JP2011099744A - Fingerprint-proof evaluation method and fingerprint-proof film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fingerprint-proof evaluation method with high objectivity and high reproducibility, for measurement by a general-purpose method. <P>SOLUTION: The fingerprint-proof evaluation method of a film includes: an initial glossiness measuring process for measuring 75 to 20-degree specular glossiness of the film formed on an object to be coated by using a glass meter to determine an initial glossiness; a fingerprint-proof evaluation liquid adhesion process for adhering a fingerprint-proof evaluation liquid on the film; a glossiness before wiping measuring process for measuring the specular glossiness of a portion on which the fingerprint-proof evaluation liquid is attached; a fingerprint-proof evaluation liquid wiping process for wiping the adhering fingerprint-proof evaluation liquid; a glossiness after wiping measuring process for measuring the specular glossiness after the fingerprint-proof evaluation liquid is wiped; and a calculation process in which the obtained measurement values are processed by the formulae: an adhesive evaluation rate (%)=(glossiness before wiping)/(initial glossiness)×100, and an after-wiping evaluation rate (%)=(glossiness after wiping)/(initial glossiness)×100, and the adhesive evaluation rate and the after-wiping evaluation rate are found. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for evaluating a fingerprint-resistant film, and a fingerprint-resistant film that exhibits excellent fingerprint resistance even in this fingerprint-resistant evaluation method.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, ABS, MS resin, AS resin and other styrene resins, vinyl chloride resins, triacetyl cellulose and other cellulose acetate products Is a base material for display devices such as containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, etc. Widely used.

  However, since these plastic products have low surface hardness, they are easily damaged and have the disadvantage that the original transparency or appearance of the resin is remarkably easily damaged. For this reason, attempts have been made to improve the wear resistance of the product surface by applying a hard coat layer. In recent years, these hard coat layers further have a fingerprint-resistant property that fingerprint traces are difficult to adhere, and a fingerprint wiping property that fingerprint traces can be easily wiped off or fingerprint traces cannot be identified ( In the present specification, these are collectively referred to as “fingerprint resistance”) and are also required to be excellent. This is because the appearance of the product is deteriorated due to inferior fingerprint resistance, and the original performance of the display device base material cannot be exhibited.

  As described above, as improvement in fingerprint resistance is required, improvement in objectivity and reproducibility of evaluation of fingerprint resistance is also important. For example, Japanese Patent No. 3886519 (Patent Document 1) describes a method for evaluating the antifouling property and fingerprint adhesion of an optical information medium using a pseudo fingerprint liquid. And in patent document 1, antifouling property and fingerprint adhesion evaluation are performed by a haze value, the rate of change of water contact angle, jitter measurement, etc. However, any of these evaluations has a problem that the correlation with the sensory evaluation when the product is actually used is not high. Therefore, also in patent document 1, it is thought that evaluation by the sensory test by visual observation of five test subjects is used together.

  Japanese Patent Application Laid-Open No. 2008-066485 (Patent Document 2) describes a contamination evaluation method using a slab type optical waveguide spectroscopic analysis method. This evaluation method is described as being highly reproducible and capable of detecting subtle stain differences. However, the slab type optical waveguide spectroscopic analysis method has a drawback in that it can basically perform spectroscopic analysis only on a transparent waveguide and is not suitable for measuring an opaque substrate. Further, this slab type optical waveguide spectroscopic analysis method is a device capable of advanced analysis such as analysis of protein orientation state or molecular structure, and therefore has a problem that it is expensive and lacks versatility.

Japanese Patent No. 3886519 JP 2008-066485 A

  Although the objectivity and reproducibility of fingerprint resistance evaluation are gaining importance as described above, no general-purpose method for fingerprint resistance evaluation with objectivity and reproducibility has been proposed. Currently. In light of these current situations, an object of the present invention is to solve the above-mentioned problems of the prior art. More specifically, an object of the present invention is to provide a fingerprint resistance evaluation method with high objectivity and reproducibility that can be measured by a general-purpose method. It is another object of the present invention to provide a fingerprint-resistant film having such a high fingerprint resistance evaluation.

The present invention
An initial glossiness measuring step for measuring a 75 to 20 degree specular glossiness of a coating film formed on an object to be an initial glossiness by using a gloss meter;
Anti-fingerprint evaluation liquid adhering process for attaching an anti-fingerprint evaluation liquid on the coating,
Measuring the glossiness of the mirror surface of the part to which the anti-fingerprint evaluation liquid is attached, measuring the glossiness before wiping,
Wipe off the anti-fingerprint evaluation liquid, the anti-fingerprint evaluation liquid wiping process,
Measuring the specular gloss after wiping off the anti-fingerprint evaluation liquid, measuring the glossiness after wiping, and processing the obtained measured value according to the following formula to obtain the adhesion evaluation rate and the evaluation rate after wiping:
Adhesion evaluation rate (%) = (Glossiness before wiping) / (Initial glossiness) × 100
Evaluation rate after wiping (%) = (Glossiness after wiping) / (Initial glossiness) × 100
A method for evaluating the anti-fingerprint property of a film, comprising:

More preferably, the wiping process in the anti-fingerprint evaluation liquid wiping step is a process in which the wiping material is reciprocated 1 to 40 times with a load of 5 to 50 g / cm ² to wipe off the anti-fingerprint evaluation liquid.

In addition, the adhesion process in the anti-fingerprint evaluation liquid adhesion process is
The lower end surface of the rubber plug having a diameter of 13 mm or more at the lower end surface portion is coated with a woven fabric or a non-woven fabric, and this coating portion is impregnated with an anti-fingerprint evaluation liquid,
The lower end surface portion of the rubber plug impregnated with the anti-fingerprint evaluation liquid is pressed onto the film with a load of 50 to 300 g / cm ² to adhere the anti-fingerprint evaluation liquid on the film.
More preferably it is a procedure.

  The anti-fingerprint evaluation solution is more preferably at least one selected from higher fatty acids, terpenes, and derivatives thereof.

［式中、Ｘは、ポリエーテル骨格を有するポリオール化合物の両末端の水酸基を除いた残基を示す。］
で示される構造を有し、および
このポリエーテル骨格含有ウレタン（メタ）アクリレート（Ａ）の水トレランスが６．０ｍｌ以下であり、溶解性パラメータが１２以下である、
耐指紋性光硬化性組成物によって形成された被膜である、耐指紋性被膜であるのが、より好ましい。 Further, in the fingerprint resistance evaluation method, the adhesion evaluation rate and the evaluation rate after wiping when the 60-degree specular gloss is measured are both 85% or more, and the anti-fingerprint film,
This coating has the following components:
Polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends,
A photopolymerizable polyfunctional compound (B), and a photopolymerization initiator (C),
Including
This polyether skeleton-containing urethane (meth) acrylate (A) has the following formula (1):

[In formula, X shows the residue except the hydroxyl group of the both ends of the polyol compound which has a polyether frame | skeleton. ]
And the polyether skeleton-containing urethane (meth) acrylate (A) has a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less.
More preferred is a fingerprint-resistant film, which is a film formed from a fingerprint-resistant photocurable composition.

Another preferred embodiment is a fingerprint-resistant coating film in which the adhesion evaluation rate and the evaluation rate after wiping are both 85% or more when the 60-degree specular gloss is measured in the fingerprint resistance evaluation method. And
This coating has the following components:
(A) An acrylic resin having an active methylene group or active methine group (a) and a saturated cycloalkyl group (b) in the molecule, or an acrylic resin having an active methylene group or an active methine group (a) and a saturated cycloalkyl group A mixture with an acrylic resin having (b),
(B) a polyfunctional polymerizable compound having two or more photocurable functional groups in the molecule;
(C) a photopolymerization initiator, and (d) a Michael reaction catalyst,
The aspect which is a fingerprint-resistant film | membrane which is a film formed with the fingerprint-resistant curable composition containing this is mentioned.

  The fingerprint resistance evaluation method of the present invention is an objective and quantitative evaluation method accompanied by quantification. Conventional visual anti-fingerprint evaluation is a sensory evaluation, and thus depends on the judgment ability of the evaluator, resulting in variations among evaluators and lack of objectivity. The evaluation method of the present invention has an advantage that it can be performed with a quantitative property called quantification using a general instrument called a gloss meter. The evaluation method of the present invention is further advantageous in that both objectivity and reproducibility are high.

  Furthermore, the method of the present invention is capable of evaluating the superiority or inferiority of the coatings between a plurality of coatings evaluated as good in the conventional method for measuring the haze value, and is capable of performing a higher evaluation. There is. The method of the present invention is further advantageous in that it is possible to evaluate the fingerprint resistance of a film provided on an opaque object, which cannot be evaluated by measuring the haze value.

  And when it evaluated using the said fingerprint-resistant evaluation method, it was discovered that the film obtained from the composition which has a specific component has the outstanding fingerprint resistance. The present invention also provides such a fingerprint-resistant film having a very high fingerprint resistance evaluation.

Fingerprint resistance evaluation method The fingerprint resistance evaluation method of the present invention comprises the following steps:
An initial glossiness measuring step for measuring a 75 to 20 degree specular glossiness of a coating film formed on an object to be an initial glossiness by using a gloss meter;
Anti-fingerprint evaluation liquid adhering process for attaching an anti-fingerprint evaluation liquid on the coating,
Measuring the specular gloss of the part to which the anti-fingerprint evaluation liquid is attached, a gloss measurement step before wiping,
Wipe off the anti-fingerprint evaluation liquid, the anti-fingerprint evaluation liquid wiping process,
Measuring the specular gloss after wiping off the anti-fingerprint evaluation liquid, measuring the gloss after wiping,
The obtained measured value is processed with the following mathematical formula, and the adhesion evaluation rate and the evaluation rate after wiping are calculated, a calculation step,
It is a method including.

  As described above, the evaluation method of the present invention is characterized in that fingerprint resistance evaluation is performed using a change in glossiness. Conventional fingerprint resistance evaluation is generally performed by haze value measurement and visual evaluation (see, for example, Japanese Patent Application Laid-Open No. 2004-359834, paragraph 0079). However, the evaluation result in the conventional method for measuring the haze value has a bad correlation with the evaluation result visually evaluated by the evaluator. This can also be understood from Japanese Patent Application Laid-Open No. 2004-359834 from the point of using visual evaluation by an evaluator after wiping after measuring the haze value in confirmation of fingerprint adhesion. On the other hand, since the evaluator's visual evaluation is a sensory evaluation, it depends on the judgment ability of the evaluator, resulting in variations among evaluators and lack of objectivity. This further lacks reproducibility.

  The evaluation method of the present invention has an advantage that fingerprint resistance evaluation, which has been mainly performed by sensory evaluation by visual observation, can be performed with a quantitative property called numericalization using a general instrument called a gloss meter. is there. The evaluation method of the present invention is further advantageous in that both objectivity and reproducibility are high. Furthermore, the method of the present invention is capable of evaluating the superiority or inferiority of the coatings between a plurality of coatings evaluated as good in the conventional method for measuring the haze value, and is capable of performing a higher evaluation. There is. The method of the present invention is further advantageous in that it is possible to evaluate the fingerprint resistance of a film provided on an opaque object, which cannot be evaluated by measuring the haze value.

