more, and the squalene contact angle is less than 30 °, preferably 25 ° or less. Examples of water contact angle and squalene angle of the anti-fingerprint layer 14 and comparative examples are shown below.

[ Reference Example 3 ]
The same as in Reference Example 1 above.

  Specifically, 100 parts by weight of solvent-soluble fluororesin, ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) is added with an equivalent part of isocyanate and EXF-CR3 curing agent (manufactured by Dainichi Seika), and this is added to methyl ethyl ketone. The dilution was adjusted so that the total solid content was 15% by weight to obtain a fingerprint-resistant layer component.

  The above prepared product is uniformly applied and dried by a bar coating method so as to have a dry film thickness of 0.5 μm on a 38 μm-thick melamine PET film as the base material 10 and then aged for 24 hours with a low-humidity 40 ° C. dryer. As a result, an anti-fingerprint layer 14 was obtained. Thereafter, the hard coat layer 16, the anchor layer 18 and the adhesive layer 20 were laminated in this order to obtain the transfer sheet 1.

  The hard coat layer 16 is formed by applying and drying Seika Beam EXF-RT01 (manufactured by Dainichi Seika) uniformly by the bar coat method so that the dry film thickness is 5 μm, and then using an 80 W / cm high-pressure mercury lamp to obtain an integrated light amount of 35 mJ / Semi-cured at cm2.

  The anchor layer 18 is a bar coating method in which an equivalent part of EXF-CR3 curing agent (manufactured by Dainichi Seika) is added to 100 parts by weight of EXF-CAMV (manufactured by Dainichi Seika), and the dry film thickness becomes 1.2 μm. After uniformly coating and drying, it was aged for 48 hours with a dryer at 40 ° C.

  For the adhesive layer 20, EXF-HS1 medium (manufactured by Dainichi Seika) was uniformly applied and dried by a bar coating method so that the dry film thickness was 1.5 μm.

The transfer sheet 1 is thermocompression bonded to a 1 mm thick transparent acrylic plate (Comoglass P (transparent), manufactured by Kuraray Co., Ltd.) by two passes at 240 ° C. with a heat roll, and after peeling off the melamine PET, 80 W / cm. Was cured with an integrated light quantity of 1200 mJ / cm ² with a high-pressure mercury lamp to obtain a transfer molded product.

[ Reference Example 4 ]
In Reference Example 3 , 20% of gentent 730FM (manufactured by Neos) was added to the component of the anti-fingerprint layer 14 in a solid content ratio. Other than that is the same as Reference Example 3 .

[ Reference Example 5 ]
In Reference Example 3 , 20% of the solvent 750FM (manufactured by Neos) was added to the anti-fingerprint layer 14 component at a solid content ratio. Other than that is the same as Reference Example 3 .

[Comparative Example 7]
In Reference Example 3 , 20% of TF 215FM (manufactured by Neos) was added to the components of the anti-fingerprint layer 14 in a solid content ratio. Other than that is the same as Reference Example 3 .

[Comparative Example 8]
In Reference Example 3 , 20% of solid ration of 245 FM (manufactured by Neos) was added to the component of the anti-fingerprint layer 14. Other than that is the same as Reference Example 3 .

[Comparative Example 9]
In Reference Example 3 , 20% of FT 710FM (manufactured by Neos) was added to the components of the anti-fingerprint layer 14 in a solid content ratio. Other than that is the same as Reference Example 3 .

  The evaluation method is as follows.

(7) Appearance Evaluation Appearance 1: The state of the melamine PET coated with the adjusted sample was visually observed.
Appearance 2: The state when the hard coat layer 16 was applied to the anti-fingerprint layer 14 was visually observed.

(8) Evaluation of fingerprint wiping property After the fingerprint was actually attached to the surface of the transfer molded product, it was rubbed 5 times with gauze to evaluate how much the fingerprint could be wiped off visually. The evaluation criteria were as follows.
○: No fingerprint mark is left. (Can be wiped off completely)
Δ: Some fingerprint marks remain. (Another 5 strokes can be wiped off completely)
X: Fingerprints grow and cannot be wiped off at all.

(9) Contact angle measurement Contact angle A: Water and squalene contact angles at room temperature of 25 ° C. immediately after the fingerprint wiping layer was formed were measured.
Contact angle B: The contact angle of water and squalene at the room temperature of 25 ° C. on the surface of the transfer molded product was measured.

(10) Steel Wool Resistance The degree of scratching when the transfer molded product surface was reciprocated 10 times with steel wool (Bonster # 0000) at a load of 300 g / cm ² was visually evaluated. The evaluation criteria were as follows.
○: No scratch.
Δ: Slightly more scratches than standard.
X: Obviously many scratches.

(11) Pencil Hardness The surface of the transfer molded product was subjected to a scratch test with a load of 750 g / cm ² using a Mitsubishi uni pencil based on JIS K5600.

(12) Adhesiveness The surface of a transfer molded product was evaluated by a cross cut method (100/100) using a cellophane tape having a width of 24 mm (manufactured by Nichiban Co., Ltd.).

The evaluation results are shown in Table 2.

Reference Example 3, Reference Example 4, and Reference Example 5 showed good fingerprint wiping properties after transfer molding. In Reference Examples 4 and 5 , the steel wool resistance was poor, but this is considered to be caused by the fact that the thermosetting property due to aging was lowered due to the influence of each material mixed in the fingerprint wiping component.

  In Comparative Example 7 and Comparative Example 8, the water contact angle was less than 70 °, and the fingerprint wiping property was not obtained.

  In Comparative Example 9, the squalene contact angle was 30 ° or more, and the adhesion was poor.

  Note that the difference in water contact angle and squalene contact angle before and after the transfer is considered to be greatly affected by the difference in orientation of the material mixed with the fingerprint wiping component.

  From the above results, the water contact angle of the surface of the molded product after transfer molding is 70 ° or more, preferably 75 ° or more, and the squalene contact angle is less than 30 °, preferably 25 ° or less, so that the fingerprint wiping property is achieved. Is good.

  10 base material, 12 release layer, 14 anti-fingerprint layer, 16 hard coat layer, 18 anchor layer, 20 adhesive layer.

Claims (1)

A release layer,
A hard coat layer,
A water-repellent and lipophilic fingerprint-resistant layer formed between the release layer and the hard coat layer;
Bei to give a,
The anti-fingerprint layer is
Formed by adding an equivalent part of an isocyanate compound and a photopolymerization initiator to a fluorine-containing copolymer resin having a solvent-soluble hydroxyl value, dispersing or dissolving in a solvent, coating, and curing or crosslinking with heat and ionizing radiation The thickness is 0.01 μm or more and less than 2 μm,
And a water contact angle of the fingerprint layer surface after the transfer formation type supporting lifting body less than 70 °, and that the transfer molded to the support using a hard coat transfer sheet squalene contact angle is less than 30 ° A method for producing a transfer molded product .