JP2012197331A - Curable composition, laminate and method for producing cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which allow excellent coating suitability to be obtained when spray-coated and from which a cured film having excellent transparency and scratch resistance can be formed and to provide a laminate having the cured film formed from the curable composition and a method for producing the cured film.SOLUTION: The curable composition contains (A) a polyfunctional (meth)acrylic monomer, (B) a photopolymerization initiator, (C) inorganic oxide particles and (D) an organic solvent. The content of the (C) component in the curable composition is 0.0001-5 parts mass when the total of all components except the (D) component is 100 parts mass. The content of particles, which are contained in the (C) component and have 200-1,000 nm particle size, is 0.0001-1 part mass.

Description

  The present invention relates to a curable composition, a laminate having a cured film formed from the curable composition, and a method for producing the cured film.

  Various bases such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin), metal, wood, paper, glass, slate, etc. As a protective coating material for preventing scratches and contamination on the surface of the material, it has excellent coating properties, and the surface of various base materials has hardness, scratch resistance, antifouling properties, abrasion resistance, There is a demand for a curable composition capable of forming a cured film excellent in any of surface slipperiness, low curling property, adhesion, transparency, chemical resistance and appearance of a coating film surface.

  In addition, a laminate (hard coat film) obtained by curing a curable composition on a film is required to have high transparency and excellent scratch resistance, particularly when used as a surface protective film. In order to satisfy such requirements, a technique for improving the abrasion resistance of a cured film by incorporating fine particles having a size that does not impair transparency into the curable composition has been studied.

  For example, in Patent Document 1, particles having a number average particle size of 30 to 200 nm mainly composed of surface-treated silica are contained in a curable composition, and a cured film is formed using the curable composition. It is described to form. According to this curable composition, a hard coat film having high hardness and scratch resistance can be formed on the surface of the substrate.

  Patent Document 2 contains, in a curable composition, surface-treated reactive inorganic particles having an average primary particle diameter of 5 to 80 nm and hydrophilic fine particles having an average primary particle diameter of 100 to 300 nm. It describes that a cured film is formed using the curable composition. According to this curable composition, it is possible to obtain a hard coat film having a desired uneven shape on the surface of the hard coat layer while maintaining transparency and scratch resistance.

JP 2008-24808 A JP 2009-132880 A

  By the way, in recent years, mobile phones, information terminals, and the like whose surfaces are hard-coated are commercially available. Since some of such mobile phones and information terminals have a curved surface appearance, there has been a need for “spray coating of a curable composition” that can be simply applied on a curved surface.

  However, when the curable composition described in Patent Document 1 and Patent Document 2 described above is spray-coated, thixotropic properties are manifested because a large amount of fine particles are contained in the curable composition. As a result, the coatability may be impaired. In order to improve the coating property in this spray, for example, if the content of fine particles in the curable composition is reduced, there is a problem that the scratch resistance of the cured film is impaired.

  Therefore, some embodiments according to the present invention can form a cured film having excellent transparency and scratch resistance as well as excellent coating properties in spray coating by solving the above-mentioned problems. The present invention provides a curable composition, a laminate having a cured film formed from the curable composition, and a method for producing the cured film.

  The present invention can be realized as the following aspects or application examples.

[Application Example 1]
One aspect of the curable composition according to the present invention is:
(A) polyfunctional (meth) acrylic monomer,
(B) a photopolymerization initiator,
A curable composition containing (C) inorganic oxide particles, and (D) an organic solvent,
The content of the component (C) in the curable composition is 0.0001 parts by mass or more and 5 parts by mass or less when the total of all components other than the component (D) is 100 parts by mass, And content of the particle | grains in the range of 200 nm or more and 1000 nm or less contained in the said (C) component is 0.0001 mass part or more and 1 mass part or less, It is characterized by the above-mentioned.

[Application Example 2]
In the curable composition of Application Example 1,
When the total content of all components other than the component (D) is 100 parts by mass, the content of particles contained in the component (C) in the range of 200 nm to 1000 nm is 0.001 part by mass or more. It can be 0.5 parts by mass or less.

[Application Example 3]
In the curable composition of Application Example 1,
When the content of particles in the range of 200 nm to 1000 nm in the particle size contained in the component (C) is 100 parts by mass with respect to the total of all components other than the component (D), 0.005 parts by mass or more It can be 0.5 parts by mass or less.

[Application Example 4]
In the curable composition of any one of Application Examples 1 to 3,
Furthermore, (E) the nonionic surfactant which consists of fatty acid ester and whose HLB value is 2-7 can be contained.

[Application Example 5]
In the curable composition of Application Example 4,
The HLB value of the component (E) can be 2-4.

[Application Example 6]
In the curable composition of Application Example 4 or Application Example 5,
The component (E) may have a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms.

