KR20120053470A - Method for forming hard coat layer, and curable composition - Google Patents

Abstract

PURPOSE: A method for forming a hard coat layer and a curable composition are provided to obtain a cured film and a stacked film with superior transparency and to obtain wet heat resistance and dry heat resistance. CONSTITUTION: A method for forming a hard coat layer includes the following: a curable composition is sprayed on a substrate to form a film; and radiation ray is irradiated to the film to form the hard coat layer. The curable composition includes multi-functional (meta)acrylmonomer, photo polymerization initiator, non-ionic surfactant, and organic solvent. The non-ionic surfactant is composed of fatty acid ester and includes a polymerizable reacting group or is composed of linear or branched C6 to C30 monovalent or divalent hydrocarbon group.

Description

Formation method of hard coat layer and curable composition {METHOD FOR FORMING HARD COAT LAYER, AND CURABLE COMPOSITION}

The present invention relates to a method for forming a hard coat layer. More specifically, it is related with the formation method of the hard-coat layer using the curable composition suitable for spray coating.

Plastics (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbornene-based resin, etc.), metal, wood, paper, glass, As a protective coating material for preventing scratches or contamination of the surface of various substrates such as slate, it has excellent coating properties and has hardness, scratch resistance, antifouling property, abrasion resistance, and surface slipperiness on the surface of various substrates. There is a demand for a curable composition capable of forming a cured film having excellent low curling properties, adhesiveness, transparency, chemical resistance, and appearance of a coating film surface.

In recent years, mobile phones, information terminals, and the like, which have been subjected to a hard coat treatment on the surface, are commercially available. By performing a hard coat treatment, the surface became a glossy surface and the designability was increased. However, the glossy coating made the adhesion of the fingerprint noticeable. For this reason, in addition to the scratch resistance and transparency required in the conventional hard coats, there is an increasing demand for antifouling properties, in particular, fingerprint wiping, but there is no current material that satisfies all of these properties. On the other hand, at the time of these coatings, there exists a request to perform spray coating in the point which can be apply | coated also to a curved surface.

Patent Literature 1 discloses a hard coat film for a touch panel or a display formed by adding a nonionic surfactant having an HLB value of 2 to 15 made of a fatty acid ester to an ionizing radiation curable resin. This film has good fingerprint resistance and fingerprint wiping resistance, but is poor in scratch resistance and inferior in transparency. This bleeded out on the surface of a cured film, in order that a fatty acid ester type | system | group surfactant might express anti-visual visibility and fingerprint wipeability, and the scratch resistance and transparency of the cured film were falling by this. Even when spray coating this composition, sufficient fingerprint visibility and fingerprint wipeability were not obtained.

Patent Literature 2 has a predetermined structure, a polyalkylene oxide chain-containing polymer (specifically, a fatty acid ester surfactant) having a polymerizable unsaturated group at all terminals, a compound having two or more (meth) acryloyl groups, and Disclosed is a curable resin composition for a hard coat layer containing inorganic fine particles having a polymerizable unsaturated group on its surface, and wherein these components can react with each other. In the cured film obtained by hardening this curable resin composition, the said polyalkylene oxide chain containing polymer, the compound which has a (meth) acryloyl group, and the inorganic particle which has a polymerizable functional group on the surface react with each other, and a polyalkylene oxide chain Scratch resistance improves because the containing polymer does not bleed out to the cured film surface, and each component can crosslink with each other. Although the cured film of patent document 2 was excellent also in abrasion resistance, sufficient fingerprint visibility and fingerprint wipeability were not acquired.

Japanese Laid-Open Patent Publication No. 2004-114355 (Special Document 2) Japanese Laid-Open Patent Publication No. 2008-165040

This invention is made | formed in view of the above-mentioned problem, Comprising: It aims at providing the curable composition for spray coating useful as a hard coating material which the cured film obtained has the outstanding fingerprint visibility and fingerprint wiping property.

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, the present inventors earnestly researched and, as a result, using the composition which mix | blended a fixed amount of fatty acid ester type surfactant with a hydroxyl group density | concentration below, it was excellent in antifouling property to the hard-coat layer formed by spray coating. It discovered that it can provide high transparency, and completed this invention.

That is, this invention provides the formation method and curable composition of the following hard-coat layer.

1. The process of forming a coating film by spray-coating the curable composition which contains the following components (A)-(D) on the base material, and has a HLB value of 2-7 of the following component (C), and radiation to the said coating film A method of forming a hard coat layer, comprising the step of irradiating:

(A) polyfunctional (meth) acrylic monomer

(B) photoinitiator

(C) Nonionic surfactant consisting of fatty acid ester

(D) an organic solvent.

2. The formation method of the hard-coat layer of said 1 whose compounding quantity of the said component (C) is more than 10 weight part and 100 weight part or less with respect to a total of 100 weight part of the said component (A) and the said component (B). .

3. The formation method of the hard-coat layer as described in said 1 or 2 whose HLB value of the said component (C) is the range of 2-4.

4. Curable composition for spray coating containing following component (A)-(D), and whose HLB value of following component (C) is 2-7.

(A) polyfunctional (meth) acrylic monomer

(B) photoinitiator

(C) nonionic surfactant consisting of fatty acid esters

(D) an organic solvent.

5. Curable composition for spray coating as described in said 4 whose compounding quantity of the said component (C) is more than 10 weight part and 100 weight part or less with respect to a total of 100 weight part of the said component (A) and the said component (B).

6. Curable composition for spray coating as described in said 4 or 5 whose said component (C) is surfactant which has a linear or branched C1-C30 monovalent or divalent hydrocarbon group in a molecule | numerator.

7. Curable composition for spray coating in any one of said 4-6 whose said component (C) is surfactant which has a (meth) acryloyl group.

8. Curable composition for spray coating in any one of said 4-7 whose HLB value of the said component (C) is the range of 2-4.

9. Furthermore, (E) Curable composition for spray coating as described in any one of said 4-8 containing inorganic oxide particle of number average particle diameter 1-200 nm.

10. Curable composition for spray coating as described in said 9 whose said component (E) is an inorganic oxide particle which has a polymerizable unsaturated group on the surface.

ADVANTAGE OF THE INVENTION According to this invention, the hard-coat layer which is excellent in fingerprint visibility and fingerprint wiping property, and has high transparency can be provided.

According to this invention, the laminated | multilayer film excellent in transparency can be provided further.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which is excellent in fingerprint visibility, fingerprint wiping property, and also excellent in abrasion resistance, has durability, such as wet heat resistance, dry heat resistance, and excellent transparency, can be provided.

Best Mode for Carrying Out the Invention [

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

I. Curable Compositions

The curable composition (henceforth a composition of this invention) of this invention can contain the following component (A)-(F). Among these, components (A)-(D) are essential components, and components (E)-(F) are arbitrary components added as needed.

(A) polyfunctional (meth) acrylic monomer

(B) photoinitiator

(C) nonionic surfactant consisting of fatty acid esters

(D) organic solvent

(E) Inorganic oxide particles having a number average particle diameter of 1 to 200 nm

(F) other additives.

The composition of the present invention, the component (C) is a nonionic surfactant having a polymerizable reactor, preferably having a polymerizable reactor, preferably a HLB (Hydrophile-Lipophile Balance) value 2 having a fatty acid ester group and (meth) acryloyl group By being a nonionic surfactant which consists of a fatty acid ester of -7, whitening of the cured film (coating film) obtained even if it mix | blends a component (C) in large quantities is prevented, and the cured film which has high transparency is obtained.

It improves the scratch resistance of a cured film. Moreover, since it has a C6-C30 monovalent or divalent hydrocarbon group of linear or branched chain, it is excellent in the wipe-ability of a fingerprint.

Hereinafter, each component of the composition of this invention is demonstrated.

(A) polyfunctional (meth) acrylic monomer

The component polyfunctional (meth) acryl monomer (A) used for this invention is a (meth) acryl monomer which has two or more (meth) acryloyl groups. Component (A) is what is called a binder component for improving the film-forming property of a composition.

In addition, although the component (E) mentioned later may be a reactive particle | grain (Ec), and the component (C) mentioned later may have two or more (meth) acryloyl groups, the polyfunctional (meth) acryl monomer in this invention. (A) shall not contain a reactive particle (Ec) and a component (C).

Specific examples of the polyfunctional (meth) acryl monomer (A) include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree (meth) Polyfunctional (meth) acryl monomers having three or more (meth) acryloyl groups such as acrylate; Ethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycoldi Polyfunctional having two (meth) acryloyl groups, such as (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate ( Hydroxyl group-containing polyfunctional (meth) acrylates, such as a meta) acryl monomer and bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and poly of ethylene oxide or a propylene oxide addition product to these hydroxyl groups (Meth) acrylates; Oligoester (meth) acrylates which have two or more (meth) acryloyl groups, oligoether (meth) acrylates, oligoepoxy (meth) acrylates, etc. are mentioned. The polyfunctional (meth) acryl monomer illustrated above may be used individually by 1 type, and may use 2 or more types together.

In these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propane Tetra (meth) acrylate etc. are preferable.

As a commercial item of such a polyfunctional (meth) acryl monomer (A), Toagosei Co., Ltd. Aronix M-400, M-404, M-408, M-450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M- 240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd. KAYARAD 'D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR- 415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, A Shaka Chemicals, can be given as to whether or manufactured manufacturing Light acrylate (Lightacrylate) PE-4A, DPE-6A, DTMP-4A, manufactured by Shin Nakamura Kagaku car manufacturing whether or NK ester A-TMM-3LM-N and the like.

It is preferable that a component (A) makes the whole quantity 100 weight%, and contains 50 weight% or more of polyfunctional (meth) acryl monomers which have three or more (meth) acryloyl groups, and 70 weight% or more More preferably, it is more preferable that it is 100 weight%.

When the compounding quantity of the component (A) in the composition of this invention makes the total amount other than a component (D) 100 weight part, the inside of the range of 40-95 weight part is preferable, It is preferable to exist in the range of 45-90 weight part, 50 It is more preferable to exist in the range of -90 weight part. By mix | blending a component (A) in the said range, the high hardness cured film can be obtained.

(B) photoinitiator

Component (B) in this invention is a photoinitiator. As a photoinitiator (B), the compound (radiation (photo) polymerization initiator) which generate | occur | produces an active radical species by radiation (light) irradiation is mentioned.

The photopolymerization initiator (B) is not particularly limited as long as it is decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenonebenzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2, 2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propylether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4- (2-hydroxyethoxy Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like.

As a commercial item of a photoinitiator (B), Irgacure (184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocure) by BASF Corporation, for example. (Darocure) # 1116, 1173, Lucirin® TPO, 8893, Uvecryl P36 manufactured by UCB, Esacure KIP150 manufactured by Lambert, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. Can be mentioned.

When content of the component (B) in the composition of this invention makes 100 weight part of totals other than a component (D), it is preferable to exist in the range of 0.1-10 weight part, and it is more preferable to exist in the range which is 0.3-5 weight part. It is more preferable to carry out in the range of 0.5-5 weight part. In addition, content of a component (B) can also be determined based on content of a component (A) within said range. For example, when content of a component (A) is 100 weight part, content of a component (B) is preferable to be 0.25-20 weight part, and it is more preferable to set it as 0.5-15 weight part. By making content of a component (B) into the said range, it becomes possible to obtain a high hardness cured film.

(C) Nonionic surfactant which consists of fatty acid ester (Hereinafter, component (C) may be called "fatty acid ester type surfactant (C).")

Component (C) is mix | blended for the purpose of making it difficult to distinguish the fingerprint attached to the hard-coat layer obtained by this invention, and to improve the wipeability of a fingerprint. The curable composition of this invention is used suitably by spray coating. When coating with a spray, since surfactant is hardly localized on the coating film surface, compared with the case where it is apply | coated by other coating methods, it is necessary to mix | blend a large amount of surfactant, but HLB value is 2-7. By using the nonionic surfactant of the range, whitening of a cured film can be suppressed. Moreover, for the same reason, it is preferable that the HLB value of component (C) is 2-4. In addition, by providing a (meth) acryloyl group to the component (C), the binder and the binder component in the composition of the present invention can be bonded and immobilized, so that the fatty acid ester surfactant (C) bleeds out to the cured film surface. You can prevent it. Thereby, durability of the cured film obtained improves. Moreover, it is preferable that component (C) has a linear or branched C6-C30 monovalent or bivalent hydrocarbon group. By having a C6-C30 hydrocarbon group, a fingerprint visibility and fingerprint wiping property can be provided to the cured film obtained. Here, "fingerprint resistance" means that it is difficult to visually identify when a fingerprint is affixed on the film surface.

Here, HLB (Hydrophile-Lipophile Balance) value is an important index which shows the characteristic of surfactant, and shows the magnitude | size of hydrophilicity or lipophilic magnitude. The HLB value can be obtained by the following formula.

HLB = 7 + 11.7Log (M _W / M _O )

M _W is a molecular weight of a hydrophilic group and M _O is a molecular weight of a lipophilic group. M _W + M _O = M (molecular weight of the surfactant). The HLB value of the fatty acid ester surfactant (C) used in the present invention needs to be in the range of 2 to 7, and preferably in the range of 2 to 4. By carrying out HLB value in the said range, even if it mix | blends surfactant in large quantity, it does not whiten and can obtain the composition suitable for spray coating.

As a method of providing a (meth) acryloyl group to component (C), it can obtain by converting the hydroxyl group of a fatty acid ester type surfactant which has a hydroxyl group, for example to a (meth) acryloyl group. Specifically, component (C) can be obtained by making the compound which has the hydroxyl group and (meth) acryloyl group which a fatty-acid ester surfactant has have reacted.

As a compound which has a (meth) acryloyl group, the compound which has an isocyanate group and a (meth) acryloyl group can be used, for example. By using such a compound, the (meth) acryloyl group is introduce | transduced by the hydroxyl group of an fatty-acid ester type surfactant, and an isocyanate group reacting, and forming a urethane bond.

As a specific example of the compound which has an isocyanate group and a (meth) acryloyl group, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryl Royloxymethyl] ethyl isocyanate etc. can be used. Moreover, the compound containing a hydroxyl group and a (meth) acryloyl group can also be obtained by making a diisocyanate compound react. As such a diisocyanate compound, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned.

As a specific example of a fatty acid ester type surfactant which has a hydroxyl group, polyoxyalkylene hardened castor oil, polyoxyalkylene fatty acid ester, etc. are mentioned, for example, A polyoxyethylene hardened castor oil and a polyoxyethylene fatty acid ester are preferable. Do.

As a commercial item of polyoxyethylene hardened castor oil, EMALEX HC series (made by Nihon Emulsion Co., Ltd.), Noigen HC series (made by Daiichi Kogyo Seiyaku Co., Ltd.), etc. are mentioned, for example.

As a commercial item of a polyoxyethylene fatty acid ester, EMALEX 'GWIS-100EX (glycerol isostearic acid, Nippon Emulsion Co., Ltd.), Neugen GIS series (made by Daiichi Kogyo Seiyaku Co., Ltd.), etc. are mentioned, for example. .

Reaction with the fatty acid ester type surfactant which has a hydroxyl group, and the compound which has an isocyanate group and a (meth) acryloyl group can be performed as follows.

Namely, by reaction of an isocyanate compound and a hydroxyl group-containing compound, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, It is preferable to use 0.01-1 weight part of urethanization catalysts, such as 2,6,7- trimethyl- 1, 4- diazabicyclo [2.2.2] octane, with respect to 100 weight part of total amounts of a reactant. In addition, in the reaction of these compounds, it can also be performed without a catalyst. It is preferable to perform reaction temperature at 0-90 degreeC and 40-80 degreeC normally. The reaction may be performed without using a solvent or may be dissolved in a solvent.

Component (C) can have a structure represented by following formula (1), for example.

In Formula (1), the meaning of each symbol is as follows. X is optionally substituted good carbons ^{3? 10 (m 1 + m} 2) represents a divalent hydrocarbon. A plurality of Y ¹ and Y ² each independently represent a divalent group or a single bond including an ether bond, an ester bond, or a urethane bond, and at least one of Y ¹ and Y ² has a structure derived from a fatty acid. Z represents a group having one or more (meth) acryloyl groups. A plurality of R ¹¹ and R ¹² each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms. m ¹ and m ² are each an integer of 0 to 10, and n ¹ and n ² are each independently an integer of 0 to 20. Provided that m ¹ and m ² are not zero at the same time.

The compound of component (C) can be synthesize | combined as follows.

It can obtain by making the surfactant which has a hydroxyl group react the isocyanate compound or (meth) acrylic acid which has a (meth) acryloyl group in the ratio which HLB value after reaction becomes 2-7. For example, when using the surfactant which has three hydroxyl groups as a raw material, when the HLB value of surfactant of a raw material is 5, the isocyanate compound which has a 1/3 molar equivalent (meth) acryloyl group of a hydroxyl group, or It is good to only make (meth) acrylic acid react. When HLB value of surfactant of a raw material is 9, it is preferable to make the isocyanate compound or (meth) acrylic acid which has the (meth) acryloyl group of the equimolar equivalent of a hydroxyl group react.

Content of the component (C) in the composition of this invention exists in the range of 10-100 weight part with respect to a total of 100 weight part of components (A) and (B), and it is more preferable to exist in the range which is 10-80 weight part. And it is more preferable to exist in the range of 10-50 weight part. By making content of a component (C) into the said range, since sufficient anti-visual visibility is obtained also in spray coating, it is preferable. In addition, when component (C) does not have a (meth) acryloyl group, since the hardness of a cured film may fall, the compounding quantity of a component (C) is 100 weight of the sum total of a component (A) and (B). It is preferable to set it as 10-50 weight part with respect to a part.

(E) inorganic oxide particles

The composition of this invention may contain the inorganic oxide particle as a component (E). A component (E) will not be specifically limited if it is particle | grains which have an inorganic oxide as a main component. The effect of improving the hardness of laminated | multilayer film or making curl small is anticipated for component (E).

A component (E) can be selected and used from a viewpoint of transparency and the color tone of the cured film of the curable composition obtained.

Preferred examples of component (E) include particles mainly composed of inorganic oxides of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Specific examples of the particles include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Among them, particles of silica, alumina, zirconia and antimony oxide are preferable from the viewpoint of high hardness. These can be used individually or in combination of 2 or more types. Furthermore, it is preferable to use a component (E) as powder form or a solvent dispersion sol. When used as a solvent dispersing sol, the dispersion medium is not particularly limited as water or an organic solvent. From the viewpoint of compatibility with other components and dispersibility, the organic solvent is preferably a dispersion medium. As such an organic solvent, For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned. Especially, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

It is preferable that the number average particle diameter of a component (E) exists in the range of 1-200 nm, It is more preferable to exist in the range of 5-150 nm, It is still more preferable to exist in the range of 10-100 nm. When number average particle diameter is the said range, both transparency and hardness at the time of using hardened | cured material are attained. The number average particle diameter of an inorganic oxide particle (E) says the average value of 20 particle diameters measured by observation with the transmission electron microscope. Moreover, in order to improve the dispersibility of particle | grains, you may add various surfactant and amines.

As a commercially available product as a silicon oxide particle (for example, a silica particle), Nissan Kagaku Kogyo Methanol Silicazol, IPA-ST, MEK-ST, NBA-ST is colloidal silica, for example. , XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like. In addition, as powdered silica, AEROSIL 130 made from Nippon Aerosol Co., Ltd., Aerosol 300, Aerosol 380, Aerosol TT600, Aerosol OX50, and Asahi Glass Co., Ltd. Sildex H31, H32 , H51, H52, H121, H122, Nippon Silica Co., Ltd. E220A, E220, Fuji Silician Co., Ltd. SYLYSIA470, Nippon Itagara Co., Ltd. SG flakes, etc. are mentioned.

As water dispersion products of alumina, Nissan Kagaku Kogyo Co., Ltd. alumina sol-100, -200, -520; As an isopropanol dispersion of alumina, Sumitomo Osaka Cement Co., Ltd. AS-150I; As a toluene dispersion product of alumina, Sumitomo Osaka Cement Co., Ltd. AS-150T; As a toluene dispersion of zirconia, Sumitomo Osaka Cement Co., Ltd. product HXU-110JC; As an aqueous dispersion of the zinc antimonate powder, Nielsan Kagaku Kogyo Co., Ltd. (Celnax); Examples of powders and solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide include Nanotech manufactured by Seaikasei Co., Ltd .; As a water dispersion sol of antimony dope tin oxide, Ishihara Sangyo Co., Ltd. SN-100D; As ITO powder, the product of Mitsubishima Real Co., Ltd. product; Examples of the cerium oxide aqueous dispersion include Tedakagaku Co., Ltd. (Needral) and the like.

The shape of the component (E) is spherical, hollow, porous, rod, plate, fibrous, or indefinite, preferably spherical. The specific surface area (by BET specific surface area measurement method using nitrogen) of component (E) becomes like this. Preferably it is 10-1000 m <2> / g, More preferably, it is 100-500 m <2> / g.

Component (E) is an inorganic oxide particle (hereinafter, referred to as "reactive particle (hereinafter referred to as" particle modifying agent (Eb) ") surface-treated with an organic compound (Eb) having a polymerizable unsaturated group and a hydrolyzable silyl group in a molecule thereof. Ec) "). The component (E) not surface-treated with the particle modifier (Eb) with respect to the reactive particle (Ec) is called "oxide particle (Ea)". Since the reactive particle (Ec) can form a covalent bond with a binder component, the cured film excellent in abrasion resistance, heat resistance, and transparency can be obtained.

Particle Modifiers (Eb)

The particle modifier (Eb) used in the present invention is not particularly limited as long as it is an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group. As a polymerizable unsaturated group, ethylenically unsaturated groups, such as a vinyl group and a (meth) acryloyl group, are mentioned. In addition, a hydrolyzable silyl group reacts with water and produces a silanol (Si-OH) group. For example, at least one methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- The thing which the alkoxy group, such as butoxy group, an aryloxy group, an acetoxy group, an amino group, and a halogen atom couple | bonded is mentioned.

As a particle modifier (Eb) used by this invention, commercial items, such as (gamma) -methacryloxypropyl trimethoxysilane, can also be used, For example, the compound of Unexamined-Japanese-Patent No. WO97 / 12942 can also be used.

Preparation of Reactive Particles (Ec)

Reactive particle (Ec) is obtained by mixing particle modifier (Eb) with oxide particle (Ea), hydrolyzing, and combining both. The ratio of the hydrolyzate and condensate of the organic polymer component, that is, the hydrolyzable silane, in the obtained reactive particles (Ec) is usually a weight loss percentage of the weight reduction percentage when the dry powder of the reactive particles (Ec) is completely burned in air. Viii), for example, it can be obtained by thermogravimetric analysis from room temperature to normal 800 ° C in air.

The binding amount of the particle modifier (Eb) to the oxide particles (Ea) is 100% by weight of the reactive particles (Ec) (total amount of the oxide particles (Ea) and the particle modifier (Eb)), preferably 0.01 to 40 It is weight%, More preferably, it is 0.1-30 weight%, Especially preferably, it is 1-20 weight%. By setting the amount of the particle modifier (Eb) to react with the oxide particles (Ea) in the above range, the dispersibility of the reactive particles (Ec) in the composition can be improved, and the effect of improving the transparency and scratch resistance of the cured product obtained is obtained. You can expect

Although the component (E) in the composition of this invention is an arbitrary component, the content at the time of adding adds 100 sum total other than a component (D) also in the case of an oxide particle (Ea) and a reactive particle (Ec). When it is weight part, it is preferable that it is 1-30 weight part, and it is more preferable to exist in the range of 2-20 weight part. When content of a component (E) is less than 1 weight%, there exists a possibility that the compounded effect may not appear, and when it exceeds 30 weight part, there exists a possibility that coatability may fall.

In addition, content of an inorganic oxide particle (E) means solid content, and when an inorganic oxide particle (E) is used in the form of a solvent dispersion sol, the content does not contain the quantity of a solvent.

(D) organic solvent

The composition of this invention is diluted and used with the organic solvent, in order to improve the coating property by spraying. For example, the viscosity in the case of using as a hard coat material is 0.1-100 mPa * sec / 25 degreeC normally, Preferably it is 0.5-50 mPa * sec / 25 degreeC.

As an organic solvent (D), For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanol; Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

It is preferable that the compounding quantity of the organic solvent (D) used as needed in the composition of this invention exists in the range of 50-10,000 weight part when the sum total of the component except a solvent is 100 weight part. The compounding quantity of a solvent can be suitably determined considering the coating film thickness, the viscosity of a composition, the shape of a spray nozzle, a nozzle diameter, etc.

(F) other additives

In addition to the said component, radically polymerizable compounds other than component (A), (C), and (Ec), antioxidant, a ultraviolet absorber, a leveling agent, etc. can be added to the composition of this invention as needed.

The composition of this invention can be prepared by adding the component arbitrarily selected from the said component (A)-(D) and if necessary, respectively, and mixing on room temperature or heating conditions. Specifically, it can prepare using well-known mixers, such as a mixer, a kneader, and a ball mill. However, when mixing under heating conditions, it is preferable to carry out below the decomposition start temperature of a polymerization initiator and a polymerizable unsaturated group.

The composition of the present invention obtained as described above can be cured by radiation (light).

II. Hard coat layer

The hard coat layer of the present invention can be obtained by coating and curing the composition of the present invention on various substrates. Specifically, the composition of the present invention is coated and, if necessary, obtained by volatilizing and removing volatile components such as an organic solvent (D) at 0 to 200 ° C, and then performing curing treatment with radiation.

As a coating method to a base material, besides spray coating, normal coating methods, for example, dipping coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. are mentioned. The thickness of the coating film in these coatings is the film thickness after drying and hardening, Preferably it is 0.1-400 micrometers, More preferably, it is 0.5-200 micrometers.

Although there is no restriction | limiting in particular as long as it can harden | cure a composition in a short time after coating as a radiation, Ultraviolet rays and an electron beam are preferable for the reason of the availability of an irradiation apparatus. As a source of ultraviolet rays, a mercury lamp, a halide lamp, a laser, or the like can be used, and as a source of electron beams, a method using hot electrons generated from commercially available tungsten filaments can be used. When using an ultraviolet-ray or an electron beam as radiation, preferable irradiation light quantity of ultraviolet-ray is 0.01-10J / cm <2>, More preferably, it is 0.1-2J / cm <2>. Moreover, as for the irradiation conditions of preferable electron beam, acceleration voltage is 10-300 kV, electron density is 0.02-0.30 mA / cm <2>, and electron beam irradiation amount is 1-10 Mrad.

III. materials

The base material to be coated is not particularly limited, but for example, polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, and the like. Plastic, glass, wood, metal and the like. In the case of direct application, when the adhesion between the substrate and the hard coat layer is poor, the substrate may be subjected to a base treatment in advance.

Ⅳ. Application example

Since the hard-coat layer of this invention is excellent in fingerprint visibility and fingerprint wiping property, it is used especially suitably as surface protection layer of various portable devices, such as a mobile telephone and an information terminal with which a person directly contacts.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In addition, "%" represents a weight% and "part" shows a weight part unless there is particular notice.

Synthesis Example 1 Preparation of Compound (C-1)

In formula (2), R <^1> is group represented by following formula (3). a + b + c = 7.

2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical Co., Ltd., YOSHINOX BHT) 0.030g, pentaerythritol triacrylate (new) to the three necked flask with a stirrer Nakamura Kagaku Co., Ltd. make, NK ester A-TMM-3LM-N) 21.05 g, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (made by Sumika Bayer Urethane Co., Ltd., Desmodur) ) I) 9.10 g and 50.00 g of methyl isobutyl ketone (made by Mitsubishi Kagaku Co., Ltd.) were put therein, and dioctyl tin dilauryl (manufactured by Kyodo Yakuhin Co., Ltd., KS-1200-A) 0.031 g After addition, it stirred at room temperature for 2 hours. Next, 19.52 g of polyoxyethylene hardened castor oil (manufactured by Nihon Emulsion Co., Ltd., EMALEX® HC-7; HLB value 6) was added. The reaction solution was heated up to 60 ° C and stirred for 2 hours to obtain compound (C-1). In addition, since the acrylate reaction advances almost quantitatively, HLB value of the compound (C-1) calculated | required from preparation amount is three.

Synthesis Example 2-6: Preparation of Compound (C-2)-(C-6)

Compounds (C-2) to (C-6) were obtained in the same manner as in Synthesis example 1 except that the compounds shown in Table 1 were used in the ratio shown in Table 1. Each HLB value is as shown in Table 1.

Compound (C-2):

In formula (4), R <^2> is group represented by following formula (5), respectively. a + b + c = 7.

Compounds (C-3), (C-4) and (C-5):

In formula (6), R <^3> is group represented by a hydrogen atom or a following formula each independently. However, when formula (6) is (C-3), R <^3> is group represented by following formula (5). a + b + c = 5.

Compound (C-6):

In formula (7), R <^4> is group represented by a hydrogen atom or following formula (8) each independently. a + b + c = 5.

Synthesis Example 7 Preparation of Compound (C-7)

In formula (9), R <^5> is group represented by a hydrogen atom or following formula (10) each independently. a + b + c = 5.

2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical Co., Ltd., Yoshinox BHT) 0.005g, 2-methacryloyloxyethyl isocyanate (Show 1.79 g of Wadenko Co., Ltd., Karenz MOI) was added, and 0.040 g of dilauryl acid dioctyl tin (Kyodo Yakuhin Co., Ltd., KS-1200-A) was added thereto, followed by room temperature. It stirred at 2 hours. Next, 48.17 g of polyoxyethylene hardened castor oil (manufactured by Nihon Emulsion Co., Ltd., EMALEX® HC-5; HLB value 5) was added. The reaction solution was heated up to 60 ° C and stirred for 2 hours to obtain compound (C-7).

Synthesis Example 8 Preparation of Compound (C-8)

To a three-necked flask equipped with a stirrer, 0.933 g of castor oil (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.036 g of 0.05 mol / l sulfuric acid were mixed and heated and stirred at 60 ° C to give a compound having a hydroxyl concentration of 6.1 mmol / g ( C-8). The HLB value of (C-8) is 2.

The compound described in Table 1 is as follows.

HC-7: EMALEX® HC-7, polyoxyethylene cured castor oil having a structure represented by the following formula, Nihon emulsion Co., Ltd. make.

EMALEX HC-7 (a + b + c = 7), HLB value: 6

TDI: Mitsui Chemical Co., Ltd. make, TOLDY-100, tolylene diisocyanate, molecular weight: 174.16

IPDI: Desmodure I, Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate, molecular weight: 222.29

Karenz MOI: Showa Denko KK, 2-methacryloxyethyl isocyanate, molecular weight: 155.15

PETA: NK ester A-TMM-3LM-N, Shin-Nakamura Chemical Co., Ltd. make, pentaerythritol triacrylate, molecular weight: 298.3

HEA: Osaka Yuki Kagaku Co., Ltd., hydroxyethyl acrylate, molecular weight: 116.11

BHT: Yoshinox BHT, manufactured by Yoshitomi Fine Chemical Co., Ltd., 2,6-di-t-butyl-p-cresol, molecular weight: 220

KS-1200-A: manufactured by Kyodo Yakuhin Co., Ltd., dioctyl tin dilauryl acid

MIBK: Methyl Isobutyl Ketone

Preparation Example 1

Synthesis of Particle Modifiers (Eb)

To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise at 50 ° C over 1 hour while stirring, followed by 3 hours at 70 ° C. It stirred by heating. NK ester A-TMM-3LM-N (60 weight% of pentaerythritol triacrylate and 40 weight% of pentaerythritol tetraacrylates) by Shin-Nakamura Kagaku Co., Ltd., and among these, participates in reaction 549 parts of pentaerythritol triacrylate which has a hydroxyl group) were dripped at 30 degreeC over 1 hour, and it heated and stirred at 60 degreeC for 10 hours, and obtained the particle | grain modifier (Eb) containing a polymerizable unsaturated group. As a result of analyzing the amount of remaining isocyanate in a product by FT-IR, it was 0.1% or less, and it showed that reaction was completed almost quantitatively. An infrared absorption spectrum of the product to be a characteristic absorption peak of 2260cm ^-1 disappeared and the absorption peak of the raw material isocyanate compound 2550cm ^-1 characteristic to a mercapto group in the raw material, the new urethane bonds, and S (C = O) NH- groups A characteristic 1660 cm ⁻¹ peak and an acryloxy group characteristic peak of 1720 cm ⁻¹ were observed, and an acryloxy group-modified alkoxy having an acryloxy group as a polymerizable unsaturated group and —S (C═O) NH— and a urethane bond It was shown that silane was produced. By the above, the composition of 773 parts and 220 parts of pentaerythritol tetraacrylates was obtained by the sum total of a particle modifier (Eb).

Production Example 2

Preparation of Reactive Particle 1 (I) which is (Ec)

2.98 parts of the composition prepared in Production Example 1 (containing 2.32 parts of the particle modifier (Eb)), silica particle dispersion (Ea) (solid content: 35% by weight, MEK-ST-L, number average particle diameter 0.08 μm, Nissan Kagaku) 89.90 parts of Kogyo Co., Ltd.), 0.12 parts of ion-exchange water, and 0.01 part of p-hydroxy phenyl monomethyl ethers are stirred at 60 degreeC for 4 hours, and then 1.36 parts of ortho formic-acid methyl esters are added, and also 1 hour The reactive particle dispersion was obtained by heating and stirring at the same temperature. After weighing 2g of this dispersion liquid to the aluminum dish, it dried for 1 hour and weighed on the 175 degreeC hotplate, and obtained solid content, and it was 36.5 weight%. Furthermore, after weighing 2 g of the dispersion liquid in a magnetic crucible, preliminary drying was carried out for 30 minutes on a hot plate at 80 ° C and calcined for 1 hour in a muffle furnace at 750 ° C. The inorganic content in the solid content was 95% by weight. . It concentrated until it became 70 weight% of solid content, and it was set as the silica particle (I) dispersion liquid. The number average particle diameter measured by the transmission electron microscope method of the obtained silica particle (I) was 80 nm.

Production Example 3

Preparation of reactive particle 2 (S) which is (Ec)

(gamma) -methacryloxypropyl trimethoxysilane (SZ6030 by Tow Dow Corning Silicone Co., Ltd.) 3.14 parts, silica particle dispersion (Ea) (solid content: 35 weight%, MEK-ST-L, number average particle diameter 0.08 micrometer) Nissan Kagaku Kogyo Co., Ltd.) 89.90 parts, 0.12 parts of ion-exchanged water, and 0.01 part of p-hydroxyphenyl monomethyl ethers are stirred at 60 degreeC for 4 hours, and then 1.36 parts of ortho formic-acid methyl esters are added, Furthermore, the reactive particle dispersion liquid was obtained by heat-stirring at the same temperature for 1 hour. After weighing 2g of this dispersion liquid to the aluminum dish, it dried for 1 hour and weighed on the 175 degreeC hotplate, and calculated | required solid content, and it was 36.5 weight%. Furthermore, after weighing 2 g of a dispersion liquid to a magnetic crucible, it preliminarily dried for 30 minutes on the hotplate of 80 degreeC, and calculated | required the inorganic content in solid content from the inorganic residue after calcining for 1 hour in the muffle furnace at 750 degreeC, It was 93 weight%. . It concentrated until solid content 70weight% and it was set as the silica particle (S) dispersion liquid. The number average particle diameter measured by the transmission electron microscope method of the obtained silica particle (S) was 50 nm.

Example 1

Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD® DPHA) 21.6 parts by weight, photopolymerization initiator (BASF Co., Ltd .: Irgacure 184) 0.6 part by weight, photopolymerization initiator (BASF Company: Irgacure 907 ) 0.4 parts by weight and 4.8 parts by weight of compound (C-1) prepared in Synthesis Example 1 were added (2.4 parts by weight of solids), further 22.6 parts of methyl isobutyl ketone and 50 parts of propylene glycol monomethyl ether acetate. Added and stirred to obtain a curable composition 1.

Examples 2-18 and Comparative Examples 1-3

Each curable composition was produced like Example 1 except having used each component with the compounding quantity shown in Table 2 and Table 3. In addition, compounding quantities other than the component (D) shown in Table 2 and Table 3 show the quantity as solid content.

<Production of a hard coat layer>

Each curable composition obtained by the said Example and the comparative example was coated by the spray coating method on the PET film of thickness 188 micrometers (film thickness 6 micrometers). After drying at 80 ° C. for 3 minutes, ultraviolet rays were irradiated with an irradiation dose of 300 mJ / cm 2 under air using a high pressure mercury lamp to photocuring to prepare each hard coat layer.

<Physical property evaluation of the hard coat layer>

Table 2 shows the results obtained by evaluating the following properties of the hard coat layer prepared as described above.

(1) Measurement of haze (%)

The haze (%) of the hard-coat layer was measured based on JIS # K7105 using the color haze meter (made by Sugashi Kenki Co., Ltd.).

(2) Measurement of total light transmittance (Tt;%)

The total light transmittance (%) of the hard coat layer was measured in accordance with JIS K7105 using a color haze meter (manufactured by Sugashi Kenki Co., Ltd.).

(3) anti-visual visibility

The back side of the film was painted black, and fingerprints were attached to the film surface. Then, it observed visually from the vertical upper direction of the film surface, and evaluated according to the following evaluation criteria.

(Circle): It is hard to identify a fingerprint.

(Triangle | delta): Although it knows that a fingerprint exists, it is not clearly identified.

X: The fingerprint is clearly identified.

(4) fingerprint wipe test

The back side of the film was painted black and fingerprints were attached to the film surface. Then, the fingerprint was wiped off with a tissue and evaluated in accordance with the following evaluation criteria.

(Circle): It is wiped off.

(Triangle | delta): It is hard to wipe.

X: It is not wiped off.

(5) Measurement of contact angle (°)

The contact angle of the hard-coat layer with respect to water and hexadecane was measured based on JIS6768 using the contact angle gauge Drop # Master500 by the Kyowa Chemical Co., Ltd ..

The compound described in Table 2 and Table 3 is as follows.

Reactive Particles 1: Reactive Particles 1 (Ec) Synthesized in Preparation Example 2

Reactive particle 2: Reactive particle 2 (Ec) synthesize | combined in manufacture example 3

Dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA

Pentaerythritol triacrylate: manufactured by Shin-Nakamura Kagaku Co., Ltd., NK ester A-TMM-3LM-N

Irg.184: Photopolymerization initiator manufactured by BASF Corporation

Ifg.907: BASF Co., Ltd., photopolymerization initiator

Each compound of component (C) is synthesize | combined by the synthesis examples 1-7.

EMALEX SPE-100S: Nihon Emulsion Co., Ltd., palm fatty acid sorbitan, HLB value 9

Emrex SPO-100: Nihon Emulsion Co., Ltd., monooleic acid sorbitan, HLB value 9

From the result of Table 2 and Table 3, it turns out that the hard-coat layer of an Example is excellent in all of transparency, fingerprint visibility, and fingerprint wiping.

In contrast, Comparative Examples 1 to 3 having an HLB value of 9 were inferior in fingerprint visibility and fingerprint wiping.

The composition of this invention can provide the cured film which is excellent in fingerprint visibility and fingerprint wiping property, and has high transparency.

The composition of the present invention is useful as a curable composition for hard coat formation suitable for spray coating.

Since the cured film formed by hardening | curing the composition of this invention is excellent in abrasion resistance, fingerprint wiping property, and is excellent in abrasion resistance, dry heat resistance, and moist heat resistance, and also has high transparency, a touch panel, a film type liquid crystal element, It is particularly useful as a protective coating material for preventing scratches or preventing contamination of plastic containers, flooring materials for building interior materials, wall materials, artificial marble, glass panels and the like.

Claims (10)

On the substrate,
Spray coating a curable composition containing the following components (A) to (D) to form a coating film, and
A method of forming a hard coat layer, comprising the step of irradiating the coating film with radiation to form a hard coat layer:
(A) polyfunctional (meth) acrylic monomer
(B) photoinitiator
(C) Nonionic surfactants consisting of fatty acid esters and having a polymerizable reactor
(D) an organic solvent. The method of claim 1,
The method for forming a hard coat layer in which the component (C) has a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms. The method according to claim 1 or 2,
The compounding quantity of the said component (C) exceeds 100 weight part with respect to a total of 100 weight part of the said component (A) and the said component (B), and the formation method of the hard-coat layer. The method according to claim 1 or 2,
The formation method of the hard-coat layer whose HLB value of the said component (C) is 2-7. Curable composition for spray coating containing following component (A)-(D):
(A) polyfunctional (meth) acrylic monomer
(B) photoinitiator
(C) nonionic surfactants consisting of fatty acid esters and having a polymerizable reactor
(D) an organic solvent. The method of claim 5,
Curable composition for spray coating in which the said component (C) has a linear or branched C6-C30 monovalent or bivalent hydrocarbon group. The method according to claim 5 or 6,
Curable composition for spray coatings whose compounding quantity of the said component (C) exceeds 10 weight part and is 100 weight part or less with respect to a total of 100 weight part of the said component (A) and the said component (B). The method according to claim 5 or 6,
Curable composition for spray coating whose HLB value of the said component (C) is 2-7. The method according to claim 5 or 6,
Furthermore, (E) curable composition for spray coating containing the inorganic oxide particle of the number average particle diameter 1-200 nm. 10. The method of claim 9,
Curable composition for spray coating in which the said component (E) has a polymerizable unsaturated group.