KR20100032322A - Fingerprint resistant photocurable composition and painted article provided with fingerprint resistant coating layer - Google Patents

Abstract

PURPOSE: A fingerprint resistant photocurable composition is provided to improve fingerprint resistance of the surface of an optical display device or finished products through a simple process. CONSTITUTION: A fingerprint resistant photocurable composition comprises a polyether skeleton-containing(meth)acrylate(A) containing at least one (meth)acrylate group at both ends, a photopolymerizable multifunctional compound(B), and a photopolymerization initiator(C). The polyether skeleton-containing(meth)acrylate(A) containing a (meth)acrylate group has a structure represented by chemical formula 1.

Description

FINGERPRINT RESISTANT PHOTOCURABLE COMPOSITION AND PAINTED ARTICLE PROVIDED WITH FINGERPRINT RESISTANT COATING LAYER}

The present invention relates to an anti-fingerprint photocurable composition capable of imparting an anti-fingerprint coating layer having excellent transparency and anti-fingerprint, and an anti-fingerprint film and a coating material provided with an anti-fingerprint coating layer formed from the anti-fingerprint photocurable composition.

BACKGROUND ART Liquid crystal displays (liquid crystal displays) have recently been used in various fields such as computers, word processors, televisions, mobile phones, portable information terminal devices, portable game machines, and the like. Moreover, what is called a touch panel display which has a mechanism which operates an apparatus by pressing the display on a screen is rapidly spreading. Such touch panel displays include, for example, information display devices installed in facilities such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimile machines, game machines, museums and department stores, car navigation systems, and multimedia stations (convenience store). It is widely used in a multi-function terminal installed in), a mobile phone, a monitor of a railroad car, and the like.

As for such an optical display device such as a liquid crystal display device and a touch panel display, so-called fingerprint properties such that fingerprint marks are not adhered to the surface of these optical display devices or can be simply wiped off even if fingerprint marks are attached are requested. It is becoming. Regarding these optical display devices, there is also a request for abrasion resistance such that no scratch marks by use remain. In particular, in the touch panel display, the touch screen is operated by touching the display surface with a finger, so that many fingerprint marks due to lipid components such as sebum adhere to the surface, and the attachment of the fingerprint marks results in visibility and operability of the device terminal. There is a problem to disturb.

Moreover, in recent years, the improvement of anti-fingerprint is calculated | required also besides a display surface. For example, in the case of a mobile phone or the like, from the viewpoint of the designability and the designability, it is a tendency that mirror finishing by metal plating processing or painting by which metal plating processing has been performed is preferably performed. In addition, in the case of household appliances, furniture, indoor daily necessities, or cosmetics, and also in terms of design and improvement of design, mirror finish is performed by metal plating processing or coating such as metal plating processing. Tend to be preferred. While these articles are highly designable, they have the drawback that the adhesion of fingerprint marks is very noticeable. Therefore, also in the article in which these mirror finishes were given, improvement of anti-fingerprint is calculated | required.

In the article on which the surface of an optical display device or mirror surface was given, the method of improving the antifouling property, such as anti-fingerprint, etc., is proposed to improve the antifouling property (water / oil repellency) of a surface by apply | coating silicone oil or a fluoropolymer. . However, since this method only applies an antifouling agent to the surface, there is a drawback that the antifouling agent immediately falls off and the effect of the antifouling property does not last long, that is, the antifouling durability is inferior. On the other hand, there also exists a method of improving antifouling property, such as anti-fingerprint, by providing a coating layer using coating composition containing these silicone oil, additives, such as a fluoropolymer. However, these additives are generally called soft blocks and have the property of providing flexibility to the resin. And by adding these, there exists a fault that mechanical strength, such as surface hardness of a coating layer, falls.

Japanese Laid-Open Patent Publication No. 2004-230562 (Patent Document 1) includes an aqueous alkaline solution such that at least one surface of the transparent base 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. The hard coat film provided with the hard coat layer surface-treated is described (claim 1). Although the hard coating film is hardened by ultraviolet irradiation etc. once, the apply | coated composition is surface-treated with alkaline aqueous solution so that the contact angle of the surface water may be 70 degrees or less using alkaline aqueous solution, but the contact angle of water is employ | adopted, In order to be below 70 °, high process control and a lot of trial and error are required, which increases the cumbersome process. In addition, problems such as the cost of treating a large amount of alkaline waste liquid generated are included, and some problems are included in industrialization.

In JP 2006-43919 A (Patent Document 2), a base film is bonded to an energy ray curable hard coating composition layer formed on a release film having an average surface roughness Ra of 0.1 μm or less, and then irradiated with energy rays after heating. A method for producing a hard coat film is described, wherein the energy ray-curable hard coat composition layer is cured to form a hard coat layer in close contact with the base film (claim 1). This hard coat film aims at the improvement of fingerprint wipeability by using the base film which has a smooth surface. Moreover, this hard coat film is characterized by providing the hard coat layer in a state sandwiched between the release film and the base film. Therefore, this manufacturing method also requires a preparation step for making the hard coating layer sandwiched, which is cumbersome. Moreover, patent document 2 considers the improvement of the wipe-ability of a fingerprint, and a technical background differs from this application.

Japanese Unexamined Patent Publication No. 2007-34027 (Patent Document 3) describes a surface material for a display having an uneven surface (claim 1). Since the surface material for displays has fine unevenness, it is described that fingerprints become difficult to be visually recognized as a result of rapid entry into the recesses of the finely formed biologically derived lipid components that form fingerprints attached to the surface of the surface material for display. (Such as paragraphs). And the uneven surface of this surface agent is formed by apply | coating an alumina sol liquid and then immersing in hot water (claim 2). That is, according to the method of patent document 3, it is necessary to form several layers which have another role on a film. The surface material thus formed also needs a post-treatment step such as immersion, and the manufacturing process is complicated and includes some problems in industrialization.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-230562

Patent Document 2: Japanese Patent Application Laid-Open No. 2006-43919

Patent Document 3: Japanese Patent Application Laid-Open No. 2007-34027

This invention solves the said conventional problem, The part made into the objective is a fingerprint-proof spectacle which can improve the fingerprint-proof property of the article on which the optical display surface or mirror surface finish was performed by the very simple process by coating etc. It is providing a chemical composition.

The present invention,

Polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group in each sock end,

Photopolymerizable multifunctional compound (B), and

Photopolymerization initiator (C),

Including,

The polyether skeleton-containing urethane (meth) acrylate (A) has a structure represented by the following formula (1),

[Formula 1]

[Wherein X represents a residue excluding the hydroxyl group of the sock end of the polyol compound having a polyether skeleton]

The water tolerance of the said polyether skeleton containing urethane (meth) acrylate (A) is 6.0 ml or less, and the solubility parameter is 12 or less,

It is providing an anti-fingerprint photocurable composition, by which the said objective is achieved.

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

Moreover, the said polyether skeleton containing urethane (meth) acrylate (A) is a polyol compound (a), a polyisocyanate (b), and a hydroxyl group containing (meth) acrylate monomer (c) which has a polyether skeleton. It is preferable that it is a polyether skeleton containing urethane (meth) acrylate prepared by making () react.

The anti-fingerprint photocurable composition,

0.5 to 40% by weight of a polyether skeleton-containing urethane (meth) acrylate (A),

30-99.5 weight% of photopolymerizable multifunctional compounds (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

0.1 to 20 parts by weight of the photopolymerization initiator (C) based on 100 parts by weight of the total weight of the components (A), (B) and (D)

It is preferable to include.

The present invention also provides an anti-fingerprint film having a transparent substrate and a coating layer, wherein the coating layer is a coating layer formed by the anti-fingerprint photocurable composition.

The present invention also provides a coating having an anti-fingerprint coating layer formed by the anti-fingerprint photocurable composition.

It is preferable that the said coating material is a touch panel display, a liquid crystal display display, a light emitting diode display, an electroluminescent display, a fluorescent display, a plasma display panel, or a mirror-finished product.

By using the anti-fingerprint photocurable composition of this invention, the coating layer which has the excellent anti-fingerprint property etc. in the surface of an optical display device, the article which mirror-finished, etc. were given can be installed more easily. The coating layer obtained by the anti-fingerprint 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 subjected to mirror finish. The coating layer obtained by the anti-fingerprint photocurable composition of the present invention also has excellent scratch resistance and film hardness of the surface. Even if it is a single | mono layer, the coating layer obtained by the anti-fingerprint photocurable composition of this invention has the outstanding anti-fingerprint property, high scratch resistance, and the film hardness of the surface. Furthermore, since the anti-fingerprint photocurable composition of the present invention is photocurable, there is an advantage that a coating layer having such excellent performance can be more easily formed on the surface of an optical display device or an article subjected to mirror finish. Therefore, by using the anti-fingerprint photocurable composition of this invention, the coating layer excellent in production efficiency and a manufacturing cost, and the anti-fingerprint film which has this coating layer can be formed. Moreover, this coating layer has the advantage that anti-fingerprint can be maintained for a long time, and also excellent anti-fingerprint durability.

Anti-fingerprint photocurable composition of the present invention,

Polyether skeleton containing urethane (meth) acrylate (A) which has at least 1 (meth) acrylate group in each sock end,

Photopolymerizable multifunctional compound (B), and

Photopolymerization Initiator (C)

It includes. The anti-fingerprint photocurable composition of this invention may further contain polyether resin or polyether (meth) acrylate (D).

Polyether skeleton containing urethane (meth) acrylate (A)

Polyether skeleton containing urethane (meth) acrylate (A) contained in the anti-fingerprint photocurable composition of this invention,

(i) having at least one (meth) acrylate group at each end of the molecule,

(ii) having a structure represented by the following formula (1), and

[Formula 1]

[Wherein X represents a residue excluding the hydroxyl group of the sock end of the polyol compound having a polyether 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 of.

In the present invention, when the component (A) has a polyether structure sandwiching the urethane bond represented by the above formula (1), excellent anti-fingerprint is obtained. In addition, when the component (A) has at least one (meth) acrylate group in each of the sock ends, good scratch resistance is obtained.

Moreover, the urethane (meth) acrylate of component (A) may have a branched structure. In this case, the term "both ends" means both ends in a 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 end of the sock end having a structure represented by the above formula (1), for example, a polyol compound having a polyether skeleton (a) ), A polyisocyanate (b) and a reactant of 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- Polyether polyols having one or more structures of hexanediol, bisphenol A polyethoxy diol, polycaprolactone, and polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide or random copolymerization; Polyether-modified polyhydric alcohols such as trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerol and polytetramethylene glycol, Polyhydric alcohols including polyether skeletons; Polyester polyols which are condensates of the polyether polyols with polybasic acids such as maleic anhydride, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid; And caprolactone-modified polyols in which caprolactone-modified polyether polyols are used.

Examples of the polyisocyanate (b) include polyisocyanates such as aromatics, aliphatics, and alicyclic systems, among which tolylene diisocyanate and diphenylmethane diisocyanate. Nate, Hydrogenated Diphenylmethane Diisocyanate, Polyphenylmethane Polyisocyanate, Modified Diphenylmethane Diisocyanate, Hydrogenated Xylene Diisocyanate, Xylene Diisocyanate Anate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3 Bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, la Polyisocyanates such as shin triisocyanate, naphthalene diisocyanate or trimer compounds of these polyisocyanates, biuret polyisocyanates, water dispersion polyisocyanates Or reaction products of these polyisocyanates and polyols.

The hydroxyl group-containing (meth) acrylate monomer (c) may be a monofunctional monomer having one (meth) acrylate group or may be a polyfunctional monomer having two or more (meth) acrylate groups. As the monofunctional monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloxyethyl 2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, and the like. As the polyfunctional monomer, for example, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 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 Etc. can be mentioned.

The polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group in each of the socks ends is a polyol compound (a), a polyisocyanate (b) and a hydride having a polyether skeleton. It can prepare by making a hydroxyl group containing (meth) acrylate monomer (c) react. In this preparation, for example, a polyol compound (a) having a polyether skeleton, a polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate monomer (c) may be reacted at once, or for example, poly After the polyol compound (a) having an ether skeleton is reacted with the polyisocyanate (b), the hydroxyl group-containing (meth) acrylate monomer (c) may be reacted.

Reaction of the polyol compound (a) and polyisocyanate (b) which have a polyether backbone is isocyanate of polyisocyanate (b) with respect to 1 equivalent of hydroxyl groups of a polyol compound (a). It is preferable to react 1.1-2.5 equivalents of groups, and it is especially preferable to react 1.3-2.0 equivalents. 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 is used. It is more preferable to promote the reaction by use.

In the case of reacting a polyol compound (a) having a polyether skeleton, a polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate monomer (c) at once, a hydroxyl group-containing (meth) acrylate It is preferable to use 1.0-1.5 equivalent with respect to 1 equivalent of polyisocyanate (b), and, as for the quantity of monomer (c), 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.

Moreover, when making a hydroxyl group containing (meth) acrylate monomer (c) react, after making polyol compound (a) and polyisocyanate (b) which have a polyether skeleton react, a polyol compound (a ) And 0.95 to 1.5 equivalents of hydroxyl groups of the hydroxyl group-containing (meth) acrylate monomer (c) with respect to 1 equivalent of isocyanate groups of the reactants of the polyisocyanate (b), , 1.0 to 1.1 equivalents is particularly preferred. The reaction temperature is preferably 60 to 100 ° C, and the reaction time is preferably 1 to 20 hours.

As for the polyether skeleton containing urethane (meth) acrylate (A) which has at least 1 (meth) acrylate group in each sock end, it is more preferable that weight average molecular weights are 3000-50000. When the weight average molecular weight of the polyether skeleton-containing urethane (meth) acrylate (A) is less than 3000, the molecular weight of the polyol compound (a) having a polyether skeleton is lowered and the urethane group content is relatively high, so the viscosity at the time of manufacture There is a fear of productivity decrease due to the increase. On the other hand, when it exceeds 50000, since the viscosity of the anti-fingerprint photocurable composition obtained becomes high, the productivity of the anti-fingerprint photocurable composition decreases, and since the acrylate group content rate decreases relatively, the mechanical strength of the coating layer finally obtained is reduced. There is concern and is not preferable. In addition, the average molecular weight here is a weight average molecular weight and can be computed from the measurement result of a gel permeation chromatography (GPC) using polystyrene as a standard.

In this invention, as a polyether skeleton containing urethane (meth) acrylate (A), a water tolerance is 6.0 ml or less, and the solubility parameter is 12 or less is used. When the water tolerance of component (A) is 6.0 ml or less and the solubility parameter is 12 or less, favorable anti-fingerprint is obtained.

Water tolerance evaluates the degree of hydrophilicity, and the higher the value, the higher the hydrophilicity. In the method of measuring the water tolerance, 0.5 g of the polyether skeleton-containing urethane (meth) acrylate (A) is mixed in 10 ml of tetrahydrofuran and dispersed in a 100 ml beaker under conditions of 23 ° C, using a burette in the mixture. Then, ion-exchanged water is gradually added, and the amount (ml) of ion-exchanged water required until cloudiness occurs in the mixture is measured. The amount (ml) of this ion-exchange water is defined by water tolerance.

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

SP value can be measured by the following method (refer to SUH, CLARKE, J. P. S. A-1, 5, 1671-1681 (1967)).

Measuring temperature: 20 ℃

Sample: 0.5 g of resin is weighed into a 100 ml beaker, 10 ml of a good solvent is added using a hole pipette, and dissolved in a magnetic stirrer.

menstruum:

Good solvent… Dioxane, acetone, etc.

Empty solvent… n-hexane, ion-exchanged water, etc.

Turbidity measurement: The poor solvent is dripped using a 50 ml burette, and the cloudy point is taken as a drop amount.

The SP value δ of component (A) is given by the following equation.

Vi: molar volume of solvent (ml / mol)

φi: volume fraction of each solvent in the turbidity point

δi: SP value of the solvent

ml: Low SP poor solvent mixture system

mh: High SP poor solvent mixture

The reason why a good anti-fingerprint is obtained by the fact that the water tolerance of component (A) is 6.0 ml or less and the solubility parameter is 12 or less is not limited by theory, but is considered as follows. Since component (A) has a urethane group, it has a locally polar part structure in a molecule | numerator. On the other hand, component (A) is said to be a compound with low polarity as a whole molecule | numerator since several tolerances are 6.0 ml or less. Here, the lipid component constituting the fingerprint mark is called a long chain fatty acid, and the long chain fatty acid is composed of a portion having a low polarity by an alkyl group and a carboxyl group having a high polarity. In order to improve anti-fingerprint, it is thought that the affinity to the lipid component constituting the fingerprint mark may be increased. Therefore, as described above, a highly polarized site (urethane group) and a low polarity property as a whole molecule are obtained. It is thought that favorable anti-fingerprint was provided by using the component (A) which has. 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 referred to as a compound having a low polarity as a whole molecule. And by this, affinity with the lipid component which comprises a fingerprint mark becomes high, and it is thought that anti-fingerprint improves. On the other hand, the water tolerance of 6.0 ml or less and the solubility parameter of 12 or less all show a low polarity property as a whole molecule. On the other hand, the present invention is not all solved by the above theory, but has a property of having a locally polar structure having a water tolerance of 6.0 ml or less, a solubility parameter of 12 or less, and having a urethane group. By using the component (A) which has both, the improvement of fingerprint-proof is achieved. The inventors have found the above facts by experiment and have come to complete the present invention.

On the other hand, as a more preferable example of the component (A) in this invention, the polyether skeleton containing urethane (meth) acrylate represented by the following general formula is mentioned, for example.

[Wherein, R ¹ is a residue excluding the hydroxyl group of the sock end of the polyol compound (a) having a polyether skeleton, and R ² is a residue except the isocyanate group of the sock end of the polyisocyanate (b). And R ³ and R ⁴ are residues excluding the hydroxyl group of the hydroxyl group-containing (meth) acrylate monomer (c), which may be the same or different, and n is an integer of 1 to 60.]

As for the said polyether skeleton containing urethane (meth) acrylate (A), it is more preferable that weight average molecular weights are 3000-50000. Moreover, it is more preferable that said n is an integer of 1-60, and it is more preferable that it is an integer of 1-30.

Photopolymerizable Multifunctional Compound (B)

The anti-fingerprint photocurable composition of this invention is characterized by containing a polyether skeleton containing urethane (meth) acrylate (A). And in the anti-fingerprint photocurable composition of this invention, a photopolymerizable polyfunctional compound (B) is further contained as a coating film formation component. As the photopolymerizable polyfunctional compound (B) is included, the photocurability of the anti-fingerprint photocurable composition is improved, and the mechanical strength (scratch resistance, etc.) of the obtained coating layer is increased. The photopolymerizable polyfunctional compound (B) is a compound having two or more photopolymerizable groups in one molecule. As a photopolymerizable polyfunctional compound (B), the compound which has two or more (meth) acrylate groups in a molecule | numerator can be used. As a photopolymerizable polyfunctional compound (B), the compound which has 3 or more (meth) acrylate groups is preferable. Moreover, as a photopolymerizable polyfunctional compound (B), if it is a compound which has two or more (meth) acrylate groups, it may be a monomer or an oligomer.

As a monomer, Alkylene glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate and a propylene glycol di (meth) acrylate; Low molecular weight polyalkylene glycol di (meth) such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate ) Acrylate or its alkylene oxide modified substance; Trimethylolpropane tri (meth) acrylate, pentaerythritol di or tri or tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylic Polyol poly (meth) acrylates or alkylene oxide modified compounds thereof such as late; Di or tri (meth) acrylate of an isocyanuric-acid alkylene oxide modified body, etc. are mentioned. By adjusting and applying the mixing ratio of the compound which has two (meth) acrylate groups in these molecules, and the compound which has three or more (meth) acrylate groups in a molecule | numerator, it is possible to adjust the physical property of the coating layer obtained. In a photopolymerizable polyfunctional compound (B), 50-100% is preferable and, as for the content rate which the compound which has three or more (meth) acrylate groups in a molecule occupies, 70-100% is more preferable. When the content rate of the photopolymerizable multifunctional compound (B) having three or more (meth) acrylate groups in the molecule is less than 50%, the wound prevention property, solvent resistance, pen slip, which is represented by the steel wool resistance of the finally obtained film It is unpreferable because there exists a possibility that mobility may fall.

As an oligomer, oligomers, such as polyester (meth) acrylate, epoxy (meth) acrylate, and acryl (meth) acrylate, are mentioned. On the other hand, it is preferable that weight average molecular weights of these oligomers which can be used as a photopolymerizable polyfunctional compound (B) are 300-5,000, and it is more preferable that they are 500-3,000. When it is larger than 5,000, it becomes high viscosity and there exists a possibility that handling may become difficult.

These photopolymerizable polyfunctional compounds (B) may be used individually by 1 type, and may use 2 or more types together.

As a photopolymerizable polyfunctional compound (B), it is preferable to use the monomer which has 3 or more photopolymerizable groups (namely, a (meth) acrylate group) in at least one molecule in 1 molecule. By using such a monomer, the mechanical strength of the coating layer obtained can be raised more. As a preferable photopolymerizable polyfunctional compound (B), pentaerythritol triacrylate, a trimethylol propane EO modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. are mentioned, for example. .

Photopolymerization Initiator (C)

It is preferable that the anti-fingerprint photocurable composition of this invention contains a photoinitiator (C). By the presence of a photoinitiator (C), the polymerizability of the anti-fingerprint photocurable composition with respect to active energy ray irradiation, such as an ultraviolet-ray, improves. As an example of a photoinitiator (C), an alkylphenone type photoinitiator, an acylphosphine oxide type photoinitiator, a titanocene type photoinitiator, an oxime ester type polymerization initiator, etc. are mentioned, for example. As alkylphenone type photoinitiators, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1 -Phenyl-propan-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-propane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. are mentioned. As an acylphosphine oxide type photoinitiator, 2,4,6- trimethylbenzoyl- diphenyl- phosphine oxide and bis (2,4,6- trimethylbenzoyl) -phenylphosphine oxide are mentioned, for example. As a titanocene type photoinitiator, For example, bis ((eta) 5-2, 4- cyclopentadien- 1-yl) -bis (2, 6- difluoro-3- (1H-pyrrol- 1-yl) -phenyl Titanium etc. are mentioned. Examples of the oxime ester polymerization initiators include, for example, 1.2-octane ion, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2 -(2-hydroxyethoxy) ethyl ester, etc. are mentioned. Hydrogen drawing initiators, such as benzophenone, 2,4,6- trimethyl benzophenone, methyl benzoyl benzoate, 2, 4- diethyl thioxanthone, 2-ethyl anthraquinone, camphor quinone, can also be used. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

In the said photoinitiator (C), 2-hydroxy- 2-methyl- 1-phenyl- propane- 1-one, 1-hydroxy cyclohexyl-phenyl- ketone, 2-methyl- 1- (4-methyl thi Ophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,2-dimethoxy-1 , 2-diphenylethan-1-one and the like are more preferably used.

Polyether or polyether (meth) acrylate (D)

The anti-fingerprint photocurable composition of this invention may contain polyether or polyether (meth) acrylate (D) as needed. When the anti-fingerprint photocurable composition contains the component (D) which is a polyether resin or a polyether (meth) acrylate, there exists an advantage that anti-fingerprint performance improves. In particular, by the inclusion of component (D), the affinity with lipids is further improved, and the specific performance of further improving fingerprint wipeability 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. As "an alkylene oxide having 3 or more carbon atoms", for example, a propylene oxide containing an isopropylene oxide represented by -O-CH ₂ -CH (CH ₃ )-, and a tetramethylene oxide represented by -O- (CH ₂ ) _4- And alkylene oxide having 3 to 4 carbon atoms, such as 3-chloropropylene oxide represented by -O-CH ₂ -CH (CH ₂ Cl)-. As for "the C3 or more alkylene oxide (d-1)", it is more preferable that it is propylene oxide, and it is more preferable that it is isopropylene oxide. Alkylene oxide (d-2) which does not occupy 3 carbon atoms of the alkyl-group part of a polyether can also be used, but since anti-fingerprint performance mainly gives "alkylene oxide of 3 or more carbon atoms", an alkylene oxide of 3 or more carbon atoms is It is preferable to constitute at least a part of component (D).

It is preferable that molecular weight is 400 or more, and, as for a polyether or polyether (meth) acrylate (D), it is more preferable that it is 700 or more. Moreover, the molecular weight here can be calculated from the measurement result of the hydroxyl value computed by JISK1557.

As the polyether or polyether (meth) acrylate (D), commercially available polyether or polyether (meth) acrylate can be used. As a polyether or polyether (meth) acrylate which can be used preferably, the polypropylene series by Kishida Chemical Co., Ltd. and the polyether diacrylate series by Shin-Nakamura Chemical Co., Ltd. are mentioned, for example.

In the anti-fingerprint photocurable composition of the present invention, the amounts of each component (A), (B) and (D) are

0.5 to 40% by weight of a polyether skeleton-containing urethane (meth) acrylate (A),

30-99.5 weight% of photopolymerizable multifunctional compounds (B),

0 to 30% by weight of polyether or polyether (meth) acrylate (D),

Is preferably.

More specifically, when the component (D) is not included,

0.5 to 40% by weight of polyether skeleton-containing urethane (meth) acrylate (A), more preferably 2 to 35% by weight

30 to 99.5% by weight of the photopolymerizable multifunctional compound (B), more preferably 65 to 98% by weight,

It is more preferable that is. Moreover, it is provided that the total weight of the said components (A) and (B) will be 100 weight%.

In addition, when a component (D) is contained,

0.5 to 40% by weight of polyether skeleton-containing urethane (meth) acrylate (A), more preferably 2 to 35% by weight,

30 to 97% by weight of the photopolymerizable multifunctional compound (B), more preferably 45 to 95% by weight,

1 to 30% by weight of polyether or polyether (meth) acrylate (D), more preferably 2 to 20% by weight

It is more preferable that is. The total weight of the components (A), (B) and (D) is set to 100% by weight. Furthermore, when the component (D) to be blended together has an alkylene oxide (d-1) having 3 or more carbon atoms and an alkylene oxide (d-2) having less than 3 carbon atoms, the component (D) included in the component (D) (d-1) It is preferable that 25 mass% or more is (d-1) in the sum total of (d-2). If the structural ratio of (d-1) is less than the said preferable minimum, the anti-fingerprint of the hard coat layer obtained may fall, and it is unpreferable. In addition, in this case, the upper limit of the said ratio of (d-1) contained in a component (D) is 100 mass%.

Moreover, the component (D) mix | blended is a polyether or polyether (meth) acrylate (D-1) derived from (d-1), and the polyether or polyether (meth) acrylate (D-2) derived from (d-1) ( In the case of the mixture of D-2), it is preferable that 10 mass% or more is (D-1) in the sum total of (D-1) and (D-2). When the compounding ratio of (D-1) is less than the said preferable minimum, the anti-fingerprint of the obtained hard coat layer may fall, and it is unpreferable. In addition, in this case, the upper limit of the said ratio of (D-1) contained in a component (D) is 100 mass%.

When the amount of the polyether skeleton-containing urethane (meth) acrylate (A) is less than the above range, there is a fear that the anti-fingerprint degradation, flex resistance, curl resistance, and the like of the obtained anti-fingerprint coating layer may be inferior. Moreover, when the quantity of polyether skeleton containing urethane (meth) acrylate (A) exceeds the said range, there exists a possibility that steel-resistant or solvent resistance etc. may fall. When the amount of the photopolymerizable polyfunctional compound (B) is less than 30% by weight, there is a possibility that the physical strength such as scratch resistance and film hardness of the surface may be inferior.

Moreover, it is preferable to contain 0.1-20 weight part of photoinitiators (C) with respect to 100 weight part of total weights of a component (A), (B), and (D). When the amount of the photopolymerization initiator (C) is out of the above range, there is a possibility that the photocurability becomes insufficient and the physical strength is inferior.

Other ingredients

The anti-fingerprint photocurable composition of this invention can mix | blend the compound which has one ethylenically unsaturated group as needed. By including such a compound, the viscosity of the coating liquid obtained, the adhesiveness of the coating layer obtained, hardness, and flexibility can be adjusted. As a compound which has one ethylenically unsaturated group, (meth) acrylate compound which has cyclic structures, such as cyclohexyl (meth) acrylate, isoboroyl (meth) acrylate, and tetrahydroperfuryl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylate compounds of alkoxy oxide adducts of phenols such as phenoxyethyl (meth) acrylate; Mono (meth) acrylates of glycols such as ethylene glycol mono (meth) acrylate, methoxyethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate and tripropylene glycol mono (meth) acrylate; Vinyl compounds, such as N-vinylpyrrolidone and N-vinyl caprolactam, etc. are mentioned.

The anti-fingerprint photocurable composition of this invention may contain fillers, such as an inorganic particle or organic particle | grains as needed. By including an inorganic particle or organic particle | grains, the scratch resistance of a coating layer and the film hardness of a surface can further be improved, or anti-glare property can be provided. As for these inorganic particles or inorganic particles, it is more preferable that they are about 5 nm-about average particle diameters. As an inorganic particle which can be used, microparticles | fine-particles of a metal or metal oxide are mentioned, for example. As a metal, Si, Ti, Al, Zn, Zr, In, Sn, Sb etc. are mentioned, for example. Specific inorganic particles include silica, alumina, zirconia, titania and the like. Moreover, as for these inorganic particles, it is more preferable to modify | denature the particle surface by UV-curable functional group, for example, an acrylate group. Moreover, as an organic particle | grain which can be used, organic particle | grains, such as an acryl and polyester, are mentioned, for example.

On the other hand, when using an inorganic particle or organic particle | grains, it is preferable to use about 0.1-50 weight% with respect to the solid content weight of an anti-fingerprint photocurable composition. When content of an inorganic particle or organic particle | grain exceeds 50 weight%, there exists a possibility that the film strength of the coating layer obtained may become weak.

The anti-fingerprint photocurable composition of this invention may further contain the organic solvent as a dilution solvent as needed. As such an organic solvent, for example, examples of the solvent used include aromatic solvents such as toluene and xylene; Aliphatic solvents such as hexane, heptane, octane and mineral spirits; Ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; 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, Ether solvents such as phentol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; Amide solvents such as dimethylformamide, diethylformamide, dimethylsulfoxide and N-methylpyrrolidone; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Ether ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Alcohol solvents such as methanol, ethanol and propanol; And halogen-based 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 includes, if necessary, additives commonly used such as photopolymerization initiators, antistatic agents, polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, pigments, and the like. You may. For example, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, dibutyl ethanol amine, methyldiethanol amine, etc. are mentioned as a photoinitiator which can be used preferably.

Anti-fingerprint photocurable composition

The anti-fingerprint photocurable composition of this invention is a polyether skeleton containing urethane (meth) acrylate (A), a photopolymerizable polyfunctional compound (B), and a photoinitiator (C), and polyether or polyether (meth) as needed. ) Acrylate (D). And by using the anti-fingerprint photocurable composition of this invention, even if it is a single | mono layer, it is possible to form the coating layer which is very excellent in anti-fingerprint, and also excellent in scratch resistance, surface film hardness and anti-fingerprint durability.

Moreover, the anti-fingerprint photocurable composition of this invention is photocurable. Therefore, it has the advantage that it does not need to heat-polymerize when forming a coating layer. Many optical display apparatuses also include a member having a low heat resistance such as a resin film. The anti-fingerprint photocurable composition of this invention has the advantage that a coating layer can be formed favorably also with respect to the optical display apparatus and resin film which comprise such a low heat resistance member.

The anti-fingerprint photocurable composition of this invention can be prepared by mixing the said component. In addition, at the time of preparation of a composition, the organic solvent which can be used for dilution can be used as needed. On the other hand, the anti-fingerprint photocurable composition of this invention may be diluted, and may be used without diluting.

As a preparation method of an anti-fingerprint photocurable composition, the said polyether skeleton containing urethane (meth) acrylate (A), a photopolymerizable polyfunctional compound (B), and a photoinitiator (C), and polyether or poly as needed, for example It can prepare by mixing ether (meth) acrylate (D), an additive, an organic solvent, etc.

Moreover, it is preferable that the anti-fingerprint photocurable composition of this invention does not contain any of 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 coating layer obtained, and improving the antifouling properties, the oil-repellent component adhering to the coating layer may be thrown off by the improvement of the water repellency and oil repellency, and the contamination may be conspicuous. Because there is.

By using the anti-fingerprint photocurable composition of this invention, an anti-fingerprint film can be easily prepared. This anti-fingerprint film has a transparent base material and a coating layer. This coating layer is a layer formed from said anti-fingerprint photocurable composition, and a fingerprint-proof is exhibited by presence of this layer.

As a transparent base material used for preparation of an anti-fingerprint film, various transparent plastic films, such as a triacetyl cellulose (TAC) film, a polyethylene terephthalate (PET) film, a diacetyl cellulose film, an acetate butyrate cellulose film, a polyether sulfone film, Polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyether ketone films, (meth) acrylonitrile films, and the like can be used. As the transparent substrate, it is preferable to use polyethylene terephthalate. In addition, although the thickness of a transparent base material can be selected timely according to a use, it is generally used in about 25-1000 micrometers.

The coating layer having anti-fingerprint is formed by coating the anti-fingerprint photocurable composition on the transparent substrate. The coating method of the anti-fingerprint photocurable composition can be selected in a timely manner according to the circumstances of the anti-fingerprint photocurable composition and the coating process, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, It may be coated by a gravure coating method or an extrusion coating method (this method is a known method described in the specification of US Patent 2681294).

The anti-fingerprint photocurable composition coated on the transparent substrate is then cured by being exposed to irradiation of active energy rays, whereby the anti-fingerprint coating layer is formed. In the present specification, the term "photocurable" is used in a broad sense, and in addition to rays such as ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X rays and γ rays, electron rays, proton rays, neutron rays, and the like. It means the property to harden | cure by irradiating the active energy ray of. Among these, hardening by ultraviolet irradiation is advantageous in terms of the curing rate, the availability of the irradiation apparatus, the price, and the like. As a method of ultraviolet-ray hardening, the method of irradiating about 100-3000mJ / cm <^2> using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, etc. which emit light of 200-500 nm wavelength range, etc. are mentioned.

Moreover, a coating layer can be formed on the surface of an optical display device by coating the anti-fingerprint photocurable composition of this invention on the surface of an optical display device. As an optical display device which can provide a coating layer using the anti-fingerprint photocurable composition of this invention, a touch panel display, a liquid crystal display, a light emitting diode display, an electroluminescent display, a fluorescent display, a plasma display panel, etc. are mentioned. A coating layer can be formed on the surface of an optical display device by apply | coating the anti-fingerprint photocurable composition of this invention to various transparent plastic films, transparent plastic plates, and glass used for the surface of these optical display devices.

Further, the anti-fingerprint photocurable composition of the present invention is coated on the surface of the article subjected to mirror finish by coating such as metal plating or metal plating, thereby forming a fingerprint-finish coating layer on the surface of these articles. can do. Examples of articles subjected to mirror finish include cases of portable information terminals, household appliances, furniture, indoor daily necessities or cosmetics. By providing an anti-fingerprint coating layer on the surface of the article subjected to these mirror finishes, adhesion of fingerprint marks can be prevented.

Examples of the coating method for the anti-fingerprint photocurable composition include a spin coating method, a dip coating method, a gravure coating method, a spray method, a roller method, a brush coating method, and the like. And a suitable coating method can be selected according to the kind of optical display apparatus to coat. In coating of an anti-fingerprint photocurable composition, it is preferable to coat so that the thickness of the coating layer obtained may be 0.1-20 micrometers. The anti-fingerprint photocurable composition coated in this way is cured as it is exposed to the irradiation of active energy rays as described above, and thereby the anti-fingerprint coating layer is formed.

Example

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on weight unless otherwise noted.

Production Example 1 Preparation of a polyether skeleton-containing urethane (meth) acrylate (A1) having at least one (meth) acrylate group in each sock end

666 parts by weight of isophorone diisocyanate (IPDI), 2000 parts by weight of polypropylene glycol (polypropylene glycol 1000, manufactured by Kishida Chemical Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mixing weight ratio 60:40) 900 weight part was added to a reaction container, Furthermore, 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, 40 as solids) are solvents. Used in an amount of%), and mixed at 80 ° C for 3 hours while blowing air.

In this way, the polyether skeleton containing urethane (meth) acrylate (A1) which has an acrylate group in a sock end was obtained. SP value and the water tolerance value of the obtained polyether skeleton containing urethane (meth) acrylate were measured, and it was SP value 10.8 and water tolerance value 3.5. In addition, the weight average molecular weight was 7000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Production Example 2 Preparation of a polyether skeleton-containing urethane (meth) acrylate (A2) having at least one (meth) acrylate group in each sock end

44 parts by weight of isophorone diisocyanate (IPDI), 800 parts by weight of polypropylene glycol (polypropylene glycol 4000, manufactured by Kishida Chemical Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mixing weight ratio 60:40) 90 weight part is added to a reaction container, Furthermore, 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, 40 as solids) are solvents. Was used in an amount of%) and stirred for 3 hours at 80 ° C while blowing air.

In this way, the polyether skeleton containing urethane (meth) acrylate (A2) which has an acrylate group at the sock end was obtained. The SP value and the water tolerance value of the obtained polyether skeleton containing urethane (meth) acrylate were measured, and it was SP value 10.7 and water tolerance value 3.7. In addition, the weight average molecular weight was 9000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Production Example 3 Preparation of a polyether skeleton-containing urethane (meth) acrylate (A3) having at least one (meth) acrylate group in each sock end

44 parts by weight of isophorone diisocyanate (IPDI), 400 parts by weight of polypropylene glycol (polypropylene glycol 2000, manufactured by Kishida Chemical Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mixing weight ratio 60:40) 90 weight part was added to a reaction container, Furthermore, 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, solid content) as a solvent Used in an amount of 40%) and stirred for 3 hours at 80 ° C while blowing air.

In this way, the polyether skeleton containing urethane (meth) acrylate (A3) which has an acrylate group in a sock end was obtained. SP value and the water tolerance value of the obtained polyether skeleton containing urethane (meth) acrylate were measured, and it was SP value 11.1 and water tolerance value 4.8. In addition, the weight average molecular weight was 8000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Production Example 4 Preparation of a polyether skeleton-containing urethane (meth) acrylate (A4) having at least one (meth) acrylate group in each sock end

44 parts by weight of isophorone diisocyanate (IPDI), 200 parts by weight of polypropylene glycol (Pluronic PE3100, manufactured by BASF Japan Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixed Weight ratio 60:40) 90 parts by weight was added to the reaction vessel, and 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, solid content of 40%) as a solvent. Was used) and was stirred at 80 ° C for 3 hours while blowing air.

In this way, the polyether skeleton containing urethane (meth) acrylate (A4) which has an acrylate group in a sock end was obtained. SP value and the water tolerance value of the obtained polyether skeleton containing urethane (meth) acrylate were measured, and it was SP value 11.7 and water tolerance value 5.6. In addition, the weight average molecular weight was 7000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Comparative Production Example 1 Preparation of Urethane Acrylate (1)

A mixture of 222 parts by weight of isophorone diisocyanate (IPDI), 1000 parts by weight of polypropylene glycol (polypropylene glycol 1000, manufactured by Kishida Chemical Co., Ltd.), pentaerythritol triacrylate, and pentaerythritol tetraacrylate (Mixing weight ratio 60:40) 450 weight part was added to a reaction container, Furthermore, 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, 40 solids) as a solvent Used in an amount of%), and the mixture was mixed at 80 ° C for 3 hours while blowing air to obtain a urethane acrylate (1).

The obtained urethane acrylate had what has an acrylate group in one terminal. Moreover, SP value and the water tolerance value of the obtained urethane acrylate were SP values 11.2 and the water tolerance value 5.2. In addition, the weight average molecular weight was 3000. In addition, the weight average molecular weight was shown by the polystyrene conversion value 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 dibutyltin dilaurate was further added as a catalyst. 1000 ppm, 1000 ppm of hydroquinone as polymerization inhibitor, and methyl isobutyl ketone (MIBK, used in an amount of 40% solids) as a solvent were added and mixed at 80 ° C for 3 hours while blowing air to obtain a urethane compound. did.

Moreover, SP value and the water tolerance value of the obtained urethane compound were measured, and it was SP value 11.0 and water tolerance value 4.7. In addition, the weight average molecular weight was 6000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Example 1 Preparation of Fingerprint Photocurable Compositions

20 parts by weight of the polyether skeleton-containing urethane (meth) acrylate obtained in Production Example 1, 80% by weight of a mixture of aronix M305 (pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixed weight ratio about 60:40)) Parts and 3 parts by weight of Irgacure 184D (1-hydroxy-cyclohexyl-phenyl-ketone) are mixed, and adjusted to a nonvolatile content of 40% by weight using MIBK as a solvent to obtain a fingerprint-curable composition. did.

The obtained composition was bar-coated with a bar coater (No. 12) on a PET film (thickness 100 µm) so as to have a dry film thickness of 5 µm, and heated at 80 ° C for 1 minute to remove the solvent. Then, the coating layer was formed by exposing and hardening | curing an ultraviolet-ray to the energy of 300mJ / cm <^{2> with} a high pressure mercury lamp (120W / cm), and obtained an anti-fingerprint film.

Examples 2 to 17 Preparation of the fingerprint-curable composition

Except for using the raw material shown in Tables 1-3 in the weight part shown in Tables 1-3, the anti-fingerprint photocurable composition was obtained like Example 1. Moreover, the coating layer was formed like Example 1 and the anti-fingerprint film was obtained. In addition, only Example 5 was coated so that a dry film thickness might be 3 micrometers.

Preparation of Comparative Examples 1 to 14 photocurable composition

Except for using the raw materials shown in Tables 4 to 5 by weight parts shown in Tables 4 to 5, the anti-fingerprint photocurable composition was obtained in the same manner as in Example 1. Moreover, the coating layer was formed like Example 1 and the anti-fingerprint film was obtained.

Evaluation of the sample having the obtained coating layer was carried out as described below. In addition, the result obtained by these evaluation methods is shown in the following table | surface.

Fingerprint evaluation (oleic acid wipe evaluation)

On the coating layer of the obtained sample, 1 drop of oleic acid was dripped. Then, 10 round trips were wiped off using a clean wiper. The haze of the sample before the evaluation test and after the evaluation test was measured in accordance with the above, and the haze value was determined. According to the value of the (triangle | delta) haze obtained, the fingerprinting evaluation was performed by the following reference | standard.

5 points | pieces: haze is less than 0.5

4 points | pieces: haze is 0.5 or more and less than 1.0

3 points | pieces: haze is 1.0 or more and less than 3.0

2 points | pieces: haze is 3.0 or more and less than 5.0

1 point: △ haze 5.0 or more

In addition, the haze value was measured as follows. Using a haze meter (manufactured by Suga Test Co., Ltd.), the diffusion transmittance (Td (%)) and the total light transmittance (Tt (%)) of the sample were measured, and the haze value was calculated. In addition, the total light transmittance (%) and haze (%) shown in the table are the values measured through the PET film part of thickness 100micrometer used as the base material in preparation of a coating layer in all.

H: haze (% litter)

T _d : Diffuse light transmittance (%)

T _t : Total light transmittance (%)

Evaluation of Steel Resistance

On the coating layer of the obtained sample, # 0000 steel wool was reciprocated 100 under a load of 500 g / cm ² . Then, visual evaluation of the surface of the cured film after an evaluation test was performed, and the steel-resistant evaluation was performed by the following reference | standard.

◎: almost no scratch

○: less than 2 wounds

△: 3 or more wounds, 10 or less

×: 11 or more wounds

Evaluation of solvent resistance

On the cured film surface, it rubbed lightly 100 times reciprocation with the cotton swab impregnated with MEK (methyl ethyl ketone), and visually evaluated the state of the coating film surface after a test visually.

○: no trace

△: slight trace

×: White flower

Evaluation of pen sliding motility

A 200 g load was applied to a polyacetal pen (tip shape: 0.8 mmR), and a linear sliding test of 40,000 times (20,000 round trips) was performed on the cured film surface. The sliding movement distance at this time was 30 mm, and the sliding movement speed was 300 mm / second. After this sliding exercise durability test, the sliding part was visually observed.

○: almost no trace

△: slight trace

×: White flower

Evaluation of Flex Resistance

The cured coating film was measured by the cylindrical mandrel method according to JIS K 5600. It evaluated as follows from the minimum diameter of the cylinder in which the crack did not enter the coating film.

○: less than 13 mm in diameter

△: diameter 13 or more and less than 18mm

X: diameter 18 mm or more

Evaluation of curl

The cured coating film was cut out to a square of 10 cm angle, and evaluated as an average value (mm) of the floating amount of the four corners at the time of standing.

○: less than 10 mm

△: less than 10mm, less than 30mm

×: 30 mm or more

The formulation and evaluation result of the said Examples 1-16 and Comparative Examples 1-14 are put together in the following table, and are shown. In addition, the symbol in a table | surface shows the following content.

UV-6100B: manufactured by Nippon Synthetic Chemicals Co., Ltd., polyether skeleton-containing urethane acrylate having at least one (meth) acrylate group in each sock end, weight average molecular weight 5000

UV-3700B: manufactured by Nippon Synthetic Chemicals Co., Ltd., polyether skeleton-containing urethane acrylate having at least one (meth) acrylate group in each sock end, weight average molecular weight 41000

UA-47: The polyether frame | skeleton containing urethane acrylate which has at least 1 (meth) acrylate group in each sock end manufactured by Toho Chemical Co., Ltd., the weight average molecular weight 2000

U-324A: Shinnakamura Chemical Co., Ltd., urethane acrylate

DPHA-40H: manufactured by Nippon Gunpowder Co., Ltd., urethane acrylate

Aronix M305: A mixture of Doa Synthetic Co., Ltd., pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixed weight ratio about 60:40)

Aronix M309: Toray Synthetic Co., Ltd. product, trimethylolpropane triacrylate

Aronix M350: Doa Synthetic Co., Ltd. product, trimethylolpropane 3EO modified triacrylate

Aronix M450: Doa Synthetic Co., Ltd. product, pentaerythritol tetraacrylate

Irgacure 184D: 1-hydroxy-cyclohexyl-phenyl-ketone

Irgacure 907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one

Polypropylene glycol 400: The product made by Kishida Chemical Co., Ltd., polypropylene glycol, average molecular weight 400

Polypropylene glycol 700: The product made by Kishida Chemical Co., Ltd., polypropylene glycol, average molecular weight 700

Polypropylene glycol 1000: The product made by Kishida Chemical Co., Ltd., polypropylene glycol, average molecular weight 1000

PE-3100: Pluronic PE3100, manufactured by BASF Japan Co., Ltd., Polypropylene glycol 90%, Polyethylene glycol 10% block polymer, Molecular weight 1000

PE-61: Sanyo Chemical Co., Ltd., 86% polypropylene glycol, 14% polyethylene glycol block polymer, molecular weight 2000

APG-700: Shinnakamura Chemical Co., Ltd., polyether diacrylate

UX-5000: Nippon Gunpowder Co., Ltd., polyester acrylate

UX-5001T: Nippon Gunpowder Co., Ltd., polyester acrylate

Epoxy ester 70PA: manufactured by Kyoeisha Chemical Co., Ltd., epoxy acrylate

Epoxy ester 80MFA: Kyoeisha Chemical Co., Ltd., epoxy acrylate

BYK320: Big Chemie Japan Co., Ltd. make, silicon type surface regulator

* In the said table, the urethane acrylate (1) of the comparative manufacturing example 1 has an acrylate group only in one terminal, and the comparative manufacturing example 2 is a urethane compound which does not have an acrylate group in the terminal.

As shown in the table, it can be confirmed that the anti-fingerprint film obtained by the anti-fingerprint photocurable composition of the embodiment is excellent in all of the anti-fingerprint, steel resistance, solvent resistance, pen sliding motion, bending resistance, curling property. there was.

Comparative Example 1 is an experimental example using urethane acrylate having an acrylate group at one terminal. In this case, while anti-fingerprint was excellent, it was inferior to steel wool resistance, solvent resistance, etc.

Comparative Example 2 is an experimental example using a urethane compound having no acrylate group at the terminal. In this case, while anti-fingerprint is excellent, it is inferior to steel wool resistance, solvent resistance, etc. greatly.

Comparative Examples 3-4 are experimental examples using the urethane acrylate whose SP value or several tolerance values are out of the range of this invention. In this case, it was confirmed that the fingerprint was inferior.

Comparative Examples 5 and 6 are experimental examples using polyether or polyether (meth) acrylate (D) instead of the polyether skeleton-containing urethane (meth) acrylate (A). In this case, it was confirmed that steel wool resistance and pen sliding movement | movement were inferior.

Comparative Examples 7 and 8 are experimental examples using polyester acrylate instead of polyether skeleton-containing urethane (meth) acrylate (A). In this case, it was confirmed that anti-fingerprint did not express.

Comparative Examples 9 and 10 are experimental examples using epoxy acrylate instead of polyether skeleton-containing urethane (meth) acrylate (A). Also in this case, it was confirmed that anti-fingerprint did not express.

Comparative Examples 11-14 are experimental examples prepared only with the photopolymerizable polyfunctional compound (B). Also in this case, it was confirmed that anti-fingerprint did not express.

By using the anti-fingerprint photocurable composition of this invention, the coating layer which has the outstanding anti-fingerprint can be installed more easily on the surface, such as an optical display device. The coating layer obtained by the anti-fingerprint photocurable composition of this invention is excellent also in transparency, and is suitable for the use on surfaces, such as an optical display device. The coating layer obtained by the anti-fingerprint photocurable composition of the present invention also has excellent scratch resistance and film hardness of the surface. Moreover, since the anti-fingerprint photocurable composition of this invention is photocurable, the coating layer which has such excellent performance can be formed more easily on the surface of an optical display device. By using the anti-fingerprint photocurable composition of this invention, it has the industrial advantage that the coating layer excellent in production efficiency and manufacturing cost can be formed. Moreover, this coating layer can maintain anti-fingerprint for a long time and is excellent also in anti-fingerprint durability.

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

Explanation of the sign

One… Anti-fingerprint film, 3... Coating layer, 5... Transparent substrate.

Claims (7)

Polyether skeleton containing urethane (meth) acrylate (A) which has at least 1 (meth) acrylate group in each sock end, Photopolymerizable multifunctional compound (B), and Photopolymerization Initiator (C) Including, The polyether skeleton-containing urethane (meth) acrylate (A) has a structure represented by the following formula (1), [Formula 1]

[Wherein X represents a residue excluding the hydroxyl group of the sock end of the polyol compound having a polyether skeleton] The water tolerance of the said polyether skeleton containing urethane (meth) acrylate (A) is 6.0 ml or less, and the solubility parameter is 12 or less, Anti-fingerprint photocurable composition. The method of claim 1, To moon-tight photocurable composition, further comprising polyether or polyether (meth) acrylate (D). The method according to claim 1 or 2, The polyether skeleton-containing urethane (meth) acrylate (A) contains a polyol compound (a), a polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate monomer (c) having a polyether skeleton. The anti-fingerprint photocurable composition which is a polyether skeleton containing urethane (meth) acrylate prepared by making it react. 4. The method according to any one of claims 1 to 3, 0.5 to 40% by weight of a polyether skeleton-containing urethane (meth) acrylate (A), 30-99.5 weight% of photopolymerizable multifunctional compounds (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 0.1 to 20 parts by weight of the photopolymerization initiator (C) based on 100 parts by weight of the total weight of the components (A), (B) and (D) Anti-fingerprint photocurable composition comprising a. An anti-fingerprint film having a transparent substrate and a coating layer, wherein the coating layer is a coating layer formed by the anti-fingerprint photocurable composition according to any one of claims 1 to 4. The coating material provided with the anti-fingerprint layer formed with the anti-fingerprint photocurable composition of any one of Claims 1-4. The method of claim 6, A coating material wherein the coating material is a touch panel display, a liquid crystal display, a light emitting diode display, an electroluminescent display, a fluorescent display, a plasma display panel, or a mirror-finished product.

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