Initial Gloss Measurement Step The method of the present invention is a method for evaluating the fingerprint resistance of a film formed on an object to be coated. First, the glossiness of the film formed on the object is measured using a gloss meter. The glossiness measured here can be measured at an arbitrary angle in the range of 75 to 20 degrees specular gloss. Specifically, 75 degree specular gloss (measured at an incident angle of 75 degrees), 60 degree specular gloss (measured at an incident angle of 60 degrees), 45 degrees specular gloss (measured at an incident angle of 45 degrees), and 20 degrees specular gloss (incident). Measurement at an angle of 20 degrees), and the like. These specular gloss measurement methods can be measured according to JIS Z8741 (1997). The specular gloss is a numerical value obtained by measuring the intensity of specular reflection light of the coating. The glossiness of the film thus measured is defined as “initial glossiness”.

Anti-fingerprint evaluation liquid attaching step Next, an anti-fingerprint evaluation liquid is attached on the film formed on the object to be coated. As the anti-fingerprint evaluation liquid used here, those generally used in anti-fingerprint evaluation can be used without particular limitation. In general, a liquid constituting human sweat and sebum and / or a liquid having properties close to that is used as an anti-fingerprint evaluation liquid.

Specific examples of the anti-fingerprint evaluation liquid include, for example, a liquid material containing at least one of the following components:
-Higher fatty acids, such as saturated and unsaturated fatty acids having 10 to 24 carbon atoms, more preferably saturated and unsaturated fatty acids having 12 to 22 carbon atoms, more preferably oleic acid, linoleic acid, linolenic acid, etc.
-Derivatives of the above higher fatty acids, such as ester derivatives of higher fatty acids (eg diglycerides, triglycerides, etc.)
Terpenes, such as monoterpenes (C ₁₀ ), sesquiterpenes (C ₁₅ ), diterpenes (C ₂₀ ), sesterterpenes (C ₂₅ ), triterpenes (C ₃₀ ), tetraterpenes (C ₄₀ ), and derivatives thereof ( For example, terpenoids).
The anti-fingerprint evaluation liquid containing the above components may be one of the above components or a mixture of two or more thereof, or may be an aqueous solution, an alcohol solution or a paraffin solution containing at least one of the above components.

  The method of attaching the anti-fingerprint evaluation liquid onto the coating film is a method of dropping the anti-fingerprint evaluation liquid onto the film or using an adhesive having a specific shape to attach the anti-fingerprint evaluation liquid onto the film. Any method such as a method can be used.

  As a preferable method for attaching the anti-fingerprint evaluation liquid on the coating film, for example, an anti-fingerprint evaluation liquid is applied on the film using an adhesive material such as a rubber plug made of an elastomer such as silicone rubber, butadiene rubber, or urethane rubber. The method of making it adhere to is mentioned. In this specification, the smaller one of the two types of circular surfaces (circular end surfaces) of the rubber plug is referred to as a “lower end surface”. It is more preferable from the viewpoint of operability to use an adhesive having a lower end surface portion with a diameter of 13 mm or more.

  As an example of the adhering material, a rubber plug made of an elastomer, for example, a rubber plug for printing an artificial fingerprint liquid used in a fingerprint removability test according to JIS K2246 (1994) (the lower end surface of a rubber plug of No. 10) (A diameter of about 26 mm) and a surface roughened by rubbing with an AA240 abrasive defined in JIS R6251 or JIS R6252.

  As another example of the adhering material, for example, a rubber plug (standard No. 1-9) having a diameter of a smaller circular surface (lower end surface) of the rubber plug of 13 to 25 mm, more preferably a smaller circle of the rubber plug. The diameter of a surface (lower end surface) is 16-25 mm (standard No. 4-9). By using such an adhering material, there is an advantage that the anti-fingerprint evaluation liquid can be adhered with a size close to an actual fingerprint. Furthermore, by covering the lower end surface of these rubber plugs with a woven or non-woven fabric, the rubber plugs can be used more easily as an adhesive material without the treatment of rubbing with an abrasive to roughen the surface. More preferable. Examples of the woven fabric include cotton gauze (for example, Japanese Pharmacopoeia regulations, type 1 gauze) generally used. In addition, as a nonwoven fabric, commonly used nonwoven fabric of natural fiber or chemical fiber, such as Bencott (manufactured by Asahi Kasei Fibers Co., Ltd.), Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.), Kuraflex (Kuralek Laurex ( Etc.).

  Next, an anti-fingerprint evaluation liquid is adhered to the adhesive material as described above. For example, when using a roughened rubber stopper as an adhesive, fill the anti-fingerprint evaluation solution into a petri dish or similar material containing a woven or non-woven fabric as necessary, and push the adhesive with a constant load. Apply the anti-fingerprint evaluation solution to the adhesive. For example, when using a rubber stopper whose lower end surface is coated with a woven or non-woven fabric as an adhesive material, the anti-fingerprint evaluation liquid can be adhered as described above, or the anti-fingerprint evaluation liquid can be adhered on the woven or non-woven fabric on the lower end surface. The fingerprint evaluation liquid may be directly dropped and adhered.

The adhesive material to which the anti-fingerprint evaluation liquid adheres is pressed against the coating on the object to be coated with a constant load, and the anti-fingerprint evaluation liquid is adhered to the coating. The load here is preferably, for example, 50 to 300 g / cm ² in consideration of the state of fingerprint adhesion in actual use.

  By attaching the anti-fingerprint evaluation liquid onto the film as described above, an artificial fingerprint can be attached on the surface of the film quantitatively and in a state of imitating the actual fingerprint attachment very well. This makes it possible to quantify the anti-fingerprint performance with good reproducibility.

Glossiness measurement process before wiping Next, the specular glossiness of the portion to which the anti-fingerprint evaluation liquid is thus attached is measured using a gloss meter. Here, the specular gloss measurement is performed using the same incident angle as the incident angle used in the initial gloss measurement process. The specular gloss measured in this way is defined as “gloss before wiping”.

  In addition, as described in the following calculation step, the adhesion evaluation rate (%) is obtained by dividing the glossiness before wiping by the initial glossiness. This “adhesion evaluation rate” is a numerical value indicating the degree of difficulty of conspicuous fingerprint marks on the coating. For example, when measuring the 60-degree specular gloss, if the adhesion evaluation rate is 90% or more, it is a film that is difficult to distinguish fingerprint traces or fingerprint traces remain, It can be said that it has excellent fingerprint resistance.

Anti-fingerprint evaluation liquid wiping step Next, the anti-fingerprint evaluation liquid adhered on the film in the anti-fingerprint evaluation liquid attaching step is wiped off, and the anti-fingerprint evaluation liquid is removed from the film. For this wiping process, a commonly used wiping material can be used. Specific examples of the wiping material include, but are not limited to, paper waste (Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.), general tissue, etc.), woven fabric (gauze, etc.), natural fiber or chemical Nonwoven fabrics of fibers (Bencot (manufactured by Asahi Kasei Fibers Co., Ltd.), Kuraflex (manufactured by Kuraray Laflex Co., Ltd.)) and the like.

The anti-fingerprint evaluation liquid on the film is wiped off with a wiping material under a constant load and angle condition. This wiping may be performed manually or mechanically using an abrasion resistance tester or the like. As a method of performing wiping by human power, for example, in order to make the wiping load constant, a method of moving the wiping material under a constant load can be mentioned. As a method of using an abrasion resistance tester, for example, a wiping material such as a waste cloth is fixed to an indenter part of a general abrasion resistance tester, and the indenter part is reciprocated on the film to thereby apply a fingerprint resistance evaluation liquid. The method of wiping off is mentioned. In any wiping method, a load of about 5 to 50 g / cm ² is a range close to an actual wiping operation, and is preferable.

Glossiness measurement step after wiping After wiping off the anti-fingerprint evaluation solution in this way, the specular glossiness of the portion where the anti-fingerprint evaluation solution is adhered is measured using a gloss meter. Here, the specular gloss measurement is performed using the same incident angle as the incident angle used in the initial gloss measurement process. The specular glossiness thus measured is defined as “glossiness after wiping”.

  By using the obtained gloss after wiping and dividing the gloss after wiping by the initial gloss as described in the following calculation step, an evaluation rate (%) after wiping is obtained.

  In addition, as needed, it can repeat measuring the glossiness after wiping off at the time of performing the wiping process an arbitrary number of times in the above-described anti-fingerprint evaluation liquid wiping step. Thereby, the evaluation items for fingerprint resistance can be subdivided. For example, when the wiping operation using a wiping material is performed 1 to 5 times, for example, the glossiness after wiping is measured, and the evaluation rate after wiping is obtained, whereby the difficulty of conspicuous fingerprint marks can be evaluated. In the initial fingerprint mark wiping process, fingerprints and anti-fingerprint liquid spread thinly on the wiping surface. When the anti-fingerprint liquid uniformly extends and spreads on the coating film, the coating film whose evaluation rate does not decrease after wiping can be determined to be a coating film in which fingerprint marks are hardly noticeable. Moreover, when the wiping operation using the wiping material is reciprocated 15 to 40 times, for example, the glossiness after wiping is measured, and the evaluation rate after wiping is obtained, whereby the fingerprint resistance after the wiping treatment can be evaluated. Even after 15 to 40 reciprocal wiping, a fingerprint mark remains in a coating film having a low evaluation rate after wiping, and it can be determined that a fingerprint or anti-fingerprint liquid is a coating film having poor fingerprint wiping property. By subdividing the evaluation items for fingerprint resistance in this way, it is possible to evaluate fingerprint resistance evaluation, which has been performed by sensory evaluation by combining various elements, more objectively and with higher reproducibility. It becomes possible.

Calculation process The specular gloss measurement value obtained from the above is processed by the following formula to obtain the adhesion evaluation rate and the post-wiping evaluation rate.
Adhesion evaluation rate (%) = (Glossiness before wiping) / (Initial glossiness) × 100
Evaluation rate after wiping (%) = (Glossiness after wiping) / (Initial glossiness) × 100

  The numerical values of these evaluation rates vary depending on the incident angle when measuring the specular gloss. In the method of the present invention, it is preferable to measure the incident angle in the range of 75 to 20 degrees (75 to 20 degrees specular gloss), and the incident angle is in the range of 60 to 45 degrees (60 to 45 degrees specular gloss). It is more preferable to measure by. In the case of specular glossiness that is out of the above range, for example, 85 degrees or more, a difference in glossiness due to the presence of fingerprint marks tends not to occur. For example, in the case of 20 degree specular gloss, a difference in glossiness tends to be large, but an error tends to occur in proportion thereto.

  The adhesion evaluation rate obtained in this way is evaluated as being superior in fingerprint resistance as the numerical value is higher. Moreover, it is evaluated that the evaluation rate after wiping is superior in fingerprint resistance as the numerical value is higher. For example, when measuring the 60 ° specular gloss, if the adhesion evaluation rate and the evaluation rate after wiping both are 85% or more, the fingerprint resistance is good, and if both are 90% or more, the fingerprint resistance is good. It can be evaluated that it is particularly excellent.

Fingerprint-resistant coating In order to realize the formation of a coating with good fingerprint resistance using the above evaluation method, the present inventors have conducted various studies and obtained from two types of compositions described in detail below. It was found that the resulting coating has excellent fingerprint resistance.