[Application Example 7]
In the curable composition of any one of Application Examples 4 to 6,
The component (E) can have a (meth) acryloyl group.

[Application Example 8]
The curable composition described in any one of Application Examples 1 to 7 can be used for spray coating.

[Application Example 9]
One aspect of the laminate according to the present invention is:
It has a cured film obtained by curing the curable composition of any one of Application Examples 1 to 8 on the substrate, and the haze value measured in accordance with JIS K7136 is 1% or less It is characterized by being.

[Application Example 10]
One aspect of the method for producing a cured film according to the present invention is as follows.
A step of spray-coating the curable composition of Application Example 8 on a substrate to form a coating film;
Irradiating the coating film with radiation;
It is characterized by including.

  According to the curable composition concerning this invention, while being able to obtain favorable coating property in spray coating, the cured film excellent in transparency and scratch resistance can be formed.

  Moreover, since the laminated body which concerns on this invention has the cured film formed from the curable composition mentioned above, it is excellent in transparency and scratch resistance.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included. In the present specification, for example, the following “(A) polyfunctional (meth) acrylic monomer” may be simply abbreviated as “(A) component”. The same applies to the components (B) to (F).

1. Curable composition The curable composition (henceforth a "composition" only) which concerns on this Embodiment may contain the following (A)-(F) component. Among these, the components (A) to (D) are essential components, and the components (E) and (F) are optional components that can be added as necessary.
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) Inorganic oxide particles (D) Organic solvent (E) Nonionic surfactant comprising fatty acid ester (F) Other additives

  In the curable composition according to the present embodiment, among the component (C), the content of particles having a particle diameter in the range of 200 nm or more and 1000 nm or less is the sum of all components other than the component (D) being 100. When the content is from 0.0001 parts by mass to 1 part by mass, a cured film having excellent transparency and abrasion resistance can be formed. Moreover, according to the curable composition which concerns on this Embodiment, expression of thixotropy can be suppressed by making content of the said (C) component into 5 mass parts or less. Thereby, favorable coating property is obtained in spray coating.

  Hereinafter, each component which may be contained in the curable composition which concerns on this Embodiment is demonstrated in detail. In the present specification, (meth) acryloyl represents acryloyl and methacryloyl, and (meth) acrylate represents acrylate and methacrylate.

1.1. (A) Polyfunctional (meth) acrylic monomer (A) The polyfunctional (meth) acrylic monomer is a (meth) acrylic monomer having two or more (meth) acryloyl groups. (A) A component is what is called a binder component for improving the film formability of a composition. In addition, although (C) component mentioned later is a reactive particle, and (E) component mentioned later may have two or more (meth) acryloyl groups, in (A) polyfunctional (meth) acryl monomer in this invention, Shall not contain reactive particles and component (E).

  (A) Specific examples of the polyfunctional (meth) acrylic monomer include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 3 or more (meth) acryloyl groups such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Polyfunctional (meth) acrylic monomer having; ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, etc. ) Polyfunctional (meth) acrylic monomer having two acryloyl groups; hydroxyl group-containing polyfunctional (meth) acrylates such as bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and ethylene oxide or propylene to these hydroxyl groups Poly (meth) acrylates of oxide adducts; oligoester (meth) acrylates having two or more (meth) acryloyl groups, oligoether (meth) acrylates, oligoepoxy (meth) acrylates, etc. That. The polyfunctional (meth) acrylic monomers exemplified above may be used alone or in combination of two or more.

  Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable. .

  As a commercial item of such (A) polyfunctional (meth) acrylic monomer, for example, 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 (above, manufactured by Toa Gosei Co., Ltd.); KAYARAD D-310, D-330, DPHA, DPCA- 0, 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 (Nippon Kayaku Co., Ltd.) Light acrylates PE-4A, DPE-6A, DTMP-4A (manufactured by Kyoeisha Chemical Co., Ltd.); NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  The total amount of the component (A) is preferably 100% by mass, and the polyfunctional (meth) acryl monomer having 3 or more (meth) acryloyl groups is preferably contained in an amount of 50% by mass or more, and more preferably 70% by mass or more. More preferably, the content is particularly preferably 100% by mass.

  The content of the component (A) in the composition according to the present embodiment is preferably in the range of 50 to 99 parts by mass when the total of all components other than the component (D) is 100 parts by mass, More preferably, it is in the range of 98 parts by mass, and particularly preferably in the range of 75 to 95 parts by mass. When the component (A) is contained in the above range, a cured film having a high hardness can be obtained.

1.2. (B) Photopolymerization initiator (B) The photopolymerization initiator is a compound that generates active radical species by radiation (light) irradiation, and examples thereof include those that are widely used.

  (B) The photopolymerization initiator is not particularly limited as long as it is decomposed by radiation (light) irradiation to generate radicals and initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2- Droxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -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-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1- Methyl vinyl) phenyl) propanone) and the like.

  Commercially available photopolymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173, Lucillin TPO, 8893 (or more Ubecril P36 (manufactured by UCB); Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (above, manufactured by Lamberti) and the like.

  Content of the component (B) in the composition which concerns on this Embodiment exists in the range of 0.1-15 mass parts, when the sum total of all the components other than (D) component is 100 mass parts. It is preferable that it is in the range of 0.3 to 15 parts by mass, and it is particularly preferable that it is in the range of 0.5 to 10 parts by mass.

1.3. (C) Inorganic oxide particle The curable composition which concerns on this Embodiment contains (C) inorganic oxide particle. The component (C) includes inorganic oxide particles having a particle size in the range of 200 nm to 1000 nm. The component (C) is not particularly limited as long as it is a particle mainly composed of an inorganic oxide. For example, the component is a particle in which the surface of an inorganic oxide particle is treated with a particle modifier and a reactive functional group is introduced on the surface. There may be.

  Generally, from the relationship between the wavelength of visible light and the refractive index of particles, when particles having a particle diameter exceeding 100 nm are added to the curable composition, the haze of the resulting cured film may increase. Are known. However, according to the curable composition according to the present embodiment, (C) the inorganic oxide particles having a particle size in the range of 200 nm to 1000 nm, the total of all components other than (D) component is 100 parts by mass. It was found that by containing 0.0001 parts by mass or more and 1 part by mass or less, haze of the obtained cured film can be suppressed low and scratch resistance can be improved.

  That is, the component (C) needs to contain particles having a particle size in the range of 200 nm to 1000 nm. By containing particles having a particle size in the above range, an effect of improving the scratch resistance of the cured film can be obtained with a small amount of inorganic oxide particles. When the particle diameter is less than the above range, scratch resistance of the cured film is difficult to obtain, and a large amount of particles is required to improve the scratch resistance, so that the appearance of the cured film may be impaired. When the particle diameter exceeds the above range, the transparency of the cured film may be impaired because the particle diameter is too large. In addition, the particle diameter of the particle | grains contained in (C) component, and the content rate of 200 nm or more and 1000 nm particle | grains can be measured with the particle size distribution measuring apparatus which uses a dynamic light scattering method as a measurement principle.

  Of the component (C) in the composition according to the present embodiment, the content of the particles whose particle diameter is included in the above range is, when the total of all components other than the component (D) is 100 parts by mass, It is 0.0001 parts by mass or more and 1 part by mass or less, preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.005 parts by mass or more and 0.5 parts by mass or less. When content of (C) component exists in the said range, while being able to suppress the haze of a cured film low, scratch resistance can be improved. When the content of the component (C) in the particle diameter range is less than the above range, it is difficult to improve the scratch resistance of the cured film. When the content of the component (C) in the particle size range exceeds the above range, the haze of the cured film may increase and the transparency may be impaired. In particular, particles having a particle diameter in the component (C) exceeding 1000 nm tend to have high haze, so that when the total of all components other than the component (D) is 100 parts by mass, 0.2 parts by mass or less. It is preferable to do. In addition, when the composition exhibits thixotropic properties, good coating properties cannot be obtained particularly in spray coating.

  The composition according to this embodiment may contain inorganic oxide particles having a particle diameter of less than 200 nm as long as the thixotropic property of the composition is not exhibited. From the viewpoint of not exhibiting thixotropic properties, the upper limit of the content of the component (C) is 5 parts by mass or less when the total of all components other than the component (D) is 100 parts by mass, and 4 parts by mass. Preferably, it is preferably 3 parts by mass or less.

  (C) component can be suitably selected and used from a viewpoint of the transparency and hue of the cured film obtained.

  As a preferred example of the component (C), particles mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Specific examples include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Among these, silica, alumina, zirconia, and antimony oxide particles are preferable from the viewpoint of high hardness. These particles can be used singly or in combination of two or more.

  The component (C) is preferably used as a powder or solvent dispersion sol. When used as a solvent-dispersed sol, examples of the dispersion medium include water and organic solvents. From the viewpoint of compatibility with other components and dispersibility, organic solvents are preferable. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as 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; dimethylformamide, dimethylacetamide, Amides such as N-methylpyrrolidone can be mentioned. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

  Examples of commercially available silicon oxide particles (for example, silica particles) include IPA-ST-ZL, MEK-ST-ZL, MEKST-2040 (manufactured by Nissan Chemical Industries, Ltd.), SO-E1, and SO-E2. , SO-C1, SO-C2, SC1050-KJA, SC2050-KD (manufactured by Admatechs Co., Ltd.) and the like.

  Examples of commercially available alumina particles include Nanofine AD-8 (manufactured by Hinomoto Abrasive Co., Ltd.), A33F (manufactured by Nippon Light Metal Co., Ltd.), and the like.

The shape of the component (C) may be spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, but spherical is preferred. (C) a specific surface area (by BET method using nitrogen) of the component is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  As described above, the component (C) is an inorganic oxide particle surface-treated with an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule (hereinafter also referred to as “particle modifier”) ( (Hereinafter also referred to as “reactive particles”). Since the reactive particles can form a covalent bond with the binder component, a cured film excellent in scratch resistance, heat resistance and transparency can be obtained.

  The particle modifier is not particularly limited as long as it is an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group. Examples of the polymerizable unsaturated group include ethylenically unsaturated groups such as vinyl group and (meth) acryloyl group. The hydrolyzable silyl group is a group that reacts with water to form a silanol (Si—OH) group. For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. Group, an alkoxy group such as n-butoxy group, an aryloxy group, an acetoxy group, an amino group, and a halogen atom bonded thereto. As the particle modifier, commercially available products such as γ-methacryloxypropyltrimethoxysilane can be used, and for example, compounds described in International Publication No. WO97 / 12942 can be used.

1.4. (D) Organic solvent The composition which concerns on this Embodiment is diluted with (D) organic solvent from a viewpoint which improves the applicability | paintability in spray coating especially. The viscosity of the curable composition at the time of spray coating is usually 0.1 to 100 mPa · sec / 25 ° C., preferably 0.5 to 50 mPa · sec / 25 ° C.

  (D) Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, 1-butanol, 2-butanol, tert-butyl alcohol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid Esters such as ethyl, 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; aroma such as benzene, toluene and xylene Group hydrocarbons; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  The content of the (D) organic solvent in the composition according to the present embodiment is within the range of 50 to 10,000 parts by mass when the total of the components excluding the (D) organic solvent is 100 parts by mass. Preferably there is. The content of (D) the organic solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the composition, the shape of the spray nozzle, the nozzle diameter, and the like.

1.5. (E) Nonionic surfactant The composition which concerns on this Embodiment can contain the nonionic surfactant which consists of (E) fatty acid ester and whose HLB value is 2-7 as needed. . The component (E) is blended for the purpose of making it difficult to see the fingerprint attached to the cured film and improving the wiping property of the fingerprint.

  As described above, the curable composition according to this embodiment can be suitably used in spray coating because thixotropic properties are suppressed. When coating by spraying, the surfactant is less likely to be unevenly distributed on the surface of the coating film, so a larger amount of surfactant is required than when coating by other coating methods. When a curable composition containing a large amount of a surfactant is used, the resulting cured film may be whitened. However, whitening of the cured film can be suppressed by using a nonionic surfactant having an HLB value in the range of 2 to 7. By setting the HLB value within the above range, even if a large amount of a surfactant is added, whitening does not occur and a composition suitable for spray coating can be obtained. In addition, it is preferable that the HLB value of (E) component is 2-4 from the point which can suppress whitening of a cured film more effectively.

Here, the HLB (Hydrophile-Lipophile Balance) value is an index indicating the characteristics of the surfactant and indicates the degree of hydrophilicity or lipophilicity. The HLB value can be obtained by the following calculation formula.
HLB = 7 + 11.7Log (M _W / M _O )
In the formula, M _W is the molecular weight of the hydrophilic groups, M _O is the molecular weight of the lipophilic group. M _W + M _O = M (molecular weight of the surfactant).

  Moreover, since the (E) component and the binder component can be bonded and fixed by adding a (meth) acryloyl group to the (E) component, the (E) component bleeds out to the surface of the cured film. This can be prevented. Thereby, durability of the cured film obtained improves.

  As a method for adding a (meth) acryloyl group to the component (E), for example, it can be obtained by converting a hydroxyl group of a fatty acid ester surfactant having a hydroxyl group into a (meth) acryloyl group. Specifically, the component (E) can be obtained by reacting a hydroxyl group of a fatty acid ester surfactant with a compound having a (meth) acryloyl group.

  As the compound having a (meth) acryloyl group, for example, a compound having an isocyanate group and a (meth) acryloyl group can be used. By using such a compound, the hydroxyl group of the fatty acid ester surfactant and the isocyanate group react to form a urethane bond, whereby a (meth) acryloyl group is introduced.

  Specific examples of the compound having an isocyanate group and a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl]. Ethyl isocyanate and the like can be used. It can also be obtained by reacting a diisocyanate compound with a compound containing a hydroxyl group and a (meth) acryloyl group. Examples of such diisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

  Specific examples of the fatty acid ester-based surfactant having a hydroxyl group include polyoxyalkylene hydrogenated castor oil and polyoxyalkylene fatty acid ester, and polyoxyethylene hydrogenated castor oil and polyoxyethylene fatty acid ester are preferable. Examples of commercially available polyoxyethylene hydrogenated castor oil include EMALEX HC series (manufactured by Nippon Emulsion Co., Ltd.) and Neugen HC series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Examples of commercially available polyoxyethylene fatty acid esters include EMALEX GWIS-100EX (glyceryl isostearate, manufactured by Nippon Emulsion Co., Ltd.), Neugen GIS series (produced by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

  The reaction between the fatty acid ester-based surfactant having a hydroxyl group and the compound having an isocyanate group and a (meth) acryloyl group can be carried out as follows. That is, it is a reaction of an isocyanate compound and a hydroxyl group-containing compound, and usually copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6, It is preferable to use 0.01 to 1 part by mass of a urethanization catalyst such as 7-trimethyl-1,4-diazabicyclo [2.2.2] octane with respect to 100 parts by mass of the total amount of the reactants. Moreover, in the reaction of these compounds, it can also carry out without a catalyst. The reaction temperature is usually from 0 to 90 ° C, preferably 40 to 80 ° C. Such a reaction may be carried out without a solvent or by dissolving in a solvent.

  Furthermore, the component (E) preferably has a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms. By having a hydrocarbon group having 6 to 30 carbon atoms, fingerprint visibility and fingerprint wiping properties can be imparted to the resulting cured film. Here, “fingerprint visibility” means the difficulty of seeing with the naked eye when a fingerprint is attached to the film surface.

  The component (E) can have a structure represented by the following general formula (1), for example.

式（１）中、各記号の意味は下記の通りである。Ｘは置換されていてもよい炭素数３〜１０の（ｍ^１＋ｍ^２）価の炭化水素基を示す。複数個あるＹ^１およびＹ^２はそれぞれ独立にエーテル結合、エステル結合、あるいはウレタン結合を含む２価の基または単結合を示し、Ｙ^１およびＹ^２の少なくとも１個は脂肪酸に由来する構造を有する。Ｚは（メタ）アクリロイル基を１個以上有する基を示す。複数個あるＲ^１１およびＲ^１２はそれぞれ独立に炭素数１〜４の直鎖または分岐の炭化水素基を示す。ｍ^１およびｍ^２はそれぞれ０〜１０の整数であり、ｎ^１およびｎ^２はそれぞれ独立に０〜２０の整数である。ただし、ｍ^１およびｍ^２は同時に０ではない。

In formula (1), the meaning of each symbol is as follows. X represents an optionally substituted (m ¹ + m ² ) -valent hydrocarbon group having 3 to 10 carbon atoms. A plurality of Y ¹ and Y ² each independently represent a divalent group or a single bond containing 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. However, m ¹ and m ² are not 0 at the same time.

  (E) The nonionic surfactant which consists of fatty acid ester and whose HLB value is 2-7 is compoundable as follows. It can be obtained by reacting a hydroxyl group-containing surfactant with an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group at a ratio such that the HLB after the reaction is 2 to 7. For example, when a surfactant having three hydroxyl groups is used as a raw material, when the HLB of the raw material surfactant is 5, an isocyanate compound having a (meth) acryloyl group of 1/3 molar equivalent of the hydroxyl group or ( It is only necessary to react the (meth) acrylic acid. When the HLB of the raw material surfactant is 9, it is preferable to react an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group having an equimolar equivalent of the hydroxyl group.

  Content of (E) component in the composition which concerns on this Embodiment exists in the range of 0.1-30 mass parts, when the sum total of all the components other than (D) component is 100 mass parts. Is preferable, it is more preferable to be in the range of 0.5 to 20 parts by mass, and it is particularly preferable to be in the range of 1 to 15 parts by mass. By making content of (E) component into the said range, since sufficient fingerprint visibility is obtained also in the cured film obtained in spray coating, it is preferable. In addition, since the hardness of a cured film may fall when (E) component does not have a (meth) acryloyl group, content of (E) component is made into the sum total of all components other than (D) component. It is preferable to set it as 0.1-10 mass parts with respect to 100 mass parts.

1.6. (F) Other additives In the composition according to the present embodiment, in addition to the above-described components, a radical polymerizable compound other than the component (A), an antioxidant, an ultraviolet absorber, a leveling agent, and the like as necessary. Can be added.

  The composition according to the present embodiment is prepared by adding each of the above components (A) to (D) and, optionally, components arbitrarily selected from (E) to (F), at room temperature or under heating conditions. Can be prepared by mixing. Specifically, it can be prepared using a known mixer such as a mixer, a kneader, or a ball mill. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the polymerization initiator or polymerizable unsaturated group. The composition according to the present embodiment obtained as described above can be cured by radiation (light).

2. Manufacturing method of laminated body and cured film The laminated body according to the present embodiment has a cured film obtained by curing the above-described curable composition on a substrate, and is measured in accordance with JIS K7136. The haze value is 1% or less. Such a laminate can be obtained by coating and curing the above-mentioned curable composition on various substrates. Specifically, the above-described composition is coated on a substrate, and (D) volatile components such as an organic solvent are volatilized and removed at 0 to 200 ° C. as necessary, followed by curing with radiation (light). Can be obtained.

  The substrate used in the laminate according to the present embodiment is not particularly limited, but from the viewpoint of high transparency, polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, polyethylene terephthalate, triacetyl Various plastic films such as cellulose, ABS, AS, cycloolefin resin, norbornene resin, and glass are preferable. Although the thickness of the transparent base material used can be suitably changed according to the use, for example, a base material having a thickness of 10 to 5000 μm can be used. In addition, when the above-mentioned curable composition is directly applied on a substrate and subjected to a curing treatment, if the adhesion between the substrate and the cured film is poor, a corona discharge treatment, a plasma treatment, Surface treatment such as easy adhesion treatment can also be performed.

  Examples of the coating method on the substrate include spray coating and usual coating methods such as dipping coating, flow coating, shower coating, roll coating, spin coating, and brush coating. In addition, the above-mentioned curable composition is sufficiently suppressed in thixotropy, and can exhibit excellent coating properties in spray coating. Therefore, spray coating is particularly preferable as a method for coating the substrate. The thickness of the coating film in these coatings is the thickness after drying and curing, and is preferably 0.1 to 400 μm, more preferably 0.5 to 200 μm.

The radiation (light) is not particularly limited as long as it can be cured in a short time after coating the composition, but ultraviolet rays and electron beams are preferred for reasons such as availability of an irradiation apparatus. As an ultraviolet ray source, a mercury lamp, a halide lamp, a laser, or the like can be used, and as an electron beam source, a method using thermoelectrons generated from a commercially available tungsten filament can be used. . When ultraviolet rays or electron beams are used as the radiation, the preferred irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

  The laminate according to the present embodiment has a haze value measured in accordance with JIS K7136 of 1% or less, preferably 0.8% or less, and more preferably 0.6% or less. . When the haze value of the laminate exceeds 1%, the transparency becomes insufficient and a cloudy appearance is exhibited. From the same viewpoint, the total light transmittance of the laminate is preferably 90% or more. If the total light transmittance is less than 90%, the visibility may be inferior depending on the application.

  Since the laminate according to this embodiment has excellent transparency and scratch resistance, and may have excellent fingerprint wiping property and fingerprint visibility, fingerprints such as mobile phones and information terminals are likely to adhere. It is suitable as a surface protective film for various portable devices used in the scene.

3. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” represents mass%, and “part” represents mass part.

3.1. Example of synthesis of component (E) 3.1.1. Synthesis Example 1: Production of Compound (E-1) A synthesis method of the compound (E-1) represented by the following general formula (2) is shown below.

式（２）中、Ｒ^１は、下記式（３）で表される基である。ａ＋ｂ＋ｃ＝７である。

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

  To a three-necked flask equipped with a stirrer, 0.030 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical Co., Yoshinox BHT), pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd., NK) 21.05 g of ester A-TMM-3LM-N), 9.10 g of 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur I), and methyl isobutyl ketone (Mitsubishi Chemical) 50.00 g) was added, and after adding 0.31 g of dioctyltin dilaurate (Kyodo Pharmaceutical Co., Ltd., KS-1200-A), the mixture was stirred at room temperature for 2 hours. Subsequently, 19.52 g of polyoxyethylene hydrogenated castor oil (Nippon Emulsion Co., Ltd., EMALEX HC-7; HLB value 6) was added. The reaction solution was heated to 60 ° C. and stirred for 2 hours to obtain compound (E-1). Moreover, since the acrylation reaction proceeds almost quantitatively, the HLB of the compound (E-1) determined from the charged amount is 3.

3.1.2. Synthesis Examples 2-3: Production of Compounds (E-2) to (E-3) The following compounds (E) were prepared in the same manner as in Synthesis Example 1 except that the compounds shown in Table 1 were used in the proportions shown in Table 1. -2) and (E-3) were obtained. The HLB value of each compound is as described in Table 1.

式（４）中、Ｒ^２は、それぞれ下記式（５）で表される基である。ａ＋ｂ＋ｃ＝７である。 Compound (E-2)

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

式（６）中、Ｒ^３は、それぞれ上記式（５）で表される基である。ａ＋ｂ＋ｃ＝５である。 Compound (E-3)

In formula (6), R ³ is a group represented by the above formula (5). a + b + c = 5.

・ＴＤＩ：三井化学ポリウレタン株式会社製、ＴＯＬＤＹ−１００、トリレンジイソシアネート、分子量：１７４．１６
・ＩＰＤＩ：デスモジュールＩ、住化バイエルウレタン社製、イソホロンジイソシアネート、分子量：２２２．２９
・ＰＥＴＡ：ＮＫエステル Ａ−ＴＭＭ−３ＬＭ−Ｎ、新中村化学株式会社製、ペンタエリスリトールトリアクリレート、分子量：２９８．３
・ＢＨＴ：ヨシノックスＢＨＴ、吉富ファインケミカル株式会社製、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、分子量：２２０
・ＫＳ−１２００−Ａ：共同薬品株式会社製、ジラウリル酸ジオクチル錫
・ＭＩＢＫ：メチルイソブチルケトン In addition, the component described in Table 1 is as follows.
HC-5: EMALEX HC-5, polyoxyethylene hydrogenated castor oil having a structure represented by the following formula (7) (however, a + b + c = 5), manufactured by Nippon Emulsion Co., Ltd., HLB value 5
HC-7: EMALEX HC-7, polyoxyethylene hydrogenated castor oil having a structure represented by the following formula (7) (however, a + b + c = 7), manufactured by Nippon Emulsion Co., Ltd., HLB value 6

* TDI: Mitsui Chemicals Polyurethane Co., Ltd., TOLDY-100, tolylene diisocyanate, molecular weight: 174.16
IPDI: Desmodur I, manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate, molecular weight: 222.29
PETA: NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol triacrylate, molecular weight: 298.3
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., dioctyltin dilaurate-MIBK: methyl isobutyl ketone

3.2. Preparation example of curable composition 3.2.1. Example 1
Silica particles 2 (manufactured by Nissan Chemical Industries, Ltd., trade name “MEK-ST-2040”) in solid content concentration of 0.05 part by mass, dipentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK ester” A-TMM-3LM-N ") 34.6 parts by mass, Irgacure 184 (manufactured by BASF Japan, photopolymerization initiator) 1.0 mass part, Irgacure 907 (manufactured by BASF Japan, photopolymerization initiator) 0 .6 parts by mass and 3.8 parts by mass of the compound (E-1) produced in Synthesis Example 1, 9.0 parts by mass of methyl isobutyl ketone, 16.8 parts by mass of propylene glycol monomethyl ether acetate, tert-butyl The curable composition which concerns on Example 1 was obtained by adding 34.2 mass parts of alcohol and stirring sufficiently.

3.2.2. Examples 2-14 and Comparative Examples 1-4
Each curable composition was produced in the same manner as in Example 1 except that each component was used in the blending amounts shown in Table 2 and Table 3. In addition, compounding quantities other than (D) component described in Table 2 and Table 3 represent the quantity as solid content.

3.3. Evaluation of cured film 3.3.1. Production of Cured Film Each curable composition obtained in the above Examples and Comparative Examples was coated on a PET film having a thickness of 188 μm by a spray coating method so as to have a film thickness of 10 μm. After drying in an oven at 80 ° C. for 3 minutes, a cured film was produced by irradiating ultraviolet rays at a dose of 300 mJ / cm ² under air using a high-pressure mercury lamp.

3.3.2. Evaluation of physical properties of cured film The following properties of the cured film obtained as described above were evaluated. The obtained results are shown in Table 2 and Table 3 together.

(1) Appearance of coating film The cured film was visually observed and evaluated according to the following evaluation criteria.
◯: A yuzu skin-like appearance cannot be confirmed in the cured film 180 mm × 100 mm.
(Triangle | delta): The yuzu skin-like surface appearance can be confirmed in part in the cured film 180 mm x 100 mm.
X: A yuzu skin-like appearance can be confirmed as a whole in the cured film 180 mm × 100 mm.

(2) Measurement of haze The haze (%) of the cured film was measured according to JIS K7136 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).

(3) Measurement of total light transmittance (Tt;%) The total light transmittance (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). .

(4) Scratch resistance test (steel wool resistance test)
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (“AB-301”, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded with a load of 300 g / Scratching was repeated 10 times under the conditions of cm ² , and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following evaluation criteria.
A: The cured film is not damaged (uninjured).
B: Several scratches are generated on the cured film.
C: Many scratches are generated on the cured film.
D: The cured film peels off.

In addition, when repeatedly rubbing 10 times under the condition of load 900 g / cm ² , when rubbing 10 times under the condition of load 1500 g / cm ² , and when rubbing 100 times under the condition of load 500 g / cm ² , The scratch resistance was evaluated in the same manner as described above.

The abbreviations described in Table 2 and Table 3 represent the following. In addition, the particle size distribution of (C) component was measured with the dynamic light scattering type particle size distribution measuring apparatus LB-550 by Horiba. Since this apparatus measures a volume distribution, it is converted as a mass as it is. (C) Component blending amount The numerical value in parentheses at the lower stage represents the amount of particles having a particle diameter of 200 to 1000 nm.
-Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd., KAYARAD DPHA
Pentaerythritol triacrylate: NK Ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.
・ Irg. 184: BASF Japan, photopolymerization initiator, Irg. 907: manufactured by BASF Japan, photopolymerization initiator / silica particles 1: manufactured by Nissan Chemical Industries, Ltd., MEK-ST-ZL, does not contain particles of 200 nm to 1000 nm.
Silica particles 2: manufactured by Nissan Chemical Industries, Ltd., MEK-ST-2040, containing 52% by mass of particles of 200 nm to 1000 nm.
Silica particle 3: SC1050-KJA, manufactured by Admatechs Co., Ltd. contains 80% by mass of particles of 200 nm to 1000 nm.
Silica particles 4: manufactured by Admatechs Co., Ltd., SC2050-KD, containing 99% by mass of 200 nm to 1000 nm particles.
Compound (E-1): Compound (E) produced in Synthesis Example 1 Compound (E-2): Compound (E) produced in Synthesis Example 2 Compound (E-3): Synthesis Example Compound (E) produced in step 3

  From the results of Table 2 and Table 3, according to the curable compositions of Examples 1 to 14 in which specific amounts of particles having a particle diameter of 200 nm to 1000 nm were blended, excellent transparency and scratch resistance (steel wool resistance) It was found that a cured film having) can be formed.

  It was found that the cured film formed from the curable composition of Comparative Example 1 containing no component (C) was excellent in transparency but was greatly inferior in scratch resistance.

  The cured film formed from the curable composition of Comparative Example 2 in which 2 parts by mass of particles having a particle size of 200 nm to 1000 nm are blended is excellent in scratch resistance but is largely inferior in transparency. understood.

  (C) Although the component is mix | blended, but the cured film formed from the curable composition of the comparative example 3 which is not mix | blended the particle | grains whose particle diameter is 200 nm-1000 nm is excellent in transparency, It was found that the scratch resistance was greatly inferior.

  The cured film formed from the curable composition of Comparative Example 4 in which 25 parts by mass of silica particles 1 were blended was found to have an inferior coating film appearance, although some improvement in scratch resistance was observed.

  The curable composition of the present invention is useful for producing a cured film having excellent transparency and scratch resistance, as well as excellent fingerprint wiping and fingerprint visibility. The composition of the present invention is useful as a curable composition suitable for spray coating.

  Since the laminate according to this embodiment has excellent transparency and scratch resistance, and may have excellent fingerprint wiping property and fingerprint visibility, fingerprints such as mobile phones and information terminals are likely to adhere. It is useful as a surface protective film for various portable devices used in the scene.

Claims (10)

(A) polyfunctional (meth) acrylic monomer,
(B) a photopolymerization initiator,
A curable composition containing (C) inorganic oxide particles, and (D) an organic solvent,
The content of the component (C) in the curable composition is 0.0001 parts by mass or more and 5 parts by mass or less when the total of all components other than the component (D) is 100 parts by mass, And the content of the particle | grains in the range of the particle diameter 200nm or more and 1000nm or less contained in the said (C) component is 0.0001 mass part or more and 1 mass part or less. In claim 1,
When the total content of all components other than the component (D) is 100 parts by mass, the content of particles contained in the component (C) in the range of 200 nm to 1000 nm is 0.001 part by mass or more. The curable composition which is 0.5 mass part or less. In claim 1,
When the content of particles in the range of 200 nm to 1000 nm in the particle size contained in the component (C) is 100 parts by mass with respect to the total of all components other than the component (D), 0.005 parts by mass or more The curable composition which is 0.5 mass part or less. In any one of Claims 1 to 3,
And (E) a curable composition comprising a nonionic surfactant comprising a fatty acid ester and having an HLB value of 2 to 7. In claim 4,
The curable composition whose HLB value of the said (E) component is 2-4. In claim 4 or claim 5,
The curable composition in which the component (E) has a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms. In any one of Claims 4 thru | or 6,
The curable composition in which the component (E) has a (meth) acryloyl group.   The curable composition according to any one of claims 1 to 7, which is used for spray coating. A cured film obtained by curing the curable composition according to any one of claims 1 to 8 on a substrate, and
The laminated body whose haze value measured based on JISK7136 is 1% or less. A step of spray-coating the curable composition according to claim 8 to form a coating film on a substrate;
Irradiating the coating film with radiation;
A method for producing a cured film, comprising: