JP4638954B2 - Fingerprint-resistant photocurable composition and painted product provided with fingerprint-resistant coating layer - Google Patents

Description

  The present invention relates to a fingerprint-resistant photocurable composition capable of providing a fingerprint-resistant coating layer having excellent transparency and fingerprint resistance, and fingerprint resistance formed from this fingerprint-resistant photocurable composition The present invention relates to a fingerprint-resistant film provided with a coating layer and a painted product.

  In recent years, liquid crystal display devices (liquid crystal displays) are used in various fields such as computers, word processors, televisions, mobile phones, portable information terminal devices, and portable game machines. Also, so-called touch panel displays having a mechanism for operating devices by holding down the display on the screen are rapidly spreading. Such touch panel displays are, for example, bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, museums, department stores, and other guidance display devices, car navigation, multimedia Widely used in stations (multifunctional terminals installed in convenience stores), mobile phones, railway vehicle monitoring devices, and the like.

  For such optical display devices such as liquid crystal display devices and touch panel displays, fingerprint marks are not formed on the surface of these optical display devices, or even if fingerprint marks are attached, they can be easily wiped off. Fingerprint resistance is required. These optical display devices are also required to have scratch resistance that does not leave scratch marks due to use. In particular, touch panel displays are operated by touching the display surface with a finger, so that a lot of fingerprint traces due to lipid components such as sebum adhere to the surface, and this fingerprint trace adheres to the visibility and operability of the device terminal. There is a problem of preventing.

  Further, in recent years, there has been a demand for improvement in fingerprint resistance other than on the display surface. For example, mobile phones and the like tend to be preferred to have a mirror finish by metal plating or painting that has been subjected to metal plating from the viewpoint of improving design and design. Furthermore, in the case of household electrical appliances, furniture, indoor furniture or cosmetic cases, mirror finishing is also applied by metal plating or painting that has been subjected to metal plating from the viewpoint of improving design and design. There is a tendency to prefer what was made. While these articles are high in design, they have the drawback that fingerprint marks are very noticeable. Therefore, an improvement in fingerprint resistance is also demanded for articles having these mirror finishes.

  As a method to improve antifouling properties such as fingerprint resistance on the surface of optical display devices or mirror-finished products, the surface antifouling properties (water / oil repellency) can be applied by applying silicon oil or fluoropolymer. ) Has been proposed. However, since this method only applies the antifouling agent to the surface, the antifouling agent can be removed immediately and the antifouling effect does not last long, that is, the antifouling durability is inferior. On the other hand, there is also a method of improving antifouling properties such as fingerprint resistance by providing a coating layer using a coating composition containing additives such as silicon oil and fluoropolymer. However, these additives are generally called soft blocks, and also have the property of imparting flexibility to the resin. And there exists a fault that mechanical strength, such as the surface hardness of a coating layer, will fall by adding these.

  In JP 2004-230562 A (Patent Document 1), at least one surface of a transparent substrate film is made of a cured product of an ionizing radiation sensitive resin composition, and the contact angle of water on the surface is 70 ° or less. Thus, a hard coat film characterized by providing a hard coat layer that is surface-treated with an alkaline aqueous solution is described (claim 1). This hard coat film is a method in which the applied composition is once cured by ultraviolet irradiation or the like, and then surface-treated with an alkaline aqueous solution using an alkaline aqueous solution so that the contact angle of water on the surface is 70 ° or less. However, in order for the contact angle of water to be 70 ° or less, advanced process management and many trials and errors are required, which increases the number of processes and is complicated. In addition, there are problems such as the cost of processing a large amount of alkaline waste liquid generated, and there are some problems in industrialization.

  In JP-A-2006-43919 (Patent Document 2), a base film is bonded to an energy ray-curable hard coat composition layer formed on a release film having an average surface roughness Ra of 0.1 μm or less, A method for producing a hard coat film is described, wherein after heating, the energy ray curable hard coat composition layer is cured by irradiating an energy ray to form a hard coat layer in close contact with the base film. (Claim 1). This hard coat film is improving the fingerprint wiping property by using a base film having a smooth surface. The hard coat film is characterized in that the hard coat layer is provided in a state of being sandwiched between the release film and the base film. Therefore, this manufacturing method also requires a preparation process for sandwiching the hard coat layer, and the manufacturing process is complicated. Further, Patent Document 2 considers improvement of fingerprint wiping, and has a different technical background from the present application.

  Japanese Unexamined Patent Application Publication No. 2007-34027 (Patent Document 3) describes a display surface material having an uneven surface (Claim 1). Since the surface material for display has fine irregularities, the biological lipid component that forms the fingerprint attached to the surface of the surface material for display quickly enters the concave portions of the irregularities formed finely. As a result, the fingerprint is visually recognized. It is described that it becomes difficult (such as [0010] paragraph). And the uneven surface of this surface agent is formed by apply | coating an alumina sol liquid and then immersing in warm water (Claim 2). That is, according to the method disclosed in Patent Document 3, it is necessary to form several layers having different roles on the film. The surface material thus formed also requires a post-treatment process such as dipping, the manufacturing process is complicated, and some problems are involved in industrialization.

JP 2004-230562 A JP 2006-43919 A JP 2007-34027 A

  The present invention solves the above-described conventional problems, and its object is to improve the fingerprint resistance of an optical display device surface or a mirror-finished article by a very simple process such as coating. An object of the present invention is to provide a fingerprint-resistant photocurable composition that can be used.

［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、を提供するものであり、これにより上記目的が達成される。 The present invention
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.
A fingerprint-resistant photocurable composition is provided, whereby the above object is achieved.

  The fingerprint-resistant photocurable composition may further contain a polyether or a polyether (meth) acrylate (D).

  The polyether skeleton-containing urethane (meth) acrylate (A) is prepared by reacting a polyol compound (a) having a polyether skeleton, a polyisocyanate (b), and a hydroxyl group-containing (meth) acrylate monomer (c). It is preferably a polyether skeleton-containing urethane (meth) acrylate.

The fingerprint-resistant photocurable composition is
0.5 to 40% by weight of polyether skeleton-containing urethane (meth) acrylate (A),
30-99.5 wt% of photopolymerizable polyfunctional compound (B),
0 to 30% by weight of polyether or polyether (meth) acrylate (D),
(Provided that the total weight of the components (A), (B) and (D) is 100% by weight), and the photopolymerization initiator (C) are added to the components (A) and (B). And 0.1 to 20 parts by weight relative to 100 parts by weight of the total weight of (D),
Is preferably included.

  The present invention further provides a fingerprint-resistant film having a transparent substrate and a coating layer, wherein the coating layer is a coating layer formed by the fingerprint-resistant photocurable composition. To do.

  The present invention further provides a coated article provided with a fingerprint-resistant coating layer formed of the fingerprint-resistant photocurable composition.

  The coated material is preferably a touch panel display, a liquid crystal display, a light emitting diode display, an electroluminescence display, a fluorescent display, a plasma display panel, or an article having a mirror finish.

  By using the fingerprint-resistant photocurable composition of the present invention, a coating layer having excellent fingerprint resistance can be more easily provided on an optical display device surface or an article having a mirror finish. The coating layer obtained by the fingerprint-resistant photocurable composition of the present invention is 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 coating layer obtained by the fingerprint-resistant photocurable composition of the present invention further has excellent scratch resistance and surface film hardness. Even if the coating layer obtained by the fingerprint-resistant photocurable composition of the present invention is a single layer, it has excellent fingerprint resistance, high scratch resistance and surface film hardness. Furthermore, since the fingerprint-resistant photocurable composition of the present invention is photocurable, a coating layer having such excellent performance can be more easily applied on the surface of an optical display device or an article having a mirror finish. There is an advantage that it can be formed. Therefore, by using the fingerprint-resistant photocurable composition of the present invention, a coating layer excellent in production efficiency and manufacturing cost and a fingerprint-resistant film having this coating layer can be formed. Furthermore, this coating layer has the advantage that fingerprint resistance can be maintained for a long period of time and is excellent in fingerprint resistance durability.

The anti-fingerprint photocurable composition of the present invention is
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 fingerprint-resistant photocurable composition of the present invention may further contain a polyether resin or a polyether (meth) acrylate (D).

Polyether skeleton-containing urethane (meth) acrylate (A)
The polyether skeleton-containing urethane (meth) acrylate (A) contained in the fingerprint-resistant photocurable composition of the present invention 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.

  In the present invention, when the component (A) has a polyether structure represented by the above formula (1) via a urethane bond, 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 50,000, 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 the relative decrease in the acrylate group content. This is not preferable because the mechanical strength of the finally obtained coating layer 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.

  In the present invention, a polyether skeleton-containing urethane (meth) acrylate (A) having a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less is 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, the present invention is not completely clarified by the above theory, and has a water tolerance of 6.0 ml or less, a solubility parameter of 12 or less, and a locally high polarity due to having a urethane group. By using the component (A) that has all the properties of having a structure, the fingerprint resistance can be improved. The present inventor has found the above facts through experiments and has completed the present invention.

  In addition, as a more preferable example of the component (A) in this invention, 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 of the present invention is characterized by containing a polyether skeleton-containing urethane (meth) acrylate (A). And in the fingerprint-resistant photocurable composition of this invention, a photopolymerizable polyfunctional compound (B) is further contained as a coating-film formation 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 layer is increased. Become. 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; and isocyanuric acid alkylene oxide modified product of di- or tri (meth) acrylate. By adjusting and applying 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, the physical properties of the resulting coating layer can be improved. It is possible to adjust. 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 layer 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 of the present invention 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 fingerprint-resistant photocurable composition of the present invention may contain a polyether or a polyether (meth) acrylate (D) as necessary. 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 fingerprint-resistant photocurable composition of the present invention, the amount of each component (A), (B) and (D) is:
0.5 to 40% by weight of polyether skeleton-containing urethane (meth) acrylate (A),
30-99.5 wt% of photopolymerizable polyfunctional compound (B),
0 to 30% by weight 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 weight, more preferably 2 to 35% by weight
30 to 99.5% by weight of the photopolymerizable polyfunctional compound (B), more preferably 65 to 98% by weight,
It is more preferable that The total weight of the components (A) and (B) is 100% by weight.
When component (D) is included,
Polyether skeleton-containing urethane (meth) acrylate (A) 0.5 to 40% by weight, more preferably 2 to 35% by weight,
30 to 97% by weight of the photopolymerizable polyfunctional compound (B), more preferably 45 to 95% by weight,
1-30% by weight of polyether or polyether (meth) acrylate (D), more preferably 2-20% by weight,
It is more preferable that The total weight of the components (A), (B) and (D) is 100% by weight. Further, 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 component ratio of (d-1) is less than the preferable lower limit, fingerprint resistance of the obtained hard coat layer 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 less than the above preferable lower limit, the fingerprint resistance of the obtained hard coat layer may be deteriorated, 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 layer may be deteriorated in fingerprint resistance, inferior in bending resistance or curling property and the like. is there. 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 weight, physical strength such as scratch resistance and surface film hardness may be deteriorated.
Moreover, it is preferable that 0.1-20 weight part of photoinitiators (C) are included with respect to 100 weight part of total weight 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 anti-fingerprint photocurable composition of the present invention can be blended with a compound having one ethylenically unsaturated group, if necessary. By including such a compound, the viscosity of the resulting coating liquid, the adhesion of the resulting coating layer, the hardness, and the flexibility can be adjusted. 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 of the present invention may contain a filler such as inorganic particles or organic particles as necessary. By including inorganic particles or organic particles, the scratch resistance and surface film hardness of the coating layer 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 to 50 weight% with respect to the solid content weight of a fingerprint-proof photocurable composition. When the content of inorganic particles or organic particles exceeds 50% by weight, the film strength of the resulting coating layer may be weakened.

  The fingerprint-resistant photocurable composition of the present invention 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 anti-fingerprint photocurable composition of the present invention further comprises a photopolymerization initiation aid, an antistatic agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, and leveling as required. Commonly used additives such as agents and pigments may be included. Examples of photopolymerization initiation assistants that can be preferably used include ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, dibutylethanolamine, and methyldiethanolamine.

Fingerprint-resistant photocurable composition The fingerprint-resistant photocurable composition of the present invention comprises a polyether skeleton-containing urethane (meth) acrylate (A), a photopolymerizable polyfunctional compound (B), and a photopolymerization initiator (C ), And optionally polyether or polyether (meth) acrylate (D). And by using the fingerprint-resistant photocurable composition of the present invention, even a single layer is very excellent in fingerprint resistance, and also excellent in scratch resistance, surface film hardness and fingerprint resistance durability. A coating layer can be formed.

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

  The fingerprint-resistant photocurable composition of the present invention 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 fingerprint-resistant photocurable composition of the present invention may be used after being diluted or may be used without being diluted.

  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.

  The fingerprint-resistant photocurable composition of the present invention 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 fingerprint-resistant photocurable composition of the present invention, 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 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.

  The coating layer 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 painted on the transparent substrate is then cured by being exposed to active energy rays, thereby forming a fingerprint-resistant coating layer. 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.

  In addition, a coating layer can be formed on the surface of the optical display device by coating the fingerprint-resistant photocurable composition of the present invention on the surface of the optical display device. Examples of the optical display device that can be provided with a coating layer using the fingerprint-resistant photocurable composition of the present invention 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. Can be mentioned. By applying the fingerprint-resistant photocurable composition of the present invention to various transparent plastic films, transparent plastic plates and glass used on the surface of these optical display devices, a coating layer is formed on the surface of the optical display device. Can be formed.

  Furthermore, by applying the fingerprint-resistant photocurable composition of the present invention onto the surfaces of articles that have been mirror-finished by metal plating or coating that has been subjected to metal plating, A coating layer having fingerprint resistance 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 coating layer 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 the coating layer so that the resulting coating layer has a thickness of 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, whereby a fingerprint-resistant coating layer is formed.

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

Production Example 1 Preparation of polyether skeleton-containing urethane (meth) acrylate (A1) having at least one (meth) acrylate group at each of both ends 666 parts by weight of isophorone diisocyanate (IPDI), polypropylene glycol (polypropylene glycol 1000, Kishida 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, a polymerization inhibitor. Add 1000 ppm of hydroquinone, and methyl isobutyl ketone (MIBK, used in an amount of 40% solid content) as a solvent, and mix at 80 ° C. for 3 hours while blowing air. did.

  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.

Production Example 2 Preparation of polyether skeleton-containing urethane (meth) acrylate (A2) having at least one (meth) acrylate group at each of both ends 44 parts by weight of isophorone diisocyanate (IPDI), polypropylene glycol (polypropylene glycol 4000, Kishida Chemical) 800 parts by weight, 90 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, a polymerization inhibitor As a solvent, hydroquinone was added at 1000 ppm, and as a solvent, methyl isobutyl ketone (MIBK, used in such an amount that the solid content was 40%) was added, and the mixture was stirred at 80 ° C. for 3 hours while blowing air. Let

  Thus, a polyether skeleton-containing urethane (meth) acrylate (A2) 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 10.7 and the water tolerance value was 3.7. The weight average molecular weight was 9000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Production Example 3 Preparation of polyether skeleton-containing urethane (meth) acrylate (A3) having at least one (meth) acrylate group at each of both ends 44 parts by weight of isophorone diisocyanate (IPDI), polypropylene glycol (polypropylene glycol 2000, Kishida Chemical Co., Ltd.) 400 parts by weight, 90 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, a polymerization inhibitor As a solvent, hydroquinone was added at 1000 ppm, and as a solvent, methyl isobutyl ketone (MIBK, used in such an amount that the solid content was 40%) was added, and the mixture was stirred at 80 ° C. for 3 hours while blowing air. Let

  Thus, a polyether skeleton-containing urethane (meth) acrylate (A3) having acrylate groups 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 11.1 and the water tolerance value was 4.8. The weight average molecular weight was 8,000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Production Example 4 Preparation of polyether skeleton-containing urethane (meth) acrylate (A4) having at least one (meth) acrylate group at each of both ends 44 parts by weight of isophorone diisocyanate (IPDI), polypropylene glycol (Pluronic PE3100, BASF Japan ( 200 parts by weight, 90 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 and a polymerization inhibitor Hydroquinone was added at 1000 ppm, and methyl isobutyl ketone (MIBK, used in an amount of 40% solid content) was added as a solvent, and the mixture was stirred at 80 ° C. for 3 hours while blowing air.

  Thus, a polyether skeleton-containing urethane (meth) acrylate (A4) having acrylate groups 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 11.7 and the water tolerance value was 5.6. The weight average molecular weight was 7000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Comparative Production Example 1 Preparation of Urethane Acrylate (1) 222 parts by weight of isophorone diisocyanate (IPDI), 1000 parts by weight of polypropylene glycol (polypropylene glycol 1000, manufactured by Kishida Chemical Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mixed weight ratio 60:40) 450 parts by weight is added to the reaction vessel, and further dibutyltin dilaurate is 1000 ppm as a catalyst, hydroquinone is 1000 ppm as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, solid content is 40%) as a solvent. The mixture was mixed at 80 ° C. for 3 hours while blowing air to obtain urethane acrylate (1).

  The obtained urethane acrylate had an acrylate group at one end. Moreover, when SP value and water tolerance value of the obtained urethane acrylate were measured, they were SP value 11.2 and water tolerance value 5.2. The weight average molecular weight was 3000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Comparative Production Example 2 Preparation of Urethane Compound 222 parts by weight of isophorone diisocyanate (IPDI) and 2000 parts by weight of polypropylene glycol (polypropylene glycol 1000, manufactured by Kishida Chemical Co., Ltd.) were added to the reaction vessel, and further 1000 ppm of dibutyltin dilaurate as a catalyst. Add 1000 ppm of hydroquinone as a polymerization inhibitor and methyl isobutyl ketone (MIBK, used in an amount that makes the solid content 40%) as a solvent, and mix at 80 ° C. for 3 hours while blowing air. Obtained.

  Moreover, when SP value and water tolerance value of the obtained urethane compound were measured, they were SP value 11.0 and water tolerance value 4.7. The weight average molecular weight was 6000. The weight average molecular weight was expressed in terms of polystyrene by GPC measurement.

Reference Example 1 Preparation of anti-fingerprint photocurable composition Polyether skeleton-containing urethane (meth) acrylate obtained by Production Example 1 40 parts by weight, Aronics M305 (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixed weight) Ratio of about 60:40) 60 parts by weight and 3 parts by weight of Irgacure 184D (1-hydroxy-cyclohexyl-phenyl-ketone) were mixed and adjusted so that the nonvolatile content was 40% by weight using MIBK as a solvent. A fingerprinting photocurable composition was obtained.

The obtained composition was bar-coated on a PET film (thickness 100 μm) with a bar coater (No. 12) so that the dry film thickness was 5 μm, and heated at 80 ° C. for 1 minute to remove the solvent. Removed and dried. Thereafter, the coating layer 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 fingerprint-resistant film.

Examples 2 to 17 Preparation of anti-fingerprint photocurable composition In the same manner as in Reference Example 1 except that the raw materials shown in Tables 1 to 3 were used in parts by weight shown in Tables 1 to 3, fingerprint resistance Photocurable composition was obtained. A coating layer was formed in the same manner as in Reference Example 1 to obtain a fingerprint-resistant film. Only Example 5 was coated so that the dry film thickness was 3 μm.

Comparative Examples 1-14 Preparation of Photocurable Composition Fingerprint-resistant photocuring in the same manner as in Reference Example 1 except that the raw materials shown in Tables 4-5 were used in parts by weight shown in Tables 4-5. Sex composition was obtained. A coating layer was formed in the same manner as in Reference Example 1 to obtain a fingerprint-resistant film.

  The samples with the resulting coating layers were evaluated as described below. The results obtained by these evaluation methods are shown in the following table.

Fingerprint resistance evaluation (Oleic acid wiping evaluation)
One drop of oleic acid was dropped on the coating layer of the obtained sample. Subsequently, it wiped off 10 times using a clean wiper. The haze of the sample before and after the evaluation test was measured according to the above, and the Δ haze value was determined. According to the obtained Δhaze value, fingerprint resistance was evaluated according to the following criteria.
5 points: ΔHaze is less than 0.5 4 points: ΔHaze is 0.5 or more and less than 1.0 3 points: ΔHaze is 1.0 or more and less than 3.0 2 points: ΔHaze is 3.0 or more , Less than 5.0 1 point: ΔHaze is 5.0 or more

The haze value was measured as follows. Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the sample was measured for the diffuse transmittance (T _d (%)) and the total light transmittance (T _t (%)), and the haze value was calculated. The total light transmittance (%) and haze (%) shown in the table are values measured through a PET film portion having a thickness of 100 μm used as a base material for the preparation of the coating layer. It is.

H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

In the coating layer of the evaluation sample obtained in steel wool resistance, a steel wool # 0000, under a load of 500 g / cm ^s, was 100 reciprocating. Thereafter, visual evaluation of the surface of the cured film after the evaluation test was performed, and steel wool resistance was evaluated according to the following criteria.
◎: Almost no scratch ○: Scratch 2 or less △: Scratch 3 or more, 10 or less ×: Scratch 11 or more

Evaluation of solvent resistance The cured film surface was lightly rubbed 100 times with a cotton swab impregnated with MEK (methyl ethyl ketone), and the state of the coating film surface after the test was visually evaluated as follows.
○: No trace Δ: Slight trace ×: Whitening

Evaluation of Pen Sliding Property A 200 g load was applied to a polyacetal pen (tip shape: 0.8 mmR), and a linear sliding test was performed 40,000 times (reciprocating 20,000 times) on the surface of the cured film. The sliding distance at this time was 30 mm, and the sliding speed was 300 mm / second. After this sliding durability test, the sliding portion was visually observed.
○: Almost no trace △: Slight trace present ×: Whitening

Evaluation of Flexibility A cured coating film was measured by a cylindrical mandrel method according to JIS K 5600. Evaluation was made as follows from the minimum diameter of the cylinder in which no cracks occurred in the coating film.
○: Less than 13 mm in diameter △: More than 13 to less than 18 mm in diameter ×: More than 18 mm in diameter

Evaluation of curling property A cured coating film was cut into a 10 cm square, and evaluated by an average value (mm) of the lifted height of the four corners at the time of standing.
○: Less than 10 mm Δ: 10 mm or more, less than 30 mm ×: 30 mm or more

The composition and evaluation results of Examples 1 to 16 and Comparative Examples 1 to 14 are summarized in the following table. The symbols in the table indicate the following contents.
UV-6100B: manufactured by Nippon Synthetic Chemical Co., Ltd., polyether skeleton-containing urethane acrylate having at least one (meth) acrylate group at each end, weight average molecular weight 5000
UV-3700B: manufactured by Nippon Synthetic Chemical Co., Ltd., polyether skeleton-containing urethane acrylate having at least one (meth) acrylate group at each end, weight average molecular weight 41000
UA-47: manufactured by Toho Chemical Co., Ltd., polyether skeleton-containing urethane acrylate having at least one (meth) acrylate group at each of both ends, weight average molecular weight 2000
U-324A: Shin-Nakamura Chemical Co., Ltd., urethane acrylate DPHA-40H: Nippon Kayaku Co., Ltd., urethane acrylate Aronix M305: Toagosei Co., Ltd., pentaerythritol triacrylate and penta Mixture of erythritol tetraacrylate (mixing weight ratio about 60:40)
・ Aronix M309: manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate ・ Aronix M350: manufactured by Toagosei Co., Ltd., trimethylolpropane 3EO modified triacrylate ・ Aronix M450: manufactured by Toagosei Co., Ltd., pentaerythritol Tetraacrylate Irgacure 184D: 1-hydroxy-cyclohexyl-phenyl-ketone Irgacure 907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one polypropylene glycol 400: Kishida chemistry Co., Ltd., polypropylene glycol, average molecular weight 400
Polypropylene glycol 700: manufactured by Kishida Chemical Co., Ltd., polypropylene glycol, average molecular weight 700
Polypropylene glycol 1000: manufactured by Kishida Chemical Co., Ltd., polypropylene glycol, average molecular weight 1000
PE-3100: Pluronic PE3100, manufactured by BASF Japan Ltd., 90% polypropylene glycol, 10% polyethylene glycol block polymer, molecular weight 1000
PE-61: Sanyo Chemical Industries, Ltd., 86% polypropylene glycol, 14% polyethylene glycol block polymer, molecular weight 2000
APG-700: Shin-Nakamura Chemical Co., Ltd., polyether diacrylate, UX-5000: Nippon Kayaku Co., Ltd., polyester acrylate, UX-5001T: Nippon Kayaku Co., Ltd., polyester acrylate Epoxy ester 70PA: manufactured by Kyoeisha Chemical Co., Ltd., epoxy acrylateEpoxy ester 80MFA: manufactured by Kyoeisha Chemical Co., Ltd., epoxy acrylate BYK320: manufactured by Big Chemie Japan Co., Ltd., silicon-based surface conditioner

＊上記表中、比較製造例１のウレタンアクリレート（１）は、片方の末端にのみアクレート基を有するものであり、比較製造例２は、末端にアクリレート基を有しないウレタン化合物である。

* In the above table, the urethane acrylate (1) of Comparative Production Example 1 has an acrylate group only at one end, and Comparative Production Example 2 is a urethane compound having no acrylate group at the end.

As shown in the above table, all of the anti-fingerprint films obtained from the anti-fingerprint photocurable compositions of the examples are anti-fingerprint, anti-steel wool, solvent resistance, pen sliding, It was confirmed that both flexibility and curling properties were excellent.
Comparative Example 1 is an experimental example using urethane acrylate having an acrylate group at one end. In this case, while fingerprint resistance was excellent, steel wool resistance and solvent resistance were inferior.
Comparative Example 2 is an experimental example using a urethane compound having no acrylate group at the terminal. In this case, fingerprint resistance is excellent, but steel wool resistance and solvent resistance are greatly inferior.
Comparative Examples 3 to 4 are experimental examples using urethane acrylate whose SP value or water tolerance value is outside the scope of the present invention. In this case, it was confirmed that the fingerprint resistance was inferior.
Comparative Examples 5 and 6 are experimental examples using polyether or polyether (meth) acrylate (D) in place of the polyether skeleton-containing urethane (meth) acrylate (A). In this case, it was confirmed that the steel wool resistance and the pen sliding property were inferior.
Comparative Examples 7 and 8 are experimental examples using polyester acrylate instead of the polyether skeleton-containing urethane (meth) acrylate (A). In this case, it was confirmed that fingerprint resistance does not appear.
Comparative Examples 9 and 10 are experimental examples using epoxy acrylate instead of the polyether skeleton-containing urethane (meth) acrylate (A). Also in this case, it was confirmed that the fingerprint resistance was not exhibited.
Comparative Examples 11-14 are experimental examples prepared only with the photopolymerizable polyfunctional compound (B). Also in this case, it was confirmed that the fingerprint resistance was not exhibited.

  By using the fingerprint-resistant photocurable composition of the present invention, a coating layer having excellent fingerprint resistance can be more easily provided on the surface of an optical display device or the like. The coating layer obtained by the fingerprint-resistant photocurable composition of the present invention has excellent transparency and is very suitable for use on the surface of an optical display device or the like. The coating layer obtained by the fingerprint-resistant photocurable composition of the present invention further has excellent scratch resistance and surface film hardness. Furthermore, since the fingerprint-resistant photocurable composition of the present invention is photocurable, a coating layer having such excellent performance can be more easily formed on the surface of the optical display device. By using the fingerprint-resistant photocurable composition of the present invention, there is an industrial advantage that a coating layer excellent in production efficiency and production cost can be formed. Furthermore, this coating layer can maintain fingerprint resistance for a long period of time, and is excellent in fingerprint resistance durability.

1 is a cross-sectional schematic view of a fingerprint-resistant film of the present invention.

  DESCRIPTION OF SYMBOLS 1 ... Fingerprint-resistant film, 3 ... Coating layer, 5 ... Transparent base material.

Claims (5)

0.5 to 40% by weight of a polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group at each of both ends,
65 to 98 % by weight of the photopolymerizable polyfunctional compound (B), and 0.1 to 20 parts by weight of the photopolymerization initiator (C) with respect to 100 parts by weight of the total weight of the components (A) and (B),
Including
The polyether skeleton-containing urethane (meth) acrylate (A) is prepared by reacting a polyol compound (a) having a polyether skeleton, a polyisocyanate (b), and a hydroxyl group-containing (meth) acrylate monomer (c). And
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. ]
A polyether skeleton-containing urethane (meth) acrylate having a weight average molecular weight of 3000 to 9000 and a water tolerance of the polyether skeleton-containing urethane (meth) acrylate (A) of 6.0 ml or less. Yes, the solubility parameter is 12 or less,
Fingerprint-resistant photocurable composition. In addition, polyether or polyether (meth) acrylate (D),
0.5 to 40% by weight of polyether skeleton-containing urethane (meth) acrylate (A),
65 to 89% by weight of the photopolymerizable polyfunctional compound (B),
Polyethers or polyether (meth) acrylate (D). 2 to 20 wt%,
(Provided that the total weight of the components (A), (B) and (D) is 100% by weight), and the photopolymerization initiator (C) are added to the components (A) and (B). And 0.1 to 20 parts by weight relative to 100 parts by weight of the total weight of (D),
including,
The fingerprint-resistant photocurable composition according to claim 1.   A fingerprint-resistant film having a transparent substrate and a coating layer, wherein the coating layer is a coating layer formed by the fingerprint-resistant photocurable composition according to claim 1 or 2.   A coated article provided with a fingerprint-resistant coating layer formed of the fingerprint-resistant photocurable composition according to claim 1 or 2.   The coated article according to claim 4, wherein the painted article is a touch panel display, a liquid crystal display, a light emitting diode display, an electroluminescence display, a fluorescent display, a plasma display panel, or an article having a mirror finish.

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