［式中、Ｘは、ポリエーテル骨格を有するポリオール化合物の両末端の水酸基を除いた残基を示す。］
で示される構造を有し、および
このポリエーテル骨格含有ウレタン（メタ）アクリレート（Ａ）の水トレランスが６．０ｍｌ以下であり、溶解性パラメータが１２以下である、
耐指紋性光硬化性組成物、が挙げられる。 As an example of a composition from which a film having excellent fingerprint resistance can be obtained as an anti-fingerprint photocurable composition ,
Polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends,
A photopolymerizable polyfunctional compound (B), and a photopolymerization initiator (C),
Including
This polyether skeleton-containing urethane (meth) acrylate (A) has the following formula (1):

[In formula, X shows the residue except the hydroxyl group of the both ends of the polyol compound which has a polyether frame | skeleton. ]
And the polyether skeleton-containing urethane (meth) acrylate (A) has a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less.
Fingerprint-resistant photocurable composition.

  This fingerprint-resistant photocurable composition may further contain a polyether resin or a polyether (meth) acrylate (D). Hereinafter, each component which comprises this fingerprint-resistant photocurable composition is explained in full detail.

Polyether skeleton-containing urethane (meth) acrylate (A)
The polyether skeleton-containing urethane (meth) acrylate (A) contained in the fingerprint-resistant photocurable composition is
(I) having at least one (meth) acrylate group at each of both ends of the molecule;
(Ii) The following formula (1):

［式中、Ｘは、ポリエーテル骨格を有するポリオール化合物の両末端の水酸基を除いた残基を示す。］
で示される構造を有すること、および
（iii）水トレランスが６．０ｍｌ以下であり、溶解性パラメータが１２以下であること、
を条件とする、ウレタン（メタ）アクリレートである。

[In formula, X shows the residue except the hydroxyl group of the both ends of the polyol compound which has a polyether frame | skeleton. ]
(Iii) the water tolerance is 6.0 ml or less and the solubility parameter is 12 or less,
It is urethane (meth) acrylate on condition.

  When the component (A) has a polyether structure via a urethane bond represented by the above formula (1), excellent fingerprint resistance can be obtained. In addition, when the component (A) has at least one (meth) acrylate group at each of both ends, good scratch resistance can be obtained.

  In addition, the urethane (meth) acrylate of component (A) may have a branched structure. In this case, “both ends” means both ends in the state where the molecular chain is the longest. And when it has such a branched structure, you may have at least 1 (meth) acrylate group also in the terminal of a branched chain.

  As a polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends having the structure represented by the above formula (1), for example, a polyol compound having a polyether skeleton ( A reaction product of a), a polyisocyanate (b), and a hydroxyl group-containing (meth) acrylate monomer (c).

  Examples of the polyol compound (a) having a polyether skeleton include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, 1,6-hexanediol, Polyether polyols having at least one structure of bisphenol A polyethoxydiol, polycaprolactone, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization; trimethylolethane, trimethylolpropane, poly Trimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannini Polyhydric alcohol containing a polyether skeleton obtained by polyether modification of polyol, glycerin, polyglycerin, polytetramethylene glycol or the like; the above polyether polyol and maleic anhydride, maleic anhydride, fumaric acid, itaconic anhydride And polyester polyols that are condensates with polybasic acids such as itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified polyols obtained by modifying polyether polyols with caprolactone; and the like.

  Examples of the polyisocyanate (b) include aromatic, aliphatic and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, Modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate , Lysine diisocyanate, lysine triisocyanate, naphthalene diiso Polyisocyanates or trimer compounds of these polyisocyanates such as Aneto, biuret type polyisocyanate, water-dispersible polyisocyanate or the reaction products of these polyisocyanates with polyols, and the like.

  The hydroxyl group-containing (meth) acrylate monomer (c) may be a monofunctional monomer having one (meth) acrylate group or a polyfunctional monomer having two or more (meth) acrylate groups. Examples of the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, Examples include 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate and caprolactone-modified 2-hydroxyethyl (meth) acrylate. Examples of the polyfunctional monomer include 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol penta (meth). ) Acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, and the like.

  A polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends is a polyol compound (a) having a polyether skeleton, a polyisocyanate (b), and a hydroxyl group-containing (meta ) It can be prepared by reacting the acrylate monomer (c). In this preparation, for example, the polyol compound (a) having a polyether skeleton, the polyisocyanate (b), and the hydroxyl group-containing (meth) acrylate monomer (c) may be reacted at once, or, for example, a polyol having a polyether skeleton. After reacting the compound (a) and the polyisocyanate (b), the hydroxyl group-containing (meth) acrylate monomer (c) may be reacted.

  The reaction between the polyol compound (a) having a polyether skeleton and the polyisocyanate (b) is 1.1 to 2.5 equivalents of the isocyanate group of the polyisocyanate (b) with respect to 1 equivalent of the hydroxyl group of the polyol compound (a). Is preferably reacted, and 1.3 to 2.0 equivalents are particularly preferably reacted. The reaction temperature is preferably 70 to 100 ° C., and the reaction time is preferably about 1 to 20 hours. In the reaction between the polyol compound (a) and the polyisocyanate (b), a metal catalyst such as butyltin dilaurate or an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7 It is more preferable to accelerate the reaction using

  When the polyol compound (a) having a polyether skeleton, the polyisocyanate (b) and the hydroxyl group-containing (meth) acrylate monomer (c) are reacted at once, the amount of the hydroxyl group-containing (meth) acrylate monomer (c) is: It is preferable to use 1.0-1.5 equivalent with respect to 1 equivalent of polyisocyanate (b), and it is more preferable to use 1.0-1.3 equivalent. The reaction temperature is preferably 60 to 100 ° C., and the reaction time is preferably 1 to 20 hours.

  In the case of reacting the polyol compound (a) having a polyether skeleton with the polyisocyanate (b) and then reacting the hydroxyl group-containing (meth) acrylate monomer (c), the polyol compound (a) and the polyisocyanate It is preferable to react 0.95 to 1.5 equivalents of the hydroxyl group of the hydroxyl group-containing (meth) acrylate monomer (c) with respect to 1 equivalent of the isocyanate group of the reaction product of (b), 1.0 to 1.1 equivalents It is particularly preferred to react. The reaction temperature is preferably 60 to 100 ° C., and the reaction time is preferably 1 to 20 hours.

  The polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends preferably has a weight average molecular weight of 3000 to 50000. When the weight average molecular weight of the polyether skeleton-containing urethane (meth) acrylate (A) is smaller than 3000, the molecular weight of the polyol compound (a) having a polyether skeleton is lowered and the urethane group content is relatively high. In addition, there is a risk of a decrease in productivity due to an increase in viscosity during production. On the other hand, if it exceeds 50000, the viscosity of the resulting fingerprint-resistant photocurable composition is increased, resulting in a decrease in the productivity of the fingerprint-resistant photocurable composition and a relative decrease in the acrylate group content. This is not preferable because the mechanical strength of the finally obtained film may be lowered. The average molecular weight here is a weight average molecular weight, and can be calculated from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.

  As the polyether skeleton-containing urethane (meth) acrylate (A), those having a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less are used. When the water tolerance of the component (A) is 6.0 ml or less and the solubility parameter is 12 or less, good fingerprint resistance can be obtained.

  Water tolerance is to evaluate the degree of hydrophilicity, and the higher the value, the higher the hydrophilicity. The water tolerance was measured by mixing 0.5 g of the polyether skeleton-containing urethane (meth) acrylate (A) in 10 ml of tetrahydrofuran in a 100 ml beaker under a condition of 23 ° C., and adding a burette to this mixture. Use ion-exchange water gradually, and measure the amount (ml) of ion-exchange water required for the mixture to become cloudy. This amount of ion-exchanged water (ml) is defined as water tolerance.

  The solubility parameter (sometimes abbreviated as SP value) is a measure of solubility. The SP value indicates that the larger the value, the higher the polarity, and the smaller the value, the lower the polarity. In addition, SP value in case a component (A) is a 2 or more types of mixture makes SP value the weighted average value of the solubility parameter of each component.

  The SP value can be measured by the following method [References: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: poor solvent such as dioxane, acetone, etc. n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.

  The SP value δ of component (A) is given by:

Vi: Molecular volume of the solvent (ml / mol)
φi: Volume fraction of each solvent at cloud point δi: SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

  The reason why a good fingerprint resistance is obtained when the water tolerance of the component (A) is 6.0 ml or less and the solubility parameter is 12 or less is not limited by theory. It seems like. Since the component (A) has a urethane group, the component (A) has a partial structure having a locally high polarity in the molecule. On the other hand, since the component (A) has a water tolerance of 6.0 ml or less, the molecule as a whole is a compound having low polarity. Here, the lipid component constituting the fingerprint trace is assumed to be a long chain fatty acid, and the long chain fatty acid is composed of a portion having a low polarity due to an alkyl group and a carboxyl group having a high polarity. In order to improve fingerprint resistance, it is thought that it is necessary to increase the compatibility with the lipid component that constitutes the fingerprint mark, and from this, as described above, a locally highly polar site (urethane group) and It is considered that good fingerprint resistance could be imparted by using the component (A) having a property of low polarity as a whole molecule. The same applies to the solubility parameter. When the solubility parameter is 12 or less, the component (A) having a highly polar urethane group is a compound having a low polarity as a whole molecule. As a result, it is considered that the conformability to the lipid component constituting the fingerprint mark is enhanced and the fingerprint resistance is improved. It should be noted that both the water tolerance of 6.0 ml or less and the solubility parameter of 12 or less indicate the property of low polarity as a whole molecule. On the other hand, not all of the above theories can be clarified, and the water tolerance is 6.0 ml or less, the solubility parameter is 12 or less, and the structure has a locally high polarity due to having a urethane group. By using the component (A) having all the properties, fingerprint resistance can be improved.

  In addition, as a more preferable example of a component (A), the polyether skeleton containing urethane (meth) acrylate shown by a following formula is mentioned, for example.

［式中、Ｒ^１は、ポリエーテル骨格を有するポリオール化合物（ａ）の両末端の水酸基を除いた残基であり、Ｒ^２はポリイソシアネート（ｂ）の両末端のイソシアネート基を除いた残基であり、Ｒ^３およびＲ^４は、同一であっても異なってよい、水酸基含有（メタ）アクリレートモノマー（ｃ）の水酸基を除いた残基であり、およびｎは１〜６０の整数である。］
このポリエーテル骨格含有ウレタン（メタ）アクリレート（Ａ）は、重量平均分子量が３０００〜５００００であるのがより好ましい。また上記ｎは１〜６０の整数であるのがより好ましく、１〜３０の整数であるのがより好ましい。

[Wherein, R ¹ is a residue obtained by removing hydroxyl groups at both ends of the polyol compound (a) having a polyether skeleton, and R ² is a residue obtained by removing isocyanate groups at both ends of the polyisocyanate (b). R ³ and R ⁴ may be the same or different and are a residue excluding the hydroxyl group of the hydroxyl group-containing (meth) acrylate monomer (c), and n is an integer of 1 to 60. ]
As for this polyether frame | skeleton containing urethane (meth) acrylate (A), it is more preferable that the weight average molecular weights are 3000-50000. Further, n is more preferably an integer of 1 to 60, and more preferably an integer of 1 to 30.

Photopolymerizable polyfunctional compound (B)
The fingerprint-resistant photocurable composition contains a polyether skeleton-containing urethane (meth) acrylate (A). The fingerprint-resistant photocurable composition further contains a photopolymerizable polyfunctional compound (B) as a film forming component. By including the photopolymerizable polyfunctional compound (B), the photocurability of the fingerprint-resistant photocurable composition is improved, and the mechanical strength (such as scratch resistance) of the resulting coating is increased. . The photopolymerizable polyfunctional compound (B) is a compound having two or more photopolymerizable groups in one molecule. As the photopolymerizable polyfunctional compound (B), a compound having two or more (meth) acrylate groups in the molecule can be used. As the photopolymerizable polyfunctional compound (B), a compound having three or more (meth) acrylate groups is preferable. The photopolymerizable polyfunctional compound (B) may be a monomer or an oligomer as long as it is a compound having two or more (meth) acrylate groups.

  Monomers include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di ( Low molecular weight polyalkylene glycol di (meth) acrylates such as (meth) acrylates and tripropylene glycol di (meth) acrylates or their modified alkylene oxides; trimethylolpropane tri (meth) acrylate, pentaerythritol di or tri or tetra (meth) Such as acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate. Orupori (meth) acrylate or an alkylene oxide modified product; etc. isocyanuric acid alkylene oxide modified product of di- or tri (meth) acrylate. The physical properties of the resulting film are adjusted by adjusting the mixing ratio of the compound having two (meth) acrylate groups in the molecule and the compound having three or more (meth) acrylate groups in the molecule. Is possible. In the photopolymerizable polyfunctional compound (B), the content of the compound having three or more (meth) acrylate groups in the molecule is preferably 50 to 100%, and more preferably 70 to 100%. When the content of the photopolymerizable polyfunctional compound (B) having three or more (meth) acrylate groups in the molecule is less than 50%, scratches represented by the steel wool resistance of the finally obtained film Preventing property, solvent resistance, and pen slidability may decrease, which is not preferable.

  Examples of the oligomer include oligomers such as polyester (meth) acrylate, epoxy (meth) acrylate, and acrylic (meth) acrylate. In addition, these oligomers that can be used as the photopolymerizable polyfunctional compound (B) preferably have a weight average molecular weight of 300 to 5,000, and more preferably 500 to 3,000. If it is greater than 5,000, the viscosity becomes high and handling may be difficult.

  These photopolymerizable polyfunctional compounds (B) may be used alone or in combination of two or more.

  As the photopolymerizable polyfunctional compound (B), a monomer having 3 or more photopolymerizable groups (that is, (meth) acrylate groups) in one molecule is preferably used at least in part. By using such a monomer, the mechanical strength of the resulting coating can be further increased. Preferred examples of the photopolymerizable polyfunctional compound (B) include pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.

Photopolymerization initiator (C)
The fingerprint-resistant photocurable composition preferably contains a photopolymerization initiator (C). The presence of the photopolymerization initiator (C) improves the polymerizability of the fingerprint-resistant photocurable composition against irradiation with active energy rays such as ultraviolet rays. Examples of the photopolymerization initiator (C) include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester polymerization initiators. Examples of alkylphenone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of titanocene-based photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned. Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester. Furthermore, hydrogen abstraction initiators such as benzophenone, 2,4,6-trimethylbenzophenone, methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-ethylanthraquinone, camphorquinone, and the like can be used. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  Among the photopolymerization initiators (C), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,2-dimethoxy-1,2-diphenylethane-1- On or the like is more preferably used.

Polyether or polyether (meth) acrylate (D)
The said fingerprint-resistant photocurable composition may contain polyether or polyether (meth) acrylate (D) as needed. When the component (D) which is a polyether resin or a polyether (meth) acrylate is contained in the fingerprint-resistant photocurable composition, there is an advantage that the fingerprint resistance is improved. In particular, by including the component (D), compatibility with lipids is further improved, and specific performance such as further improving the fingerprint wiping property is achieved.

Examples of the polyether as the component (D) include polyether dialkyl ethers, polyether monools or polyether polyols containing alkylene oxides having 3 or more carbon atoms. Examples of the “alkylene oxide having 3 or more carbon atoms” include propylene oxide including isopropylene oxide represented by —O—CH ₂ —CH (CH ₃ ) —, and tetra represented by —O— (CH ₂ ) ₄ —. Examples include methylene oxide, 3-chloropropylene oxide represented by —O—CH ₂ —CH (CH ₂ Cl) —, and alkylene oxides having 3 to 4 carbon atoms. The “alkylene oxide (d-1) having 3 or more carbon atoms” is more preferably propylene oxide, and even more preferably isopropylene oxide. Alkylene oxide (d-2) in which the alkyl group part of the polyether has less than 3 carbon atoms can also be used, but the fingerprint resistance is mainly imparted by “alkylene oxide having 3 or more carbon atoms”. It is preferable that the alkylene oxide of several or more comprises at least one part of a component (D).

  The polyether or the polyether (meth) acrylate (D) preferably has a molecular weight of 400 or more, and more preferably 700 or more. The molecular weight here can be calculated from the measurement result of the hydroxyl value calculated according to JIS K1557.

  A commercially available polyether or polyether (meth) acrylate may be used as the polyether or polyether (meth) acrylate (D). Examples of the polyether or polyether (meth) acrylate that can be preferably used include a polypropylene series manufactured by Kishida Chemical Co., Ltd. and a polyether diacrylate series manufactured by Shin Nakamura Chemical Co., Ltd.

In the above fingerprint-resistant photocurable composition, the amount of each component (A), (B) and (D) is:
0.5-40% by mass of a polyether skeleton-containing urethane (meth) acrylate (A),
30-99.5 mass% of photopolymerizable polyfunctional compound (B),
0 to 30% by mass of polyether or polyether (meth) acrylate (D),
Is preferred.
More specifically, when component (D) is not included,
Polyether skeleton-containing urethane (meth) acrylate (A) 0.5 to 40% by mass, more preferably 2 to 35% by mass
Photopolymerizable polyfunctional compound (B) 30 to 99.5% by mass, more preferably 65 to 98% by mass,
It is more preferable that The total mass of the components (A) and (B) is 100% by mass.
When component (D) is included,
0.5 to 40% by mass of the polyether skeleton-containing urethane (meth) acrylate (A), more preferably 2 to 35% by mass,
30 to 97% by mass of the photopolymerizable polyfunctional compound (B), more preferably 45 to 95% by mass,
1-30% by weight of polyether or polyether (meth) acrylate (D), more preferably 2-20% by weight,
It is more preferable that The total mass of the components (A), (B), and (D) is 100% by mass. Furthermore, when the component (D) to be blended has both an alkylene oxide (d-1) having 3 or more carbon atoms and an alkylene oxide (d-2) having less than 3 carbon atoms, it is included in the component (D) (d- Of the total of 1) and (d-2), 25% by mass or more is preferably (d-1). When the constituent ratio of (d-1) is less than the above preferable lower limit, the fingerprint resistance of the resulting film may be lowered, which is not preferable. In this case, the upper limit of the ratio of (d-1) contained in the component (D) is 100% by mass.

  Moreover, the component (D) mix | blended is a polyether or polyether (meth) acrylate (D-1) derived from (d-1) and a polyether or polyether (meth) acrylate (D) derived from (d-2). -2), it is preferable that 10% by mass or more of (D-1) and (D-2) is (D-1) in the total of (D-1) and (D-2). When the blending ratio of (D-1) is lower than the above-mentioned preferable lower limit, the fingerprint resistance of the resulting film may be lowered, which is not preferable. In this case, the upper limit of the ratio of (D-1) contained in the component (D) is 100% by mass.

When the amount of the polyether skeleton-containing urethane (meth) acrylate (A) is less than the above range, the resulting fingerprint-resistant coating film may be deteriorated in fingerprint resistance, inferior in bending resistance or curling property, etc. . Moreover, when the quantity of polyether frame | skeleton containing urethane (meth) acrylate (A) exceeds the said range, there exists a possibility that steel wool resistance or solvent resistance may fall. When the amount of the photopolymerizable polyfunctional compound (B) is less than 30% by mass, physical strength such as scratch resistance and surface film hardness may be deteriorated.
Moreover, it is preferable that a photoinitiator (C) contains 0.1-20 mass parts with respect to 100 mass parts of total mass of component (A), (B) and (D). When the amount of the photopolymerization initiator (C) is out of the above range, the photocurability may be insufficient and the physical strength may be deteriorated.

Other Components The above fingerprint-resistant photocurable composition can be blended with a compound having one ethylenically unsaturated group, if necessary. By including such a compound, it is possible to adjust the viscosity of the resulting coating liquid, the adhesion, hardness, and flexibility of the resulting film. Examples of the compound having one ethylenically unsaturated group include (meth) acrylate compounds having a cyclic structure such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; 2-hydroxyethyl (meta ) Acrylates, hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate; (meth) acrylate compounds of alkoxy oxide adducts of phenols such as phenoxyethyl (meth) acrylate; ethylene glycol mono (meth) acrylate, methoxy Glycol mono (medium) such as ethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and tripropylene glycol mono (meth) acrylate. ) Acrylate; N- Binirupidoriron, vinyl compounds such as N- vinyl caprolactam.

  The fingerprint-resistant photocurable composition may contain a filler such as inorganic particles or organic particles as necessary. By containing inorganic particles or organic particles, the scratch resistance and surface hardness of the coating can be further improved, or antiglare properties can be imparted. These inorganic particles or inorganic particles are more preferably those having an average particle diameter of about 5 nm to several μm. Examples of inorganic particles that can be used include fine particles of metal or metal oxide. Examples of the metal include Si, Ti, Al, Zn, Zr, In, Sn, and Sb. Specific examples of the inorganic particles include silica, alumina, zirconia, and titania. Furthermore, it is more preferable that these inorganic particles have a particle surface modified with a UV curable functional group such as an acrylate group. Examples of organic particles that can be used include organic particles such as acrylic and polyester.

  In addition, when using an inorganic particle or an organic particle, it is preferable to use about 0.1-50 mass% with respect to solid content mass of a fingerprint-proof photocurable composition. When the content of inorganic particles or organic particles exceeds 50% by mass, the film strength of the obtained coating film may be weakened.

  The fingerprint-resistant photocurable composition may further contain an organic solvent as a dilution solvent, if necessary. Examples of such organic solvents include, for example, aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, octane, and mineral spirit; methyl ethyl ketone, acetone, and methyl Ketone solvents such as isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; Esters such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate Amide solvents such as dimethylformamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone; cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; ether ester systems such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate Solvents; Alcohol solvents such as methanol, ethanol and propanol; Halogen solvents such as dichloromethane, dichloroethane and chloroform; These solvents may be used alone or in combination.

  The above-mentioned fingerprint-resistant photocurable composition further comprises a photopolymerization initiation aid, an antistatic agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, if necessary. It may contain commonly used additives such as pigments. Examples of photopolymerization initiation assistants that can be preferably used include ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, dibutylethanolamine, and methyldiethanolamine.

Preparation of fingerprint-resistant photocurable composition and coating preparation The above-mentioned fingerprint-resistant photocurable composition comprises a polyether skeleton-containing urethane (meth) acrylate (A), a photopolymerizable polyfunctional compound (B), and photopolymerization initiation. It contains an agent (C) and optionally a polyether or polyether (meth) acrylate (D). And by using the above-mentioned fingerprint-resistant photocurable composition, a film having excellent fingerprint resistance even with a single layer, and excellent scratch resistance, surface film hardness and fingerprint resistance durability can be obtained. Can be formed.

  The fingerprint-resistant photocurable composition is photocurable. Therefore, when forming a film, it has the advantage that it is not necessary to carry out heat polymerization. Many optical display devices include a member having a low heat resistance such as a resin film. The fingerprint-resistant photocurable composition has an advantage that a coating film can be satisfactorily formed even on an optical display device and a resin film including such a member having low heat resistance.

  The fingerprint-resistant photocurable composition can be prepared by mixing the above components. Moreover, you may use the organic solvent which can be used for dilution as needed at the time of preparation of a composition. In addition, the said fingerprint-resistant photocurable composition may be used diluted, and may be used without diluting.

  As a method for preparing a fingerprint-resistant photocurable composition, for example, the above polyether skeleton-containing urethane (meth) acrylate (A), photopolymerizable polyfunctional compound (B) and photopolymerization initiator (C), and necessary Can be prepared by mixing a polyether or polyether (meth) acrylate (D) according to the above, an additive, an organic solvent, and the like.

  In addition, it is preferable that the said fingerprint-resistant photocurable composition does not contain both a silicone type additive and a fluorine type additive. While these additives have the effect of improving the water repellency and oil repellency of the resulting coating and improving the antifouling property, the improvement in water repellency and oil repellency repels the oil and fat components adhering to the coating. This is because the dirt may be noticeable.

  By using the fingerprint-resistant photocurable composition, a fingerprint-resistant film can be easily prepared. This fingerprint-resistant film has a transparent substrate and a coating. This film is a layer formed from the above-mentioned fingerprint-resistant photocurable composition, and the presence of this layer exhibits fingerprint resistance.

  Transparent substrates used for preparing the fingerprint-resistant film include various transparent plastic films such as triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetyl cellulose film, acetate butyrate cellulose film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used. Polyethylene terephthalate is preferably used as the transparent substrate. In addition, although the thickness of a transparent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  A film having fingerprint resistance is formed by coating the above-mentioned fingerprint-resistant photocurable composition on a transparent substrate. The coating method of the fingerprint-resistant photocurable composition can be selected as appropriate according to the fingerprint-resistant photocurable composition and the state of the coating process, such as dip coating, air knife coating, curtain coating, The coating can be performed by a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (this method is a known method described in US Pat. No. 2,681,294).

The fingerprint-resistant photocurable composition coated on the transparent substrate is then cured by being exposed to active energy rays, thereby forming a fingerprint-resistant film. In this specification, the term “photocurability” is used in a broad sense, and in addition to rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, It means the property of curing when irradiated with active energy rays such as proton rays and neutron rays. Among these, curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation apparatus, price, and the like. Examples of the ultraviolet curing method include a method of irradiating about 100 to 3000 mJ / cm ² using a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp or the like that emits light in a wavelength range of 200 to 500 nm.

  Moreover, a film can be formed on the surface of the optical display device by coating the fingerprint-resistant photocurable composition on the surface of the optical display device. Examples of the optical display device that can be provided with a film using the fingerprint-resistant photocurable composition include a touch panel display, a liquid crystal display, a light emitting diode display, an electroluminescence display, a fluorescent display, and a plasma display panel. A film is formed on the surface of the optical display device by applying the above-mentioned fingerprint-resistant photocurable composition to various transparent plastic films, transparent plastic plates and glass used on the surface of these optical display devices. Can do.

  Furthermore, the above-mentioned fingerprint-resistant photocurable composition is coated on the surface of articles that have been mirror-finished by metal plating or metal-plated coating. A fingerprint-like film can be formed. Examples of the article having a mirror finish include portable information terminals, household electrical appliances, furniture, indoor furniture, and cosmetic cases. By providing a fingerprint-resistant film on the surface of the article having such a mirror finish, it is possible to prevent fingerprint marks from being attached.

  Examples of the coating method for the fingerprint-resistant photocurable composition include a spin coating method, a dip coating method, a gravure coating method, a spray method, a roller method, and a brush coating method. A suitable coating method can be selected in accordance with the type of optical display device to be coated. In the application of the fingerprint-resistant photocurable composition, it is preferable to apply so that the thickness of the obtained film is 0.1 to 20 μm. The fingerprint-resistant photocurable composition thus coated is cured by being exposed to active energy rays in the same manner as described above, thereby forming a fingerprint-resistant film.

  By using the above-mentioned fingerprint-resistant photocurable composition, it is possible to more easily provide a coating film having excellent fingerprint resistance on an optical display device surface or a mirror-finished article. The film obtained from the above fingerprint-resistant photocurable composition is also excellent in transparency, and is very suitable for use on the surface of an optical display device or the surface of an article having a mirror finish. The film obtained from the above fingerprint-resistant photocurable composition further has excellent scratch resistance and surface film hardness. Even if this film is a single layer, it has excellent fingerprint resistance, high scratch resistance and surface film hardness. Furthermore, since the above-mentioned fingerprint-resistant photocurable composition is photocurable, it is possible to more easily form a film having such excellent performance on the surface of the optical display device or an article having a mirror finish. There is an advantage. Therefore, by using the above-mentioned fingerprint-resistant photocurable composition, a film excellent in production efficiency and production cost and a fingerprint-resistant film having this film can be formed. Furthermore, this coating film has the advantage that it can maintain fingerprint resistance for a long period of time and is excellent in fingerprint resistance durability.

As another example of a composition for obtaining a film having excellent fingerprint resistance, an anti-fingerprint curable composition ,
(A) An acrylic resin having an active methylene group or active methine group (a) and a saturated cycloalkyl group (b) in the molecule, or an acrylic resin having an active methylene group or an active methine group (a) and a saturated cycloalkyl group A mixture with an acrylic resin having (b),
(B) a polyfunctional polymerizable compound having two or more photocurable functional groups in the molecule;
(C) a photopolymerization initiator, and (d) a Michael reaction catalyst,
The anti-fingerprint curable composition containing this. Hereinafter, each component will be described in detail.

Ingredient (I)
Component (a) of the anti-fingerprint curable composition is an acrylic resin having an active methylene group or active methine group (a) and a saturated cycloalkyl group (b) in the molecule, or an active methylene group or an active methine group. It is a mixture of an acrylic resin having (a) and an acrylic resin having a saturated cycloalkyl group (b). The acrylic resin of component (a) is synthesized by copolymerizing an acrylic monomer having an active methylene group or an active methine group (a), an acrylic monomer having a saturated cycloalkyl group (b), and other acrylic monomers. . Moreover, as other acrylic monomers, carboxyl group-containing monomers such as (meth) acrylic acid, epoxy group-containing monomers such as glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ester (meth) acrylate, Plaxel FM-1 (addition of 2-hydroxyethyl acrylate and polycaprolactone, an acrylic monomer having a reactive group such as a hydroxyl group-containing monomer such as manufactured by Daicel Chemical Industries, Ltd.) and then an addition reaction It is also possible to introduce a polymerizable unsaturated bond into the acrylic resin by means of, etc. The polymerizable unsaturated bond is reactive with this acrylic resin when an acrylic resin containing only a saturated cycloalkyl group (b) is used. Since there is no group and the curability is insufficient, a polymerizable unsaturated group is introduced. It can increase the degree of cure by.

  An active methylene group is a methylene group sandwiched between two carbonyl groups, in an electron-excess state due to the carbonyl group, and in a state where a proton is easily released to generate a carbanion. It is a methine group that is sandwiched between carbonyl groups and is in an electron-excess state due to the carbonyl group and is likely to generate a carbanion by releasing protons. The active methylene group or active methine group undergoes a Michael addition reaction with an unsaturated double bond when heated.

  Specific examples of the acrylic monomer having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, and N- (2-propionyl). Examples include acetoxybutyl) acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide, 2- (N-acetoacetylaminoethyl) (meth) acrylate, and the like.

  An acrylic monomer having an active methine group is a methanetricarboxylic acid or a derivative thereof as described in EP 0310011 and an acrylic monomer having a hydroxyl group (for example, 2-hydroxyethyl methacrylate, N- (2-hydroxyethyl) methacrylamide and the like).

  The acrylic monomer having a saturated cycloalkyl group (b) is a (meth) acrylate having a saturated cycloalkyl group, preferably having a saturated cycloalkyl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. (Meth) acrylate. Some specific examples include, for example, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclododecyl (meth) acrylate, Examples include tricyclodecane monomethanol mono (meth) acrylate. A saturated cycloalkyl group having less than 6 carbon atoms is not preferred because the lipophilicity is not sufficient. Moreover, in the case of a cycloalkyl group having more than 18 carbon atoms, appearance defects such as a decrease in compatibility with the polyfunctional polymerizable compound (B) and the coating becoming cloudy occur. In addition, it is desirable that the composition does not contain silicon (mainly polydimethylsiloxane) or fluorine (mainly perfluoroalkyl group) which is usually used as a water repellent group. While these monomers have the effect of improving the water repellency and oil repellency of the resulting coating layer and improving the antifouling property, the improvement of the water repellency and oil repellency repels the oil and fat components adhering to the coating layer. This is because the dirt may be noticeable.

  In addition to the acrylic monomer having an active methylene group or active methine group (a) and the acrylic monomer having a saturated cycloalkyl group (b), the acrylic resin (a) may be copolymerized with other acrylic monomers. Acrylic monomers having no functional groups such as methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, etc. of acrylic acid or methacrylic acid, 2-hydroxyethyl, 2 -Hydroxypropyl ester, Plaxel FM-1 (addition product of 2-hydroxyethyl acrylate and polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.), an acrylic monomer having a hydroxyl group, and an epoxy group such as glycidyl (meth) acrylate Acrylic monomers having acrylamide, derivatives thereof such as N-methylolacrylamide, acrylonitrile and the like, and examples of non-acrylic monomers include styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

  The acrylic resin (a) is obtained by copolymerizing the above acrylic monomer. In general, it is preferable to use a solvent in the copolymerization in order to improve uniformity. Such solvents include alcohol solvents such as methanol, ethanol, isopropanol (IPA), isobutanol, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), tetrahydrofuran, dioxane, methoxyethanol, ethylene glycol mono Ether solvents such as ethyl ether, ethylene glycol dimethyl ether and propylene glycol monomethyl ether, carboxylic acid ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl propionate and butyl butyrate, propylene glycol monomethyl ether acetate (PGMAc), 2 -Ether ester solvents such as ethoxyethyl acetate, aromatic hydrocarbon solvents such as benzene, toluene and xylene, dimethylform Bromide, organic solvents such as dimethylacetamide is used. Moreover, you may add water in the range which does not impair the uniformity of a reaction system.

  As the radical polymerization initiator for obtaining the acrylic resin (a), known initiators generally used for radical polymerization can be used. Representative examples include organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, 2,2′-azobisbutyronitrile, 2,2′-azobis (2,4 An azo compound such as -dimethylvaleronitrile) (V65) or 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) is particularly preferably used. The total concentration of the monomers in the polymerization solution is usually 10 to 60% by mass, and the polymerization initiator is usually used in an amount of 0.1 to 15% by mass, preferably 1 to 10% by mass, based on the monomer mixture. Is done.

  The preferred polymerization temperature varies depending on the radical polymerization initiator used, but the polymerization temperature is 20 to 150 ° C., and the polymerization time is 1 to 72 hours.

  In the acrylic resin (A), the acrylic monomer having an active methylene group or active methine group (a) is contained in an amount of 10 to 80% by mass, preferably 25 to 70% by mass, based on the total mass of the acrylic monomer. And the acrylic monomer which has a saturated cycloalkyl group (b) contains 2-60 mass% with respect to the total mass of the whole acrylic monomer, Preferably it contains in the quantity of 15-60 mass%. If the amount of the acrylic monomer having an active methylene group or an active methine group (a) is less than the lower limit, the Michael addition reaction is not sufficient and the solvent resistance is insufficient or the wear resistance is insufficient. When an article provided with a film having insufficient solvent resistance is provided to a consumer, the film may be dissolved when the article is cleaned with a cleaning agent containing a solvent such as alcohol. Further, when the amount of the acrylic monomer having a saturated cycloalkyl group (b) is less than the lower limit, the fingerprint resistance is insufficient, and conversely, when the amount of the acrylic monomer is larger than the upper limit, the polyfunctional polymerizable compound (b) and As a result, the appearance of the coating becomes cloudy.

The acrylic resin (a) can have two types of embodiments. The first is the case of using an acrylic resin in which both the active methylene group or active methine group (a) and the saturated cycloalkyl group (b) are present in one acrylic resin molecule, and the second is the active methylene group or active acrylic resins having an acrylic resin (b ₁₎ and a saturated cycloalkyl group (b) having a methine group (a) a (b ₂₎ synthesized separately, mixed both acrylic resin (b _{1 +} b ₂₎ Is used. In any case, the anti-fingerprint effect can be exhibited.

The acrylic resin (A) preferably has a weight average molecular weight of 5,000 to 50,000, more preferably 5,000 to 15,000 in any of the above cases. When the weight average molecular weight is less than 5,000 in terms of polystyrene, the solvent resistance after the Michael addition reaction becomes insufficient. When the weight average molecular weight exceeds 50,000, the viscosity increases after mixing the two liquids. When the pot life is shortened, the compatibility with the polyfunctional polymerizable compound (B) is lowered, and the coating becomes cloudy. When the pot life is less than 8 hours after mixing the two liquids, it may be necessary to change the process so that the paint is consumed within the operation time in the factory, which is not preferable in practice. However, an acrylic resin having an active methylene group or active methine group (a) (b ₁₎ an acrylic resin having a saturated cycloalkyl group (b) (i ₂₎ synthesized separately, both of the acrylic resin (b ₁ When + a ₂ ) is used as a mixture, the acrylic resin (a ₂ ) having a saturated cycloalkyl group (b) does not participate in the Michael addition reaction, so the molecular weight may not be within the above range. There is no particular problem if the molecular weight is less than 200,000.

  The acrylic resin of component (I) is preferably present in the fingerprint-resistant curable composition in a solid content of 10 to 50% by mass, more preferably 20 to 40% by mass. When the amount is less than 10% by mass, the Michael addition reaction becomes insufficient, and the solvent resistance after the Michael addition reaction becomes insufficient. When the amount exceeds 50% by mass, the amount of the polyfunctional polymerizable compound (B) decreases. Therefore, the photocuring reaction becomes insufficient and the wear resistance is insufficient.

Ingredient (b)
The component (b) of the anti-fingerprint curable composition is a polyfunctional polymerizable compound having two or more photocurable functional groups (namely, ethylenically unsaturated groups) in the molecule. Specifically, the polyfunctional polymerizable compound is a polymerizable unsaturated monocarboxylic acid ester compound of a polyhydric alcohol (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diester). Methacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol diacrylate, Glycerol dimethacrylate, glycerol acoxydimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethanetri Acrylate, 1,1,1-trishydroxymethylethane trimethacrylic 1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate, etc., polybasic acid polymerizable unsaturated alcohol ester compounds (eg diallyl terephthalate, diallyl) Phthalates, triallyl trimellitate, etc.) aromatic compounds substituted with two or more vinyl groups (eg divinylbenzene), epoxy group-containing ethylenically unsaturated monomers and carboxyl group-containing ethylenically unsaturated monomers Adducts with monomers (for example, reaction products of glycidyl acrylate or glycidyl methacrylate and acrylic acid, methacrylic acid, crotonic acid, maleic acid, etc.), (poly) diisocyanate and hydroxyl group-containing ethylenically unsaturated monomer ( For example, hydroxyethyl acrylate, hydride And urethane compounds obtained by reacting loxyethyl methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc.).

  These polyfunctional polymerizable compounds can be used alone or in admixture of two or more.

  The polyfunctional polymerizable compound having two or more photocurable functional groups in the molecule of the component (b) is preferably 50 to 90% by mass, more preferably in solid content in the fingerprint-resistant curable composition. Is present at 60-80% by weight. When the amount is less than 50% by mass, the photocuring reaction becomes insufficient and wear resistance is insufficient. When the amount exceeds 90% by mass, the amount of the acrylic resin (i) having an active methylene group or an active methine group decreases. In addition, the Michael addition reaction becomes insufficient, and the solvent resistance after the Michael addition reaction becomes insufficient.

  The solid content blending ratio (component (I) / component (B)) between the acrylic resin of component (I) and the polyfunctional polymerizable compound of component (B) is preferably 10/90 to 50/50. Preferably it is 20 / 80-40 / 60. When the blending ratio is out of the above range, the solvent resistance after the Michael addition reaction becomes insufficient, or the photocuring reaction becomes insufficient, resulting in insufficient wear resistance.

Ingredient (C)
The photopolymerization initiator of component (c) is blended in order to promote curing of the polyfunctional polymerizable compound of component (b).

  Examples of photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, benzophenone, 2,4,6-trimethylbenzoin diphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Michler's ketone, N, -Isoamyl dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and the like. Two or more photopolymerization initiators can be used in combination as appropriate.

  The photopolymerization initiator (c) is 10% by mass or less, preferably 1 to 5% of the total solid content of the anti-fingerprint curable composition comprising the components (a), (b), (c) and (d). Used in an amount of mass%. When it is less than 1% by mass, the photocurability is insufficient. When it exceeds 10 mass%, abrasion resistance and pencil hardness will fall.

Ingredient (d)
Component (d) of the anti-fingerprint curable composition is a Michael reaction catalyst. In the Michael reaction catalyst (d), two electron-withdrawing groups such as two carbonyl groups adjacent to methylene (methine) increase the acidity of methylene (methine) protons and generate a carbanion (enolate anion). It is a compound required for. Examples of the Michael reaction catalyst (d) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium ethoxide; quaternary ammonium halides and quaternary ammonium carbonates. Onium salts such as quaternary ammonium hydroxide and quaternary ammonium tetrahydroborate; tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, diazabicyclo [4.3.0] nona-5 -Tertiary amines such as ene and quaternary salts thereof with organic acids; guanidine; amidine; tertiary phosphines such as triphenylphosphine. Further, as a co-catalyst for these Michael reaction catalysts (d), for example, epoxy compounds known from JP-A-7-173262 can be used.

  As the cation part of the onium salt, specifically, tetrabutylammonium cation, tetramethylammonium cation, tetrapropylammonium cation, tetrahexylammonium cation, tetraoctylammonium cation, tetradecylammonium cation, tetrahexadecylammonium cation, Quaternary ammonium cations such as triethylhexylammonium cation, 2-hydroxylethyltrimethylammonium (choline) cation, methyltrioctylammonium cation, cetyltrimethylammonium cation, 2-chloroethyltrimethylammonium cation, and methylpyridinium cation; tetrabutylphosphonium cation, etc. Quaternary phosphonium cations; trimethylsulfonium It can be exemplified tertiary sulfonium cation and the like of the thione or the like. It is preferable that it is a quaternary ammonium cation which can obtain various kinds industrially.

  The anion portion of the onium salt specifically includes halide anions such as a fluoride anion, chloride anion, bromide anion, iodide anion; acetate anion; benzoate anion, salicylate anion, maleate anion, phthalate anion Carboxylate anions such as methanesulfonate anion, p-toluenesulfonate anion, dodecylbenzenesulfonate anion, etc .; sulfate anions such as sulfate anion, methosulfate anion; nitrate anions such as nitrate anion; phosphate anions And phosphate anions such as di-t-butyl phosphate anion. Moreover, a hydroxide anion, a carbonate anion, a tetrahydroborate anion, etc. can be mentioned. From the viewpoint of curability, the above halide anions and carboxylate anions are preferable.

  Specific examples of onium salts include tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium fluoride, tetraethylammonium bromide, diethyldibutylammonium chloride, octyltrimethylbromide, tetrabutylammonium acetate, dioctyldimethylammonium salicylate. Benzyllauryldimethylammonium chloride, 2-hydroxyethyltrimethylammonium chloride, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride, trimethylsulfonium chloride and the like.

  As the Michael reaction catalyst (d), the above compounds may be used singly or in combination of two or more.

  The Michael reaction catalyst (d) is 0.1 to 10% by mass, preferably 1 of the total solid content of the anti-fingerprint curable composition comprising the components (a), (b), (c) and (d). Used in an amount of ˜7% by weight. When it is less than 0.1% by mass, the Michael addition reactivity is insufficient. When it exceeds 10 mass%, abrasion resistance falls.

Other Components The anti-fingerprint curable composition may contain a compound having one ethylenically unsaturated group as described above, an inorganic filler, an organic solvent, and the like, if necessary.

Method for Forming Fingerprint-Resistant Film Using the above-mentioned fingerprint-resistant curable composition, a fingerprint-resistant film (sometimes referred to as a hard coat layer in this specification) can be formed on the housing surface. In that case, after applying the above-mentioned curable resin composition to the transparent film, it is heated to obtain a multilayer transparent film, and the casing having the multilayer transparent film is bonded to the casing. The fingerprint-resistant film is formed on the surface of the casing by irradiating the casing having the obtained multilayer transparent film with active energy rays. For example, when pasting on a case such as a computer or a mobile phone, it is desirable that the film thickness is about 100 μm so that the base is recognizable and can be further colored, but it is colorless and transparent. It is particularly preferred. The heating process and active energy ray irradiation may be switched in order or performed simultaneously. By using the above-mentioned fingerprint-resistant curable composition, a coating (that is, a hard coat) that has excellent fingerprint resistance even in a single layer, and excellent scratch resistance, surface film hardness, and fingerprint resistance. Layer) can be formed.

  The fingerprint-resistant curable composition can be prepared by mixing the above components. Moreover, you may use the organic solvent which can be used for dilution as needed at the time of preparation of a composition. In addition, the said anti-fingerprint curable composition may be used diluted, and may be used without diluting.

  As a method for preparing the anti-fingerprint curable composition, for example, it can be prepared by mixing the above components (A) to (D) and, if necessary, other components (for example, additives). .

  The fingerprint-resistant curable composition preferably contains neither a silicone-based additive nor a fluorine-based additive. While these additives have the effect of improving the water repellency and oil repellency of the resulting coating layer and improving the antifouling property, the improvement of the water repellency and oil repellency repels the oil and fat components adhering to the coating layer. This is because the dirt may be noticeable.

  By using the above-mentioned fingerprint-resistant curable composition, a fingerprint-resistant film can be easily prepared. This fingerprint-resistant film has a transparent substrate and a coating layer. This coating layer is a layer formed from the above-mentioned fingerprint-resistant curable composition, and the presence of this layer exhibits fingerprint resistance. By attaching such a film including a transparent base material and a coating layer to the casing, fingerprint resistance can be easily imparted to the casing having a complicated three-dimensional design.

  Transparent substrates used for preparing the fingerprint-resistant film include various transparent plastic films such as triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetyl cellulose film, acetate butyrate cellulose film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used. Polyethylene terephthalate is preferably used as the transparent substrate. In addition, although the thickness of a transparent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The coating layer having fingerprint resistance is formed by applying the above-mentioned fingerprint-resistant curable composition on a transparent substrate. The application method of the anti-fingerprint curable composition can be selected as appropriate according to the anti-fingerprint curable composition and the state of the coating process, such as dip coating, air knife coating, curtain coating, roller coating. It can be applied by a method, a wire bar coating method, a gravure coating method, an extrusion coating method (this method is described in US Pat. No. 2,681,294). In the application of the fingerprint-resistant curable composition, it is preferable to apply the coating layer so that the resulting coating layer has a thickness of 0.1 to 20 μm.

In general, a fingerprint-resistant photocurable composition coated on a transparent substrate is first heated and thermally cured to obtain a multilayer transparent film, and then the multilayer transparent film is attached to a housing. Then, it hardens | cures by irradiation of an active energy ray, and, thereby, a fingerprint-resistant film is formed. It is preferable from the viewpoint of productivity that the heating temperature at the first thermosetting is high temperature and in a short time, but it is necessary to be not more than the softening temperature of the transparent substrate. In the case of a polyethylene terephthalate film, 60 to 150 ° C The temperature is preferably 80 to 120 ° C. Moreover, it is preferable to irradiate 100-5000 mJ / cm < ² > by integrated light quantity using the light of a wavelength of 200-500 nm for irradiation of an active energy ray. When the integrated light quantity is 100 mJ / cm ² or less, the photocuring reaction becomes insufficient and the wear resistance is insufficient. On the other hand, when the integrated light quantity is 5000 mJ / cm ² or more, a photodegradation reaction occurs on the surface of the film, resulting in a decrease in fingerprint resistance or yellowing of the film.

  Specific examples of products coated with the fingerprint-resistant photocurable composition include mobile terminal products such as mobile phones and notebook computers. In addition, the thermosetting film of the above-mentioned fingerprint-resistant curable composition is applied to various transparent plastic films, transparent plastic plates and glass used on the surface of optical display devices such as liquid crystal display devices, CRT (CRT) display devices and touch panel displays. By adhering a multilayer transparent film having a coating layer, a coating layer can be formed on the surface of the optical display device. Moreover, it becomes possible to apply | coat the said anti-fingerprint curable composition to a transparent plastic board, and to process it to the shield of a helmet, or the front face protection board of a speedometer by carrying out a heat bending process.

  The above-mentioned fingerprint-resistant curable composition is a polyvalent compound having an active methylene group or active methine group (a) of acrylic resin (a) and two or more photocurable functional groups in the molecule by a Michael addition reaction in a heating process. The photocurable group of the functional polymerizable compound (b) reacts to crosslink. In the light irradiation process, the photopolymerizable group of component (b) reacts to crosslink. By these two reactions, hardness and abrasion resistance are obtained, and the saturated cycloalkyl group in the acrylic resin (a) imparts fingerprint resistance and fingerprint resistance. As for these two types of curing methods, any one of the curing methods may be performed first, and the other method may be performed later, or may be performed simultaneously. In general, the Michael addition reaction by heat curing is performed first, and then the entire curing is performed by photocuring.

  The fingerprint-resistant curable composition can be cured in two stages as described above. Since the elongation rate of the hard coat layer of the prior art is extremely small, it follows the expansion and contraction of the thermoplastic resin substrate when it is formed on the surface of the thermoplastic resin substrate and heat-processed with the hard coat layer. In some cases, the hard coat layer may be cracked or the hard coat layer may be peeled off. On the other hand, when the composition is cured in the above-described two stages, it is in a semi-cured state that is not completely cured in the pre-curing stage. It becomes possible to follow expansion and contraction during thermal processing. In addition, the curable composition of the present invention exhibits a remarkably large elongation after precuring when the semi-cured film is first formed using a thermosetting reaction and the curing reaction is adjusted. That is, the film is semi-cured by the Michael addition reaction in the first heating process to facilitate handling, and in this state, it is attached to the object to be coated (casing) and processing such as thermal bending is performed at the same time. A hard coat layer with high fingerprint resistance having an appropriate hardness is formed by completely irradiating with a line.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Example of Preparation and Comparative Preparation Example Preparation of Fingerprint Resistant Curable Composition and Production of Hard Coat Film for Evaluation A curable composition having a difference in fingerprint resistance is produced, and the obtained composition is placed on a PET film. Bar coating was applied, and the solvent was removed by drying with a hot air dryer. Thereafter, the coating film was formed by exposing and curing ultraviolet rays with a high-pressure mercury lamp (120 W / cm) so as to have an energy of 300 mJ / cm ² , thereby obtaining a hard coat film. Detailed contents of the composition are shown below.

Example of Preparation 1 Preparation of anti-fingerprint photocurable composition 1
Production Example 1
Preparation of polyether skeleton-containing urethane (meth) acrylate (A1) having at least one (meth) acrylate group at each of both ends Isophorone diisocyanate (IPDI) 666 parts by mass, polypropylene glycol (polypropylene glycol 1000, average molecular weight 1000, kida Chemical Co., Ltd.) 2000 parts by weight, 900 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing weight ratio 60:40) is added to the reaction vessel, and 1000 ppm of dibutyltin dilaurate as a catalyst is prohibited. Hydroquinone 1000 ppm as an agent and methyl isobutyl ketone (MIBK, used in an amount that makes the solid content 40%) as a solvent were added, and 80 ° C. while blowing air. 3 hours were mixed.

  Thus, a polyether skeleton-containing urethane (meth) acrylate (A1) having an acrylate group at both ends was obtained. When the SP value and water tolerance value of the obtained polyether skeleton-containing urethane (meth) acrylate were measured, the SP value was 10.8 and the water tolerance value was 3.5. The weight average molecular weight was 7000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Preparation of Fingerprint Resistant Photocurable Composition 1 20 parts by mass of a polyether skeleton-containing urethane (meth) acrylate obtained by Production Example 1, Aronix M305 (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing mass ratio of about 60:40) 80 parts by mass and 3 parts by mass of Irgacure 184D (1-hydroxy-cyclohexyl-phenyl-ketone) were mixed, and MIBK was used as a solvent to adjust the non-volatile fraction to 40% by mass to improve fingerprint resistance. A photocurable composition 1 was obtained.

Preparation of Fingerprint Resistant Hard Coat Film 1 The composition obtained was coated on a PET film (thickness: 100 μm) with a bar coater (No. 12) so as to have a dry film thickness of 5 μm. The solvent was removed by heating at 0 ° C. for 1 minute to dry. Then, a high-pressure mercury lamp (120 W / cm) was exposed to ultraviolet rays so as to have a process energy of 300 mJ / cm ² and cured to form a film, whereby a fingerprint-resistant hard coat film 1 was obtained.

Example of Preparation 2 Preparation of anti-fingerprint curable composition 2
Production Example 2
A monomer mixture (1) consisting of 222.7 g of cyclohexyl methacrylate and 137.3 g of acetoacetoxyethyl methacrylate was mixed. This mixed solution was added to 273.6 g of n-butyl acetate heated to 120 ° C. under a nitrogen atmosphere in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel, and then tert-butyl peroxy- At the same time as a mixed solution (2) of 24.0 g of n-butyl acetate containing 18.0 g of 2-ethylhexanoate, the solution was added dropwise at a constant rate over 3 hours, and then reacted at 120 ° C. for 30 minutes. Thereafter, 1.8 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise to a solution of 28.8 g of n-butyl acetate, followed by reaction for 2 hours. An acrylic copolymer (resin (1)) having a number average molecular weight of 3,000 and a weight average molecular weight of 6,000 was obtained.

Preparation of Fingerprint Resistant Curable Composition 2 30 parts by mass of an active methylene group-containing acrylic copolymer (resin (1)) obtained by Production Example 2, Aronix M-402 (dipentaerythritol hexaacrylate and dipentaerythritol penta) A mixture of acrylates, 70 parts by mass of Toa Gosei Co., Ltd.) and 5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184D, Ciba Japan Co., Ltd.) are mixed, and MEK (methyl ethyl ketone) After adjusting so that a non-volatile fraction might be 40 mass%, 1 part by weight of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by San Apro Co., Ltd.)) was added. A fingerprint-resistant curable composition 2 was obtained.

Preparation of fingerprint-resistant hard coat film 2 Fingerprint-resistant curable composition 2 is bar-coated on a PET film (thickness 125 μm) with a bar coater (No. 12) and heated at 100 ° C. for 2 minutes. The photocurable film was obtained by removing the solvent and drying. The film thickness at that time was 7 μm. Thereafter, an ultraviolet ray with a high pressure mercury lamp (120 W / cm) was exposed to a factory energy of 300 mJ / cm ^2, by curing, to obtain a fingerprint hard coat film 2.

Comparative Preparation Example 1 Adjustment of Hard Coat Composition (Ratio 1) Aronix M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toa Gosei Co., Ltd.) 100 parts by mass, Irgacure 184D (1- 5 parts by mass of hydroxy-cyclohexyl-phenyl-ketone) and 0.1 part by mass of TEGORAD-2200N (manufactured by Degussa) were mixed and adjusted so that the nonvolatile fraction was 50% by mass using MIBK as a solvent, and photocuring A hard coat composition (ratio 1) was obtained.

Production of Hard Coat Film (Ratio 1) The obtained composition was bar coated with a bar coater (No. 8) on a PET film (thickness 100 μm) so that the dry film thickness was 5 μm. The solvent was removed by heating at 0 ° C. for 1 minute to dry. Thereafter, the coating film was formed by exposing and curing the ultraviolet ray with a high-pressure mercury lamp (120 W / cm) so as to have a working energy of 300 mJ / cm ² to obtain a hard coat film (ratio 1).

Comparative Preparation Example 2 Preparation of fingerprint-resistant composition (ratio 2) 20 parts by mass of cyclohexyl methacrylate and Aronix M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.) 80 Part by mass, 5 parts by mass of Irgacure 184D (1-hydroxy-cyclohexyl-phenyl-ketone) and 0.02 parts by mass of TEGORAD-2200N (manufactured by Degussa), and a non-volatile fraction of 50% by mass using MIBK as a solvent Thus, a fingerprint-resistant photocurable composition (ratio 2) was obtained.

Preparation of Fingerprint Resistant Hard Coat Film (Ratio 2) The composition obtained was coated on a PET film (thickness 100 μm) with a bar coater (No. 8) so that the dry film thickness was 5 μm. And heated at 80 ° C. for 1 minute to remove the solvent and dry. Thereafter, the coating film was formed by exposing and curing the ultraviolet ray with a high-pressure mercury lamp (120 W / cm) so as to have a working energy of 300 mJ / cm ² to obtain a fingerprint-resistant hard coat film (ratio 2).

  The hard coat film sample produced by the above method was evaluated for fingerprint resistance according to the following.

Measurement of Specular Gloss Using a gloss meter MALUTI GROSS 268 (manufactured by Konica Minolta Sensing Co., Ltd.), specular gloss at an incident angle of 20, 60, and 85 degrees was measured.
The specular gloss at an incident angle of 75 degrees was measured using VG2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
Using these measuring instruments, the glossiness of the obtained hard coat film sample was measured and used as the initial glossiness.

Anti-fingerprint evaluation liquid adhesion process and pre-wipe gloss measurement process A cloth impregnated with oleic acid, which is an anti-fingerprint evaluation liquid, was prepared. Silicone rubber stopper No. The lower end face (diameter 16 mm) of No. 4 was coated with a nonwoven fabric waste (Bencot M-1 manufactured by Asahi Kasei Kogyo Co., Ltd.). The part covering the vicinity of the end of the silicone rubber plug of Wes was impregnated with oleic acid by placing a weight of 300 g on a cloth (stamp base) impregnated with oleic acid and impregnating it with oleic acid. A silicone rubber stopper was pressed against a weight of 300 g to attach an anti-fingerprint evaluation solution (oleic acid).
Subsequently, the specular glossiness of the part to which the anti-fingerprint evaluation liquid adhered was measured and used as the glossiness before wiping.

Anti-fingerprint evaluation liquid wiping process and post-wiping gloss measurement process For each hard coat film, after attaching the anti-fingerprint evaluation liquid, a weight of 45 mm in diameter and 300 g load is placed on the waste (Bencot M-1 manufactured by Asahi Kasei Kogyo Co., Ltd.). The anti-fingerprint evaluation solution was wiped off. The specular glossiness (glossiness after wiping) was measured at each time point after wiping times of 5, 10, 15, and 20 times.

Evaluation of anti-fingerprint using specular glossiness Using the initial glossiness, glossiness before wiping and glossiness after wiping measured as described above, the adhesion evaluation rate (%) and the evaluation rate after wiping ( %).
Adhesion evaluation rate (%) = (Glossiness before wiping) / (Initial glossiness) × 100
Evaluation rate after wiping (%) = (Glossiness after wiping) / (Initial glossiness) × 100
In the table below, the adhesion evaluation rate (%) is described as “wipe count 0 times”, and the post-wipe evaluation rate (%) is described as “wipe count 5 times, 10 times, 20 times”. Yes.

  Using the obtained adhesive evaluation rate (%) and post-wiping evaluation rate (%), fingerprint resistance was evaluated according to the following criteria. It can be said that the higher the numerical value of the adhesion evaluation rate (%), the harder a fingerprint mark is and the better the fingerprint resistance. Moreover, the evaluation rate (%) after wiping can be said that the higher the numerical value, the better the wiping property of the oil and fat component and the better the fingerprint resistance.

Evaluation with 20-degree specular gloss The lowest value is 5 to 20 times of wiping.
◎: Wiping rate is 85% or more ○: Wiping rate is 75% or more to less than 85% Δ: Wiping rate is 65% or more to less than 75% ×: Wiping rate is less than 65%

Evaluation with 60-85 degree specular gloss The lowest value is the wiping rate of 5-20 wipes.
A: The wiping rate is 95% or more. B: The wiping rate is 90% to less than 95%. Δ: The wiping rate is 80% to less than 90%. X: The wiping rate is less than 80%.

Comparative Evaluation Example 1 Fingerprint resistance evaluation 1 using haze value
The haze value of the obtained hard coat film sample was measured. Next, oleic acid, which is an anti-fingerprint evaluation solution, was added with silicone rubber stopper No. 4 was applied in the same manner as described above. For each sample, after attaching the anti-fingerprint evaluation solution, then wipe the anti-fingerprint evaluation solution on a rag (Bencot M-1 manufactured by Asahi Kasei Kogyo Co., Ltd.) with a diameter of 45 mm and a load of 300 g, and the number of times of wiping was 5 times. At each time point after 10 times and after 20 times, the haze of the sample was measured according to the following. The Δhaze value was determined as the difference between the haze values before adhesion of the anti-fingerprint evaluation liquid and after adhesion of the anti-fingerprint evaluation liquid or after wiping off the anti-fingerprint evaluation liquid. The obtained Δhaze value and evaluation results are shown in the table. It can be said that the smaller the Δhaze value, the better the wiping property of the fat and oil component, that is, the better the fingerprint resistance.

Measurement of haze (cloudiness value) and total light transmittance Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the diffuse light transmittance (Td (%)) of the sample and the total light transmittance (Tt (%)) were determined. Measured and calculated haze value.
H = Td / Tt × 100
H: Haze (cloudiness value) (%)
Td: Diffuse light transmittance (%)
Tt: Total light transmittance (%)

Evaluation of fingerprint resistance (evaluation based on haze value)
The highest value was calculated | required among the (DELTA) haze value in the frequency | count of wiping 5-20 times, and fingerprint resistance was evaluated by the following reference | standard.
◎: Δ haze is 0.5 or less ○: Δ haze is 1.0 or less to less than 0.5 Δ: Δ haze is 5.0 or less to less than 1.0 ×: Δ haze is 5.0 or more

Comparative Evaluation Example 2 Fingerprint Resistance Evaluation 2 Using Haze Value
One drop of oleic acid was dropped on the film of the obtained sample. Subsequently, it was wiped once, 10 times, 20 times and 30 times using Wes (Bencot M-1 manufactured by Asahi Kasei Kogyo Co., Ltd.). The haze value before the evaluation test and after wiping was measured to obtain the Δ haze value. The obtained Δhaze value and evaluation results are shown in the table. It can be said that the smaller the Δhaze value, the better the wiping property of the fat and oil component, that is, the better the fingerprint resistance.

Evaluation of fingerprint resistance (evaluation based on haze value)
The highest value was calculated | required among (DELTA) haze value in the frequency | count of wiping 1-30 times, and fingerprint resistance was evaluated by the following reference | standard.
◎: Δ haze is 0.5 or less ○: Δ haze is 1.0 or less to less than 0.5 Δ: Δ haze is 5.0 or less to less than 1.0 ×: Δ haze is 5.0 or more

Reference evaluation: Visual evaluation A fingerprint was attached to the coating, and it was wiped lightly 10 times with a clean wiper. The visibility of the fingerprint and the wiping trace at the time of wiping and whether the fingerprint was wiped off were evaluated by the following criteria by visual evaluation.
◎: Fingerprints do not stand out easily when wiping off, and no fingerprint trace remains. ○: Fingerprints are slightly noticeable when wiping off, but no fingerprint trace remains.
Δ: Fingerprints are slightly conspicuous at the time of wiping, and a slight trace of wiping remains.
X: Fingerprints are conspicuous at the time of wiping, and a trace of wiping remains and cannot be easily wiped off.

  The evaluation results are summarized in the following table. However, “85 degree specular gloss” in “Example of evaluation” in the table below is a reference evaluation.

As shown in the practical evaluation examples and comparative evaluation examples, it has been confirmed that the fingerprint resistance evaluation using the specular gloss at an incident angle of 20 to 75 degrees has a high correlation with the conventional visual evaluation. It was.
On the other hand, the anti-fingerprint evaluation using the specular gloss at an incident angle of 85 degrees is also a good result in Comparative Preparation Example 2, which is compared with the visual evaluation as compared with the incident angle of 20 to 75 degrees. It can be seen that there is a lack of correlation.
In Comparative Evaluation Examples 1 and 2 using Δhaze, there is no clear difference in evaluation between Example Preparation Examples 1 and 2 and Comparative Preparation Example 2, indicating that there is a lack of correlation with visual evaluation.

  In addition, the hard coat samples obtained using the compositions of Example Preparation Examples 1 and 2 have superior fingerprint resistance compared to the hard coat samples obtained using the compositions of Comparative Preparation Examples 1 and 2. It was also confirmed that it has.

  The fingerprint resistance evaluation method of the present invention can quantitatively evaluate the sensory evaluation visually. This evaluation method is an evaluation method using the difference in light reflection, while the conventional method of measuring the haze value evaluates the difference in light transmission, and also considers the angle dependency during visual evaluation. This is the evaluation method. The fingerprint resistance evaluation method of the present invention can also be applied to various objects to be evaluated, and in particular, the resistance of a hard coat layer (fingerprint resistance film) on the surface of an opaque housing that cannot be evaluated by a haze value. There is an advantage that it can also be used for evaluation of fingerprint property.

Claims (6)

An initial glossiness measuring step for measuring a 75 to 20 degree specular glossiness of a coating film formed on an object to be an initial glossiness by using a gloss meter;
An anti-fingerprint evaluation liquid adhering step for attaching an anti-fingerprint evaluation liquid on the coating;
Measuring the glossiness of the specular surface of the part to which the anti-fingerprint evaluation liquid is adhered, a glossiness measuring step before wiping,
Wipe off the anti-fingerprint evaluation liquid, the anti-fingerprint evaluation liquid wiping process,
Measuring the specular gloss after wiping off the anti-fingerprint evaluation liquid, measuring the gloss after the wiping process, and processing the obtained measured value according to the following formula to obtain the adhesion evaluation rate and the evaluation rate after wiping:
Adhesion evaluation rate (%) = (Glossiness before wiping) / (Initial glossiness) × 100
Evaluation rate after wiping (%) = (Glossiness after wiping) / (Initial glossiness) × 100
A method for evaluating fingerprint resistance of a coating, comprising: The wiping process in the said anti-fingerprint evaluation liquid wiping process is a process which reciprocates a wiping material 1-40 times by a load of 5-50 g / cm < ² >, and wipes off the anti-fingerprint evaluation liquid of Claim 1. Fingerprint evaluation method. The adhesion process in the fingerprint resistance evaluation liquid adhesion process is as follows:
The lower end surface of the rubber stopper having a diameter of 13 mm or more at the lower end surface portion is coated with a woven fabric or a non-woven fabric, and the coating portion is impregnated with an anti-fingerprint evaluation liquid,
The lower end surface portion of the rubber stopper impregnated with the anti-fingerprint evaluation liquid is pressed onto the film with a load of 50 to 300 g / cm ² to adhere the anti-fingerprint evaluation liquid on the film.
The method for evaluating fingerprint resistance of a coating according to claim 1 or 2, which is a procedure.   The method for evaluating fingerprint resistance of a coating film according to any one of claims 1 to 3, wherein the fingerprint resistance evaluation liquid is at least one selected from higher fatty acids, terpenes and derivatives thereof. An anti-fingerprint film having an adhesion evaluation rate and a post-wiping evaluation rate of 85% or more when the 60 ° specular gloss is measured in the fingerprint resistance evaluation method according to claim 1. There,
The coating has the following components:
Polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends,
A photopolymerizable polyfunctional compound (B), and a photopolymerization initiator (C),
Including
The polyether skeleton-containing urethane (meth) acrylate (A) has the following formula (1):

[In formula, X shows the residue except the hydroxyl group of the both ends of the polyol compound which has a polyether frame | skeleton. ]
And the polyether skeleton-containing urethane (meth) acrylate (A) has a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less.
A fingerprint-resistant film, which is a film formed from a fingerprint-resistant photocurable composition. An anti-fingerprint film having an adhesion evaluation rate and a post-wiping evaluation rate of 85% or more when the 60 ° specular gloss is measured in the fingerprint resistance evaluation method according to claim 1. There,
The coating has the following components:
(A) An acrylic resin having an active methylene group or active methine group (a) and a saturated cycloalkyl group (b) in the molecule, or an acrylic resin having an active methylene group or an active methine group (a) and a saturated cycloalkyl group A mixture with an acrylic resin having (b),
(B) a polyfunctional polymerizable compound having two or more photocurable functional groups in the molecule;
(C) a photopolymerization initiator, and (d) a Michael reaction catalyst,
A fingerprint-resistant coating film, which is a coating formed by a fingerprint-resistant curable composition comprising: