KR102329391B1 - Photocurable resin composition, cured film formed of composition and base material with coating film, and method for producing cured film and base material with coating film - Google Patents

Abstract

Forms a cured film with excellent weather resistance, scratch resistance and anti-glare properties. An aliphatic urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a spherical silica particle (C), an ultraviolet absorber (D), and a fluorine-based compound (E) having a photopolymerizable unsaturated group, A photocurable resin composition containing a photoinitiator (F) is provided.

Description

A photocurable resin composition, a cured film formed from the composition, a substrate having a film, and a method for manufacturing a substrate having a cured film and film CURED FILM AND BASE MATERIAL WITH COATING FILM}

The present invention relates to a photocurable resin composition, a cured film formed from the composition and a substrate having a film, and a method for manufacturing a cured film and a substrate having a film.

BACKGROUND ART A display or touch panel used outdoors, a protective film for window glass of a building or vehicle, a light-shielding film, etc. are lightweight and have excellent transparency, and are easily scratched. Therefore, the cured film as a protective film is provided on the surface of these films. A cured film is formed by apply|coating and hardening a photocurable resin composition (coating agent) on the surface of a film, for example.

In this cured film, there is little deterioration even when exposed to light (ultraviolet rays) or water for a long period of time, and it is difficult to discolor (weather resistance) and scratch-resistant (scratch resistance). Antiglare properties are required from the viewpoint of suppression.

Therefore, in order to impart weather resistance to the cured film, an ultraviolet absorber or light stabilizer is blended into the photocurable resin composition, or in order to improve the scratch resistance of the cured film, a component that improves the hardness of the cured film is used. The method is generally known. Moreover, in order to provide antiglare property to a cured film, it is known to add microparticles|fine-particles, such as a silica and an acrylic resin bead, to a photocurable resin composition (for example, refer patent document 1). According to the microparticles|fine-particles, the glare of the light to a hardened film can be suppressed by forming the surface of a hardened film in an uneven|corrugated shape, and scattering or diffusing light by the unevenness|corrugation.

Japanese Patent Laid-Open No. 2004-25787

However, when microparticles|fine-particles are mix|blended with a photocurable resin composition in order to provide anti-glare property, when a hardened film receives impacts, such as friction, there exists a possibility that the microparticles|fine-particles in a convex part may fall off. When microparticles|fine-particles fall off, the drop-off|omission location may become a defect and the scratch resistance of a cured film may fall. Moreover, when a ultraviolet absorber etc. are mix|blended in order to provide weather resistance, when hardening a coating film by light irradiation, hardening inhibition is raised, and there exists a possibility that the hardness and scratch resistance of a cured film may fall. Thus, in the cured coating film, it is difficult to obtain a good balance of weather resistance, scratch resistance and anti-glare properties at a high level.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a technique for forming a cured film excellent in weather resistance, scratch resistance and antiglare properties.

According to a first aspect of the present invention,

An aliphatic urethane (meth)acrylate (A),

(meth) acrylate monomer (B) and,

Spherical silica particles (C);

UV absorber (D) and

A fluorine-based compound (E) having a photopolymerizable unsaturated group, and

The photopolymerization initiator (F) is contained, and the spherical silica particles (C) have a particle size of 10% and 90%, respectively, of D10 and D90 in the volume-based particle size distribution, D90/D10 of 2.0 or less. A chemical conversion resin composition is provided.

According to a second aspect of the present invention,

A cured film formed from the photocurable resin composition according to the first aspect is provided.

According to a third aspect of the present invention,

There is provided a base material having a base material and a film having a cured film according to the second aspect provided on the base material.

According to a fourth aspect of the present invention,

A method for producing a cured film having a curing step of curing the photocurable resin composition according to the first aspect by light irradiation is provided.

According to a fifth aspect of the present invention,

An application step of applying the photocurable resin composition according to the first aspect to at least one main surface of the substrate;

There is provided a method for manufacturing a base material having a coating film, comprising a curing step of curing the photocurable resin composition by light irradiation after the coating step to form a cured coating film.

According to the present invention, a high level of weather resistance, scratch resistance and anti-glare properties can be obtained in a well-balanced manner in a cured coating film.

The present inventors studied a polymer component that can obtain excellent scratch resistance in a cured film, and reacted with an aliphatic urethane (meth)acrylate and a (meth)acrylate monomer to a urethane (meth)acrylate. conceived. According to such a urethane (meth)acrylate, even when a ultraviolet absorber is mix|blended in order to provide weather resistance, the cured film excellent in scratch resistance with high hardness is obtained.

Moreover, when the method of further improving the weather resistance of a cured film was examined, it was discovered that what is necessary is just to mix|blend fluorine-type compounds, such as a fluorine-containing oligomer which has a photopolymerizable unsaturated group, with a photocurable resin composition. Since the fluorine-based compound is excellent in water repellency and oil repellency, the weather resistance of the cured film is improved, and further, by having a photopolymerizable unsaturated group, it is possible to maintain the weather resistance over a long period of time by bonding with the polymer component of the cured film.

Furthermore, when a method for imparting anti-glare properties to the cured film was studied, it was found that spherical silica particles may be blended as fine particles. There are spherical and irregular (non-spherical) silica particles, but according to the studies of the present inventors, when irregularities are formed on the surface of the cured film by spherical silica particles, the silica particles are compared with the case of using an amorphous one. It was found that it was possible to suppress the drop-off and maintain high scratch resistance. Furthermore, it was discovered that scratch resistance could be maintained highly, so that the sphericity of a spherical silica particle approached 1, ie, the shape of a silica particle approached a true sphere. The mechanism is not clear, but it is speculated as follows. That is, the silica particles tend to be hardened by being spherical and spherical rather than amorphous, and it is estimated that the strength of the convex portions formed by the silica particles increases with the hardness of the silica, thereby increasing the scratch resistance.

In addition, since the higher the purity of the silica particles, the higher the hardness. For example, it is estimated that the scratch resistance is further improved by using the high-purity silica particles produced by the sol-gel method.

Thus, by mixing an aliphatic urethane (meth)acrylate, a (meth)acrylate monomer, a fluorine-based compound having a photopolymerizable unsaturated group, spherical silica particles and a UV absorber to prepare a photocurable resin composition, weather resistance, scratch resistance and antiglare A cured film having excellent properties can be formed.

This invention was made based on the said knowledge.

(1) one embodiment of the present invention

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of this invention is described.

At this time, in this specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acryl" represents acryl and methacryl, and "(meth)acryloyl" is acryloyl. work and methacryloyl. In addition, the photopolymerizable unsaturated group represents an unsaturated group which participates in a polymerization reaction by light. In addition, "light" means an active energy ray or radiation, and means including, for example, visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, and the like. The numerical range shown using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

<Photocurable resin composition>

The photocurable resin composition which concerns on this embodiment, an aliphatic urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a spherical silica particle (C), a ultraviolet absorber (D), and light The fluorine-type compound (E) which has a synthetic|combination unsaturated group, and a photoinitiator (F) are contained. The photocurable resin composition hardens|cures by irradiation of an ultraviolet-ray, and turns into a cured film. Hereinafter, each of (A) component - (F) component is demonstrated.

[aliphatic urethane (meth)acrylate (A)]

The aliphatic urethane (meth)acrylate (A) is at least one of an oligomer and a polymer having at least one (meth)acryloyl group and an arbitrary number of urethane bonds as a photopolymerizable unsaturated group in the molecule. When component (A) irradiates an ultraviolet-ray to a photocurable resin composition, it superposes|polymerizes with the (meth)acrylate monomer (B) and fluorine-type compound (E) which have a photopolymerizable unsaturated group, and forms a cured film. Component (A) has a chemical structure excellent in weather resistance, and is polymerized with component (B) and component (E) to form a cured film excellent in weather resistance with scratch resistance.

(A) A component is obtained by making an isocyanate compound (a1), the (meth)acrylate (a2) which has a hydroxyl group, and a polyol compound (a3) react as needed.

(A) As an isocyanate compound (a1) which forms component, For example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, etc. Chain hydrocarbon group-containing isocyanates can be used.

Further, for example, branched hydrocarbon group-containing isocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2-methylpentane-1,5-diylbisisocyanate Can be used.

Moreover, isocyanate (alicyclic isocyanate) containing cyclic hydrocarbon groups, such as hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) and isophorone diisocyanate, can be used, for example.

Further, for example, modified products such as isocyanurate, biuret, and adduct bodies of the above-listed isocyanate compounds can be used.

From a viewpoint of improving the scratch resistance of a cured film, it is preferable that (A) component has an alicyclic skeleton. Therefore, it is preferable that the isocyanate compound (a1) which forms (A) component is an alicyclic isocyanate.

Specifically, as alicyclic isocyanate, hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) represented by the following general formula (1-1), and represented by the following general formulas (1-2) to (1-4) Hydrogenated xylene diisocyanate (hydrogenated XDI), hydrogenated torylene diisocyanate (hydrogenated TDI) represented by the following general formulas (1-5) and (1-6), represented by the following general formula (1-7) norbornane diisocyanate represented by the following, cyclohexylene diisocyanate represented by the following general formulas (1-8) to (1 to 10), and 1,1-bis(isocyanatemethyl)cyclo represented by the following general formula (1-11) Hexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]-1-cyclohexane represented by the following general formula (1-12), the following general formula (1-13) to The decalin diisocyanate represented by (1-16), the isophorone diisocyanate represented by the following general formula (2), etc. can be used.

As the isocyanate compound (a1), among the compounds listed above, at least two reactive groups having an isocyanate group are bonded to the alicyclic skeleton represented by the general formulas (1-1) to (1-16), and the reactive groups are the same. It is more preferable that it is an alicyclic isocyanate which has a chemical structure. As an alicyclic skeleton, a cyclo ring, a bicyclo ring, a decalin ring, etc. are mentioned, for example. A reactive group bearing an isocyanate group refers to the isocyanate group (—NCO) itself, or an isocyanate containing group comprising an isocyanate group _{, such as, for example, —CH 2 —NCO.} In such compounds, two or more reactive groups have the same chemical structure, and the reactivity of each reactive group is the same. According to the component (A) obtained by reacting such a compound, in comparison with component (A) obtained by reacting a compound in which two or more reactive groups bonded to the alicyclic skeleton represented by the general formula (2) do not become the same, it is cured The scratch resistance of the film can be made higher.

It is preferable that alicyclic isocyanate has a cyclo ring as an alicyclic skeleton, and it is more preferable that it has two or more cyclo rings. Further, in the alicyclic isocyanate, it is preferable that each of the plurality of reactive groups is bonded to the alicyclic skeleton so as to be symmetrical, and it is more preferable that the isocyanate group as the reactive group is directly bonded to the alicyclic skeleton, and furthermore, the alicyclic It is more preferable that no substituent other than a reactive group is bonded to the formula skeleton. That is, as alicyclic isocyanate, the hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) represented by General formula (1-1) is preferable. According to hydrogenated MDI, the scratch resistance and weather resistance of the cured film can be further improved while suppressing cure shrinkage.

The (meth)acrylate monomer (a2) has at least one (meth)acryloyl group and a hydroxyl group as a photopolymerizable unsaturated group in the molecule. The component (a2) reacts with the component (a1) by means of a hydroxyl group to form an aliphatic urethane (meth)acrylate (A), and introduces a photopolymerizable unsaturated group into its chemical structure.

(a2) As a component, a hydroxyl-group containing monofunctional (meth)acrylate, a hydroxyl-group containing polyfunctional (meth)acrylate, etc. can be used, for example.

Examples of the hydroxyl group-containing monofunctional (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, 2-hydroxy-3-phenoxy Cypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. are mentioned.

As the hydroxyl group-containing polyfunctional (meth)acrylate, for example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth)acrylate etc. are mentioned.

The component (a2) preferably has three or more photopolymerizable unsaturated groups ((meth)acryloyl groups) in the molecule from the viewpoint of improving the hardness of the cured film and obtaining high scratch resistance, pentaerythritol tri ( Hydroxyl group-containing polyfunctional (meth)acrylates, such as meth)acrylate and dipentaerythritol penta (meth)acrylate, are more preferable.

Aliphatic urethane (meth)acrylate (A) may further make a polyol compound (a3) react with (a1) component and (a2) component. Although it does not specifically limit as a component (a3), From a viewpoint of the weather resistance of a cured film, it is preferable that it is a compound which does not contain an aromatic ring in a chemical structure, A polyether type diol, polyester type diol, polyolefin type diol, etc. are well-known of diols can be used. For example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, 1,2-cyclohexane diol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, 4,4'- (1-methylethylidene)biscyclohexanol, the ethylene oxide adduct of bisphenol A, the propylene oxide adduct of bisphenol A, polycaprolactone diol, alkylene diol, etc. are mentioned.

The aliphatic urethane (meth)acrylate (A) is a photopolymerizable unsaturated group from the viewpoint of improving the hardness of the cured film to obtain high scratch resistance, and also improving the weather resistance (adhesiveness with the substrate after UV irradiation) of the cured film. It is so preferable that there are many numbers, and it is preferable that it is three or more.

Although the molecular weight of an aliphatic urethane (meth)acrylate (A) is not specifically limited, It is preferable that they are 800 or more and 30,000 or less in weight average molecular weight, and it is more preferable that they are 1,500 or more and 28,000 or less. When a weight average molecular weight will be less than 800, there exists a possibility that the cure shrinkage amount at the time of hardening of a photocurable resin composition may become large. As a result, for example, when forming a cured film on a thin base material, there exists a possibility that a base material may curl. On the other hand, when a weight average molecular weight exceeds 30,000, since the viscosity of a photocurable resin composition rises and coatability falls, or crosslinking density falls, there exists a possibility that the hardness of a cured film may fall.

Although the compounding quantity of (A) component is not specifically limited, It is preferable that it is 10 mass parts - 80 mass parts with respect to 100 mass parts of solid content of a photocurable resin composition from a viewpoint of the scratch resistance and weather resistance of a cured film, 20 It is more preferable that they are mass parts - 70 mass parts. At this time, in this embodiment, solid content removes volatile components, such as an organic solvent, from the photocurable resin composition, and shows the component which remains as a cured film when it is made to harden.

[(meth)acrylate monomer (B)]

A (meth)acrylate monomer (B) has a photopolymerizable unsaturated group ((meth)acryloyl group), and superposes|polymerizes with (A) component and (E) component. (B) component has a small molecular weight compared with (A) component, raises the hardness of a cured film, and improves scratch resistance.

(B) As a component, it is preferable that it is a trifunctional or more than trifunctional monomer which has 3 or more photopolymerizable unsaturated groups. Examples of the trifunctional monomer include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, and the like. As a tetrafunctional monomer, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc. are mentioned. Dipentaerythritol penta(meth)acrylate etc. are mentioned as a 5 functional monomer, Dipentaerythritol hexa(meth)acrylate etc. are mentioned as a 6 functional monomer. These (meth)acrylate monomers may be used individually by 1 type, and may use 2 or more types together. Among these, from a viewpoint of making a cured film more high hardness and improving scratch resistance more, the monomer more than tetrafunctional is preferable, and dipentaerythritol hexa(meth)acrylate is more preferable. At this time, the compound similar to the component (a2) mentioned above may be sufficient as a component (B).

(B) The blending amount of the component is not particularly limited, but from the viewpoint of scratch resistance and weather resistance of the cured film, it is preferably 10 parts by mass to 80 parts by mass with respect to 100 parts by mass of the solid content of the photocurable resin composition, 20 It is more preferable that they are mass parts - 70 mass parts.

Although the mixing ratio of (A) component and (B) component is not specifically limited, From a viewpoint of the scratch resistance of a cured film, the mixing|blending ratio of (B) component with respect to (A) component [(B) component/(A) component] is preferably in the range of 0.5 to 10, more preferably in the range of 1 to 8. At this time, the ratio here shows mass ratio at the time of solid content conversion of each of (A) component and (B) component.

[Spherical Silica Particles (C)]

When a spherical silica particle (C) hardens a photocurable resin composition, it forms fine unevenness|corrugation on the surface of a cured film, and provides anti-glare property to a cured film.

It is preferable that a spherical silica particle (C) is a spherical shape close to 1 spherical shape. According to the studies of the present inventors, the hardness of component (C) tends to increase as it approaches a spherical shape, increases the strength at the convex portions of the cured film, and the scratch resistance decreases due to desorption of component (C) due to impact. can be deterred from doing

Although the hardness of a spherical silica particle (C) is not specifically limited, In order to raise the intensity|strength of the convex part of a cured film so that hardness is high, desorption of (C) component by an impact can be suppressed, and scratch resistance can be improved. . At this time, the hardness of the silica particles here includes not only the hardness of the material forming the particles, but also the hardness resulting from the shape of the particles.

(C) Although the average particle diameter of a component is not specifically limited, It is preferable that they are 1 micrometer - 10 micrometers, and it is more preferable that they are 2 micrometers - 8 micrometers. By setting it as 1 micrometer or more, the unevenness|corrugation of moderate roughness can be formed in the surface of a hardened film, and favorable anti-glare property can be acquired. On the other hand, by being referred to as 10 micrometers or less, drop-off|omission of (C)component from a cured film can be suppressed, and scratch resistance can be maintained highly. That is, when the average particle diameter of (C)component shall be 1 micrometer - 10 micrometers, the cured film excellent in scratch resistance and anti-glare property can be formed. At this time, in this embodiment, the average particle diameter represents the particle diameter (so-called median diameter D50) of 50% of accumulation in the particle size distribution on a volume basis.

(C) From a viewpoint of improving the scratch resistance of a cured film more, it is preferable that the nonuniformity of a particle diameter is small, and, as for component (C), a particle size distribution is sharp. Specifically, it is preferable that D90/D10 be 2.0 or less when the particle diameters of 10% and 90% cumulative in the volume-based particle size distribution are D10 and D90, respectively. Moreover, in the volume-based particle size distribution, when the cumulative 50% particle size is D50, it is preferable that both D50/D10 and D90/D50 be 1.5 or less.

Up to now, it was considered that the fine particles used to form a cured film having an uneven surface should have a certain degree of variation in the particle diameter thereof. However, according to the studies of the present inventors, it has been found that, when fine particles are blended with the above-mentioned predetermined component (A) or component (B), the scratch resistance of the cured film can be improved as the non-uniformity of the particle diameter is reduced. . In general, when the cured film is in contact with another member, the fine particles fall off due to the convex portion being caught on or impacted by another member. It is estimated that this is because a cured film having an average interval of irregularities can be formed.

At this time, the particle size distribution is measured with a laser diffraction type particle size distribution measuring apparatus, for example.

As the component (C), although those synthesized by a dry or wet method can be used, those synthesized by a wet method, particularly a sol-gel method, are preferable. According to the sol-gel method, fine particles with a sharp particle size distribution and uniform particle diameter can be synthesized, and silica particles with high purity can be obtained. As such (C)component, "High Freshica N2N" (made by Ube Eximo Corporation) etc. can be used, for example.

(C) The compounding quantity of component is not specifically limited, Although it can change suitably according to characteristics, such as scratch resistance and anti-glare property required for a cured film, In order to obtain various characteristics in a cured film with good balance, photocurability 0.5 mass parts - 15 mass parts are preferable with respect to 100 mass parts of solid content of a resin composition, and 1 mass part - 10 mass parts are more preferable.

[Ultraviolet absorbent (D)]

The ultraviolet absorber (D) has a structure of ultraviolet absorption and improves the weather resistance of the cured film. (D) As a component, it is preferable to use at least 1 of the ultraviolet absorber (d1) which has a triazine skeleton, and the ultraviolet absorber (d2) which has a benzotriazole skeleton.

As the ultraviolet absorber (d1) having a triazine skeleton, for example,

2-(2-hydroxy-4-[isooctyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5 represented by the following general formula (3-1) -Triazine ("Chinuvin 479" manufactured by BASF Japan),

2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4) represented by the following general formula (3-2) -dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2, A mixture with 4-dimethylphenyl)-1,3,5-triazine ("Chinuvin 400" manufactured by BASF Japan Co., Ltd.);

2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-tri represented by the following general formula (3-3) Ajin ("Chinubin 460" manufactured by BASF Japan),

2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis represented by the following general formula (3-4) (2,4-dimethylphenyl)-1,3,5-triazine ("Chnuvin 405" by BASF Japan Co., Ltd.) etc. are mentioned.

As the ultraviolet absorber (d1) having a triazine skeleton, among these, those having a biphenyl group in the triazine skeleton are preferable, and the compound represented by the above formula (3-1) ("Chnuvin 479" manufactured by BASF Japan Co., Ltd.) is more preferable. desirable. Since such a compound is excellent in ultraviolet absorption ability compared with other compounds, not only can the deterioration and discoloration of the cured film by ultraviolet-ray be suppressed further, but the fall of the adhesiveness of a cured film and a base material can be suppressed. That is, the weather resistance of the cured film can be maintained over a long period of time.

The blending amount of the ultraviolet absorber (d1) having a triazine skeleton is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of solid content of the photocurable resin composition from the viewpoint of making the hardness and weather resistance of the cured film compatible, More preferably 9 parts by mass or more.

As the ultraviolet absorber (d2) having a benzotriazole skeleton, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (“RUVA” manufactured by Otsuka Chemical Co., Ltd.) -93", Yamato Kasei Co., Ltd. "DAINSORB T-31"), 2-(4-allyloxy-2-hydroxyphenyl)-2H-benzotriazole (Yamato Kasei Co., Ltd. "DAINSORB T-84"), 2 -(2H-Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3,-tetramethyl butyl)phenol (BASF Japan Co., Ltd. "chi" Nubin 928") and the like can be used. Among these, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole is preferable from a viewpoint of improving the weather resistance of a cured film more. This compound has a photopolymerizable unsaturated group, and when curing the photocurable resin composition, it is polymerized with component (A) or component (B) to be incorporated into the cured film, and component (d2) is cured by ultraviolet rays or dew condensation. Bleeding from the film can be suppressed. That is, the weather resistance of a cured film can be maintained over a longer period of time.

The compounding quantity of the ultraviolet absorber (d2) which has a benzotriazole skeleton is 1 mass parts - 15 mass parts with respect to 100 mass parts of solid content of a photocurable resin composition from a viewpoint of making the hardness of a cured film and weather resistance compatible, and 3 mass Parts by mass to 10 parts by mass are more preferable.

As a ultraviolet absorber (D), it is preferable to use together (d1) component and (d2) component. Thereby, not only the deterioration and discoloration of the cured film by an ultraviolet-ray can be suppressed further, but the fall of the adhesiveness of a cured film and a base material can be suppressed further. When used in combination, the mixing ratio of the component (d1) and the component (d2) is preferably in the range of 99:1 to 1:99, more preferably in the range of 90:10 to 50:50. At this time, the ratio here shows mass ratio at the time of solid content conversion of each of a component (d1) and a component (d2).

[Fluorine-based compound (E) having a photopolymerizable unsaturated group]

The fluorine-based compound (E) having a photopolymerizable unsaturated group is at least one of a monomer and an oligomer having a fluorine atom and a photopolymerizable unsaturated group in the chemical structure, and is excellent in water repellency and weather resistance, so that the cured film can be coated with moisture or ultraviolet rays such as rain or condensation. It improves weather resistance by protecting it from Furthermore, since component (E) has a photopolymerizable unsaturated group, it is inserted into the cured film by polymerization with component (A) or component (B) when curing the photocurable resin composition, so that the cured film is deteriorated by ultraviolet rays or dew condensation. Even if it is, it is difficult to bleed. Moreover, (E) component does not deteriorate easily by combined use with (A) component which is excellent in weather resistance. Therefore, according to (E) component, the weather resistance of a cured film can be maintained over a long period of time.

As the component (E), for example, a perfluoropolyether compound having a perfluoropolyether skeleton and having a (meth)acryloyl group as a photopolymerizable unsaturated group at one or both ends thereof can be used. The perfluoropolyether skeleton is, for example, -(O-CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ )-, or -(O-CF ₂ C(CF ₃ )F)-, etc. represents the repeating structure of The photopolymerizable unsaturated group in component (E) is not specifically limited, (meth)acryloyl group, (meth)acryloyloxy group, a vinyl group, an allyl group, etc. are mentioned, Component (A) A (meth)acryloyl group is preferable from the viewpoint of reactivity with the component (B).

As such component (E), for example, "Megapac RS-75" (manufactured by DIC Corporation), "KY-1203" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "FLUOROLINK AD1700" and "FLUOROLINK MD700" (Solvay Solexis) Co., Ltd.), "Optool DAC-HP" (manufactured by Daikin Chemical Industries, Ltd.), "CN4000" (manufactured by Satoma Corporation), etc. can be used.

(E) The blending amount of the component is not particularly limited, but from the viewpoint of obtaining a high level and well-balanced hardness and weather resistance of the cured film, 0.1 parts by mass to 20 parts by mass is preferable with respect to 100 parts by mass of the solid content of the photocurable resin composition, , 0.2 mass parts - 8 mass parts are more preferable, and 0.3 mass parts - 4.0 mass parts are still more preferable. (E) If the blending amount of the component is less than the above range, the weather resistance of the cured film may be impaired. If it is more than the above range, not only the hardness of the cured film will decrease but also the appearance of the cured film may be damaged.

[Photoinitiator (F)]

A photoinitiator (F) generates a radical or a cation by light irradiation, and hardens a photopolymerizable composition by bonding said (A) component, (B) component, and (E) component. It will not specifically limit as a photoinitiator (F), if a radical etc. can be generate|occur|produced by light irradiation, For example, an alkylphenone type, an acylphosphine oxide type, a hydrogen extraction type initiator etc. are mentioned.

As the alkylphenone type, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, phenylglyoxylic acid methyl ester, 2-hydroxy hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4 -Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; and the like.

Examples of the acylphosphine oxide type include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Examples of the hydrogen extraction initiator include benzophenone, 2,4,6-trimethylbenzophenone, methylbenzoylbenzoate, 2,4-diethylthioxanthone, 2-ethylanthraquinone, camphor quinone, and the like. .

Among these, 1-hydroxy-cyclohexyl-phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable. At this time, these photoinitiators (F) may be used individually by 1 type, and may use 2 or more types together.

(F) To [ the compounding quantity of component / 100 mass parts of solid content of a photocurable resin composition ], Preferably 0.1 mass part - 10 mass parts, More preferably, 2 mass parts - 8 mass parts, More preferably, 3 mass parts -7 parts by mass. When a compounding quantity is less than the said range, when hardening the photocurable resin composition, sclerosis|hardenability of a coating film becomes inadequate, and there exists a possibility that the hardness of a cured film may fall. On the other hand, when it is more than the above range, since the excess content remains in the coating film as unreacted, not only the hardness of the cured film decreases, but also the cured film is liable to yellow by ultraviolet rays, and there is a risk that the adhesion to the substrate may decrease. .

[Other additives]

A light stabilizer (G) may be mix|blended with the photocurable resin composition which concerns on this embodiment in order to suppress further yellowing of the cured film by an ultraviolet-ray. As the light stabilizer (G), a hindered amine light stabilizer is preferable. As the hindered amine type, for example, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4) -piperidinyl)sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6 -(2-hydroxyethylamine)-1,3,5-triazine, decane diacid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, etc. can be heard As a commercial item, "Chinubin 292", "Chinubin 144", and "Chinubin 123" (made by BASF Corporation) are mentioned.

As for the compounding quantity of a light stabilizer (G), 0.1 mass part - 5 mass parts are preferable with respect to 100 mass parts of solid content of a photocurable resin composition from a viewpoint of making the hardness of a cured film and weather resistance compatible, and 0.5 mass part - 3 mass parts more desirable.

You may make the photocurable resin composition which concerns on this embodiment contain components other than the above-mentioned components as needed. Examples of the other components include an organic solvent, a polymerization inhibitor, a viscosity modifier, a non-reactive diluent, a matting agent, an antifoaming agent, an antisettling agent, a dispersing agent, and a heat stabilizer. These compounding quantities can be suitably changed in the range which does not impair the effect of this embodiment.

Examples of the organic solvent include aromatic hydrocarbons (eg, xylene, toluene, etc.), ketones (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, etc.), esters (eg, ethyl acetate, butyl acetate, Various organic solvents, such as isobutyl acetate, etc.), alcohols (eg, isopropyl alcohol, butanol, etc.), glycol ethers (eg, propylene glycol monomethyl ether, etc.) can be used. These organic solvents may be used individually by 1 type, or may be used in combination of 2 or more type.

As the viscosity modifier, a bifunctional (meth)acrylate monomer can be used. For example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. are mentioned. A viscosity modifier can be used in the range which does not impair the scratch resistance of a cured film.

As an antifoaming agent, various antifoaming agents of an acrylic type and a silicone type can be used, for example. According to an antifoamer, generation|occurrence|production of the bubble in a photocurable resin composition can be suppressed and the external appearance of a cured film can be made favorable.

At this time, the photocurable resin composition of this embodiment is an aliphatic urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a spherical silica particle (C), an ultraviolet absorber (D), light in an organic solvent It can manufacture by adding and mixing the fluorine-type compound (E) which has a synthetic|combination unsaturated group, a photoinitiator (F), and an optical stabilizer (G) or another additive as needed.

<Substrate having a coating film>

The base material with a film apply|coats the above-mentioned photocurable resin composition on a base material, it hardens|cured, and formed the cured film.

As a base material, transparent base materials, such as a plastic base material, can be used. Examples of the transparent substrate include various transparent plastic films such as triacetyl cellulose film, polyethylene terephthalate (PET) film, diacetyl cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic film, A polyurethane-based film, a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth)acrylonitrile film, etc. are mentioned. Among them, a polyethylene terephthalate film is preferable from the viewpoints of balance of strength, optical properties, and the like.

A cured film is formed by apply|coating a photocurable resin composition on a base material, irradiating light (active energy ray or radiation), such as an ultraviolet-ray, and hardening it. The thickness of the cured film is not particularly limited as long as it is thick enough to protect the substrate, but it is preferably 2 µm to 10 µm, and 3 µm from the viewpoint of obtaining a high level of weather resistance, scratch resistance and hardness in a well-balanced manner. It is more preferable that it is -5 micrometers.

As a coating (coating) method of the photocurable resin composition, it can be appropriately selected according to the conditions of the coating process corresponding to the kind or composition of the photocurable resin composition, the kind of the substrate, etc. For example, the spray coating method, the dip coating method, The air knife coat method, the curtain coat method, the roller coat method, the wire bar coat method, the gravure coat method, the extrusion coat method, etc. are mentioned.

Examples of active energy rays for curing the photocurable resin composition include, in addition to rays such as far ultraviolet, ultraviolet, near ultraviolet, and infrared rays, electromagnetic waves such as X-rays and γ-rays, electron beams, proton rays, and neutron rays, Among them, ultraviolet rays are preferable from the viewpoints of curing rate, easiness of availability of an irradiator, price, and the like.

As a method of curing with ultraviolet rays, using a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, etc. that generate light in a wavelength range of 200 to 500 nm, a method of irradiating about 100 to 3,000 mJ/cm2 and the like.

Moreover, in order to shorten drying and hardening time, you may dry and harden the said film by heating at about 5-120 degreeC.

<Effect according to the embodiment of the present invention>

According to this embodiment, one or more effects shown below are exhibited.

The photocurable resin composition of this embodiment has an aliphatic urethane (meth)acrylate (A), a (meth)acrylate monomer (B), a spherical silica particle (C), an ultraviolet absorber (D), and a photopolymerizable unsaturated group. It contains a compound (E) and a photoinitiator (F), and when light is irradiated, (A) component, (B) component, and (E) component superpose|polymerize and harden|cure, a cured film is formed. According to (A) component and (B) component, even when (D) component is mix|blended, high hardness is obtained and scratch resistance can be maintained highly. Moreover, according to (D) component and (E) component which has water repellency and oil repellency, the weather resistance of a cured film can be improved. In addition, according to component (E), since it polymerizes with component (A) and component (B) and is inserted into the cured film, it is difficult to bleed even when it is deteriorated by exposure to ultraviolet rays or dew condensation for a long time, and weather resistance can be maintained over a long period of time. have. Furthermore, according to the component (C), fine irregularities are formed on the surface of the cured film composed of the reactant of the component (A), the component (B) and the component (E), so that the haze on the surface of the cured film is adjusted to an appropriate value. By adjusting it, anti-glare property can be provided. Therefore, according to the photocurable resin composition of this embodiment, it is possible to form a cured film that can obtain a high level of scratch resistance, weather resistance, and anti-glare properties with good balance.

The spherical silica particles (C) preferably have D90/D10 of 2.0 or less when the particle diameters of 10% and 90% of the spherical silica particles are D10 and D90, respectively, in the volume-based particle size distribution. Further, in the volume-based particle size distribution, when the cumulative 50% particle size is D50, it is preferable that both D50/D10 and D90/D50 be 1.5 or less. According to the component (C) which has such a particle size distribution, since a particle size distribution is sharp and the dispersion|variation in particle diameter can be made small, the scratch resistance of a hardened film can be improved more.

It is preferable to contain a spherical silica particle (C) in 0.5 mass part or more and 15 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition. By setting it as such a compounding quantity, in a cured film, scratch resistance and anti-glare property can be obtained with good balance.

It is preferable that the average particle diameters of a spherical silica particle (C) are 1 micrometer - 10 micrometers. By setting it as 1 micrometer or more, the unevenness|corrugation of moderate roughness can be formed in the surface of a hardened film, and favorable anti-glare property can be acquired. On the other hand, by being referred to as 10 micrometers or less, drop-off|omission of (C)component from a cured film can be suppressed, and scratch resistance can be maintained highly. That is, a cured film excellent in scratch resistance and anti-glare properties can be formed.

It is preferable that the aliphatic urethane (meth)acrylate (A) has an alicyclic skeleton. More preferably, it is obtained by reacting an isocyanate compound (a1) with a (meth)acrylate monomer (a2) having a hydroxyl group, wherein the isocyanate compound (a1) is bonded to an alicyclic skeleton with at least two reactive groups having an isocyanate group, , is an alicyclic isocyanate in which the reactive groups have the same chemical structure. According to the component (A) obtained from such a compound, the scratch resistance of a cured film can be improved more.

The hardened film formed of the photocurable resin composition of this embodiment has the fine unevenness|corrugation which makes it 1 % - 30% of haze is formed, and has anti-glare property. In addition, it has scratch resistance so that the difference in haze ΔHZ before and after the test is 4% or less when a table wear test is performed under the conditions of abrasion wheel CS-10, load 500g, rotation speed 60rpm, and number of rotations of 100 times. . After irradiating ultraviolet rays with an illuminance of 0.71 W/m 2 in an environment of 60° C. for 4 hours, condensing in an environment of 50° C. 98% RH for 4 hours is 1 cycle, and when this is performed 18 cycles to accelerate degradation, b before and after degradation It has weather resistance such that the difference Δb* of the values is 1 or less.

[Example]

Next, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these Examples.

First, the synthesis example of an aliphatic urethane (meth)acrylate (A) is demonstrated.

(Synthesis Example 1)

As the isocyanate compound (a1), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) was prepared, which is an alicyclic isocyanate in which at least two reactive groups having an isocyanate group are bonded to an alicyclic skeleton and the reactive groups have the same chemical structure.

Moreover, as a component containing the (meth)acrylate monomer (a2) which has a hydroxyl group, the Satoma company "SR444DNS" was prepared. "SR444DNS" contains pentaerythritol tetraacrylate (B2) as a (meth)acrylate monomer (B) other than pentaerythritol triacrylate as (a2) component.

Further, diethylene glycol was prepared as the polyol compound (a3).

Then, in a 200 mL reaction vessel equipped with a stirring device, a thermometer, and an air introduction tube, 32.8 g of hydrogenated MDI as (a1) component, "SR444DNS" ((a2) pentaerythritol triacrylate as component, and (B) component 102 g of pentaerythritol tetraacrylate (B2)), 3.3 g of diethylene glycol as component (a3), 0.05 g of p-methoxy phenol, 0.17 g of dibutylhydroxy toluene, and dibutyltin dilaurate 0.17 g and 15.4 g of butyl acetate were added, and the mixture of the urethane acrylate oligomer (A1) and pentaerythritol tetraacrylate (B2) was obtained by making it react at 80 degreeC for 5 hours. In this mixture, (A1) component 57%, (B2) component 33%, butyl acetate which is an organic solvent was 10%, and solid content was 90%. Moreover, the number of functional groups and the weight average molecular weight (MW) of this (A1) component were 2,500.

(Synthesis Example 2)

As the isocyanate compound (a1), an isocyanurate form (HDI isocyanurate) of hexamethylene diisocyanate which is an isocyanate having no alicyclic skeleton ("Colonate HXR" manufactured by Tosoh Corporation) was prepared.

Moreover, as a thing containing the (meth)acrylate monomer (a2) which has a hydroxyl group, similarly to the synthesis example 1, "SR444DNS" manufactured by Sartoma Corporation was prepared.

Then, 143 g of HDI isocyanurate, "SR444DNS" (pentaerythritol triacrylate (a2) and pentaerythritol tetraacrylate (B2) ) of 435 g, p-methoxyphenol 0.25 g, dibutylhydroxy toluene 0.85 g, dibutyltin dilaurate 0.4 g, (meth) acrylate monomer (B) trimethylolpropane triacryl The mixture of the urethane acrylate oligomer (A2), (B2) component, and (B3) component was obtained by adding 260g of rate (B3) and making it react at 80 degreeC in air atmosphere for 5 hours. In this mixture, the (A2) component was 43%, the (B2) component was 26%, and the (B3) component was 31%, and the solid content which summed this up was 100%. In addition, the number of functional groups and the weight average molecular weight (MW) of this (A2) component were 25,800.

<Material>

Materials used in Examples and Comparative Examples are as follows.

As the aliphatic urethane (meth)acrylate (A), the following (A1) to (A4) were used.

(A1): urethane acrylate oligomer obtained in Synthesis Example 1 (the number of functional groups 6, weight average molecular weight 2,500, solid content 100%)

(A2): urethane acrylate oligomer obtained in Synthesis Example 2 (the number of functional groups 9, weight average molecular weight 25,800, solid content 100%)

(A3): aliphatic urethane acrylate ("CN991" manufactured by Satoma Corporation, number of functional groups 2, weight average molecular weight 1,500, solid content 100%)

(A4): aliphatic urethane acrylate (“KRM8200” manufactured by Daicel Allnex Co., Ltd., number of functional groups 6, weight average molecular weight 1,000, solid content 100%)

As the comparative oligomer (A') of the aliphatic urethane (meth)acrylate (A), the following (A1') to (A3') were used.

(A1'): Aromatic urethane acrylate (“EBECRYL220” manufactured by Daicel Allnex Co., Ltd., number of functional groups 6, weight average molecular weight 1,000, solid content 100%)

(A2'): Polyester acrylate (“Aronix M-8560” manufactured by Dong-A Synthetic Co., Ltd., 100% solid content)

(A3'): Epoxy acrylate ("VR-77" manufactured by Showa Denko Co., Ltd., number of functional groups 1.9, weight average molecular weight 510, solid content 100%)

As the (meth)acrylate monomer (B), the following (B1) to (B3) were used.

(B1): polyfunctional acrylic monomer (“Laromer DPHA-A ap.” manufactured by BASF Japan Co., Ltd.);

A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, number of functional groups 5 and 6, solid content 100%)

(B2): Pentaerythritol tetraacrylate ("SR444DNS" manufactured by Satoma Corporation (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)

(B3): trimethylolpropane triacrylate

As the spherical silica particle (C), the following (C1) was used.

(C1): "Hyfrecica N2N" manufactured by Ube Eximo Co., Ltd. (spherical silica produced by sol-gel method, average particle diameter (D50) = 4.80 µm, D10 = 3.740 µm, D90 = 6.590 µm, D50/D10 = 1.28 , D90/D50=1.37, D90/D10=1.76, 100% solids)

As microparticles|fine-particles (C') for comparison of the spherical silica particle (C), the following (C1') - (C5') were used.

(C1'): Sekisui Processing Co., Ltd. "Tec Polymer SSX-105" (acrylic beads, average particle diameter (D50) = 5.07 µm, D10 = 3.919 µm, D90 = 6.883 µm, D50/D10 = 1.29, D90/ D50=1.36, D90/D10=1.76, 100% solids)

(C2'): Mizusawa Chemical Industry Co., Ltd. "Mizukasil P-802Y" (amorphous silica particles, average particle diameter (D50) = 5.88 mu m, D10 = 3.584 mu m, D90 = 9.667 mu m, D50/D10 = 1.64, D90 /D50=1.64, D90/D10=2.70, 100% solids)

(C3'): "Pyloid ED30" manufactured by Grace Japan Co., Ltd. (amorphous silica particles, average particle diameter (D50) = 6.48 µm, D10 = 3.972 µm, D90 = 10.31 µm, D50/D10 = 1.63, D90/D50 = 1.59 , D90/D10=2.60, 100% solids)

(C4'): "Syloid 305C" manufactured by Grace Japan Co., Ltd. (amorphous silica particles, average particle diameter (D50) = 5.69 µm, D10 = 3.517 µm, D90 = 13.81 µm, D50/D10 = 1.62, D90/D50 = 2.43 , D90/D10=3.93, 100% solids)

(C5'): "Ace Matt EXP3600" manufactured by Evnik Japan Co., Ltd. (Irregular silica particles, average particle diameter (D50) = 5.04 µm, D10 = 3.430 µm, D90 =7.575 µm, D50/D10 = 1.47, D90/D50 = 1.50, D90/D10=2.21, 100% solids)

At this time, D10, D50 and D90 of (C) component and (C') component were measured under the following conditions using a laser diffraction/scattering particle diameter distribution measuring apparatus ("MT-3300II" manufactured by Microtrack Bell Corporation). became

Measurement method: wet method (permeation)

Refractive Index: 1.46

Dispersion medium: butyl acetate

Ultrasonic Dispersion Time: 2 minutes

As the ultraviolet absorber (D), the following (d1) and (d2) were used.

(d1): UV absorber having a triazine skeleton ("Chinuvin 479" manufactured by BASF Japan Co., Ltd., (2-(2-hydroxy-4-[isooctyloxycarbonylethoxy]phenyl)-4,6-bis (4-phenylphenyl)-1,3,5-triazine), solid content 100%)

(d2): UV absorber having a benzotriazole skeleton ("RUVA-93" manufactured by Otsuka Chemical Co., Ltd., (2-[2-hydroxy-5-[2-methacryloyloxy)ethyl]phenyl]-2H- benzotriazole), solid content 100%)

As the fluorine-based compound (E) having a photopolymerizable unsaturated group, the following (E1) was used.

(E1): "Megapac RS-75" manufactured by DIC Corporation (perfluoropolyether oligomer having a (meth)acrylic group, solid content 40%)

As the photopolymerization initiator (F), the following (F1) and (F2) were used.

(F1): "IRGACURE 184D" manufactured by BASF Japan Co., Ltd. (1-hydroxy-cyclohexyl-phenyl-ketone, solid content 100%)

(F2): "IRGACURE TPO" manufactured by BASF Japan Co., Ltd. (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, solid content 100%)

As other additives, the following light stabilizers (G1) were used.

(G1): BASF Japan Co., Ltd. "Chinuvin 123" (decane diacid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, 1,1-dimethyl Reaction product of ethyl hydroperoxide and octane, solid content 100%)

At this time, butyl acetate was used as the organic solvent.

<Preparation of photocurable resin composition>

In Examples, a photocurable resin composition was prepared by mixing the above materials in the formulation shown in Table 1 below.

(Example 1)

In Example 1, first, 17.5 parts by mass of a composition containing (A1) component prepared in Synthesis Example 1, etc. to 45.75 parts by mass of butyl acetate as an organic solvent (10.0 parts by mass of (A1) component, 10.0 parts by mass of (B2) component) 5.8 parts by mass and 1.7 parts by mass of the organic solvent), (B1) 25.0 parts by mass, (d1) 2.0 parts by mass, (d2) 4.0 parts by mass, (E1) component 0.5 mass part and (F1) component 2.0 mass part, (F2) component 1.0 mass part, and (G)component 1.0 mass part added and melt|dissolved. Then, 1.25 mass parts of (C1) component was added to the solution, and it stirred. Thereby, the photocurable resin composition which (C1) component disperse|distributes was obtained.

(Example 2)

In Example 2, first, 13.9 parts by mass of a composition containing (A2) component prepared in Synthesis Example 2, etc., to 49.35 parts by mass of butyl acetate as an organic solvent (6.0 parts by mass of (A2) component, (B2) component) 3.6 parts by mass and 4.3 parts by mass of component (B3)), 25.0 parts by mass of component (B1), 2.0 parts by mass of component (d1), 4.0 parts by mass of component (d2), (E1) 0.5 mass parts of components, 2.0 mass parts of (F1) components, 1.0 mass parts of (F2) components, and 1.0 mass parts of (G)components were added and dissolved for a component. Then, 1.25 mass parts of (C1) component was added to the solution, and it stirred. Thereby, the photocurable resin composition which (C1) component disperse|distributes was obtained.

(Examples 3 and 4)

In Examples 3 and 4, the type of component (A) was changed from component (A1) to component (A3) and component (A4), respectively, and their compounding amount was also changed, except that the amount of the organic solvent was appropriately changed prepared a photocurable resin composition in the same manner as in Example 1.

(Examples 5 and 6)

In Examples 5 and 6, the photocurable resin composition was prepared similarly to Example 1 except having changed the compounding quantity of (A1) component and (B) component, respectively, and having changed the quantity of the organic solvent suitably.

(Examples 7 to 9)

In Examples 7-9, the photocurable resin composition was prepared similarly to Example 1 except having changed suitably the compounding quantity of (C1) component, and having changed the quantity of the organic solvent suitably.

(Comparative Examples 1-3)

In Comparative Examples 1 to 3, as shown in Table 2 below, from alicyclic urethane acrylate as component (A1), aromatic urethane acrylate as component (A1'), polyester acrylate as component (A2'), ( A3') The photocurable resin composition was prepared similarly to Example 1 except having changed each into the epoxy acrylate which is a component, its compounding quantity was changed suitably, and having changed the quantity of the organic solvent suitably.

(Comparative Example 4)

In Comparative Example 4, a photocurable resin composition was prepared in the same manner as in Example 1 except that the component (C1) was not blended, and various materials were blended in the composition shown in Table 2.

(Comparative Examples 5 to 9)

In Comparative Examples 5 to 9, the spherical silica particles as (C1) were changed to (C1') components which are acrylic beads or (C2') components to (C5') components which are amorphous silica particles, and various materials were shown in Table 2 A photocurable resin composition was prepared in the same manner as in Example 1 except that it was blended with the composition shown in .

(Comparative Example 10)

In Comparative Example 10, a photocurable resin composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber (D) was not blended, and various materials were blended as the composition shown in Table 2.

(Comparative Example 11)

In Comparative Example 11, a photocurable resin composition was prepared in the same manner as in Example 1 except that the fluorine-based compound (E) having a photopolymerizable unsaturated group was not blended, and various materials were blended in the composition shown in Table 2.

<Preparation of a substrate having a coating film>

To a PET film "Cosmoshine A4300" manufactured by Toyobo Co., Ltd., the photocurable resin composition prepared above was applied once so that the dry film thickness was about 3 μm, and irradiated with ultraviolet light with an electrodeless lamp (Irradiation amount: 400 mJ/cm 2 ) ), the coating film was cured, a cured film was formed, and a substrate having a film was obtained.

<Evaluation method>

Next, evaluation shown below was performed about the base material which has the obtained film.

(anti-glare)

The anti-glare property of the cured film was evaluated by haze (HZ). Specifically, the haze of the cured film is measured using a haze meter (haze meter NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the haze is preferably 1% or more and 30% or less, and 1% or more and 10% or less It is more preferable, and when it is 1 % or more and 6 % or less, it evaluated as more preferable. When the haze was less than 1%, the turbidity of the cured film was low and the glare to the film could not be sufficiently suppressed, so that the antiglare property was judged to be low.

(transparency)

Transparency of the cured film was evaluated by the total light transmittance. Specifically, using a haze meter (haze meter NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), the total light transmittance of the cured film is measured in accordance with JISK7361, and when the total light transmittance is 80% or more, the film has excellent transparency was evaluated as

(Hardness)

The hardness of the cured film was evaluated by the pencil hardness of the cured film using a pencil scratch tester in accordance with JIS K5600. On the cured film (film) to be measured, a pencil was set at an angle of 45 degrees, a weight of 750 g was applied and scratched about 5 cm, and the hardness of the pencil was evaluated with no scratches 3 or more times out of 5 times. In this example, 2H or more was judged as pass.

(Scratch resistance)

The scratch resistance of the cured film was evaluated using a Teibo abrasion tester (manufactured by Futoshi Hiroshi Materials Co., Ltd.). Specifically, abrasion wheel: CS-10, load: 500 g, rotation speed: 60 rpm, number of rotations: 100 times. Then, the haze of the cured film was measured with a haze meter (haze meter NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the difference ΔHZ from the haze before the Teibo abrasion test was obtained. ΔHZ was 4% or less as pass.

(weather resistance)

The weather resistance of the cured film was evaluated by performing an accelerated weather resistance test on the cured film, and the degree of yellowing and adhesion before and after the test.

The accelerated weather resistance test was performed using an accelerated weather resistance tester (QUV, manufactured by Q-Lab). In this tester, the cured film of the substrate having the film is irradiated with ultraviolet rays at an illuminance of 0.71 W/m 2 in an environment of 60° C. for 4 hours, and then dew condensation is performed in an environment of 50° C. 98% RH for 4 hours. cycle was performed. At this time, ultraviolet irradiation was performed using a UVB-313 type lamp.

The degree of yellowing was measured using a color difference meter (JP7100F, manufactured by Color Techno Systems, Inc.) in accordance with JIS Z8722:2000. The difference Δb* between the b values before and after the accelerated weathering test was 1 or less as a pass.

Adhesiveness was evaluated by performing a peeling test according to the method of the checkerboard peeling test described in JIS K5400. Specifically, on the cured film after the accelerated weathering test, a 1 mm wide, 100-mass wound was put with a cutter to prepare a checkerboard test piece, and "Cellotape" (registered trademark, manufactured by Nichiban Co., Ltd.) was applied to the test piece, This tape was quickly pulled upward at an angle of 45 degrees with respect to the checkerboard to be peeled off, and the number of the remaining cured films of the checkerboard was used as an index of adhesion. In this embodiment, it is judged that the higher the residual ratio of the cured film remaining with respect to 100 masses, the higher the adhesiveness. If it was 79/100 or less, it was set as x.

<Evaluation result>

The evaluation results of each Example and Comparative Example are shown in Tables 3 and 4 below.

As shown in Table 3, it was confirmed that Examples 1 to 9 all had a haze of 1% to 30%, and while having a suitable haze, desired antiglare properties were obtained, and excellent scratch resistance and weather resistance were confirmed. Moreover, it was confirmed that hardness and transparency were also high.

In particular, in Example 1, since the component (A1) having an alicyclic skeleton was used as the aliphatic urethane (meth)acrylate (A), Examples (A2) to (A4) having no alicyclic skeleton were used. Compared with 2 to 4, ΔHZ in the tabi abrasion test was small, and it was confirmed that higher scratch resistance could be obtained.

On the other hand, as shown in Table 4, in Comparative Examples 1 to 3, instead of the aliphatic urethane (meth)acrylate (A), aromatic urethane acrylate (A1'), polyester acrylate (A2'), epoxy acrylate ( Since A3') was used, scratch resistance and weather resistance became insufficient, and it was confirmed that various characteristics could not be obtained in good balance at a high level.

In the comparative example 4, since the spherical silica particle (C) was not mix|blended, although transparency was high, since haze was too low, it was confirmed that the anti-glare property which makes it possible to suppress glare cannot be obtained. Moreover, although the spherical silica particle (C) was not mix|blended, it was confirmed that not only the scratch resistance fell, but also the weather resistance fell.

In Comparative Example 5, instead of the spherical silica particles (C), acrylic beads (C1') having a sharp particle size distribution and a small variation in particle diameter were used, but the hardness of the acrylic beads (C1') itself is insufficient. It was confirmed that scratch resistance was inferior.

In Comparative Examples 6 to 9, it was confirmed that the amorphous silica particles (C2') to (C5') having a wide particle size distribution and large dispersion in particle diameters were used, so that scratch resistance and weather resistance were inferior.

In Comparative Example 10, since the ultraviolet absorber (D) was not blended, it was confirmed that sufficient weather resistance could not be obtained.

In Comparative Example 11, since the fluorine-based compound (E) having a photopolymerizable unsaturated group was not blended, it was confirmed that sufficient weather resistance could not be obtained.

Thus, aliphatic urethane (meth)acrylate (A), (meth)acrylate monomer (B), spherical silica particles (C), ultraviolet absorber (D), fluorine-based compound having a photopolymerizable unsaturated group (E) and a photopolymerization initiator ( According to the photocurable resin composition containing F), it is possible to form a cured film excellent in weather resistance, scratch resistance and anti-glare properties.

<Preferred aspect of the present invention>

Hereinafter, it adds about the preferable aspect of this invention.

[Annex 1]

According to one aspect of the present invention,

An aliphatic urethane (meth)acrylate (A),

(meth) acrylate monomer (B) and,

Spherical silica particles (C);

UV absorber (D) and

A fluorine-based compound (E) having a photopolymerizable unsaturated group, and

A photocurable resin composition containing a photoinitiator (F) is provided.

[Annex 2]

In the photocurable resin composition of Appendix 1, preferably,

The average particle diameter of the said spherical silica particle (C) is 1 micrometer or more and 10 micrometers or less.

[Annex 3]

In the photocurable resin composition of Appendix 1 or 2, preferably,

D90/D10 of the said spherical silica particle (C) is 2.0 or less, when the particle size of 10% and 90% of accumulation is D10 and D90, respectively, in the particle size distribution on a volume basis.

[Annex 4]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 3, preferably,

As for the said spherical silica particle (C), when the particle diameter of 50% of accumulation is D50 in the particle size distribution on a volume basis, both D50/D10 and D90/D50 are 1.5 or less.

[Annex 5]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 4, preferably,

The said spherical silica particle (C) is contained in 0.5 mass part or more and 15 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.

[Annex 6]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 5, preferably,

The aliphatic urethane (meth)acrylate (A) has an alicyclic skeleton.

[Annex 7]

In the photocurable resin composition of Appendix 6, preferably,

The aliphatic urethane (meth)acrylate (A) is formed by polymerizing an isocyanate compound (a1) and a (meth)acrylate monomer (a2) having a hydroxyl group, and the isocyanate compound (a1) is an isocyanate in an alicyclic skeleton It is an alicyclic isocyanate in which at least two reactive groups having a group are bonded, and the reactive groups have the same chemical structure.

[Annex 8]

In the photocurable resin composition of Appendix 7, preferably,

The said isocyanate compound (a1) is hydrogenated diphenylmethane diisocyanate.

[Annex 9]

In the photocurable resin composition of Appendix 7 or 8, preferably,

The (meth)acrylate monomer (a2) forming the aliphatic urethane (meth)acrylate (A) has three or more photopolymerizable unsaturated groups in one molecule.

[Annex 10]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 9, preferably,

The weight average molecular weights of the said aliphatic urethane (meth)acrylate (A) are 800 or more and 30,000 or less.

[Annex 11]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 10, preferably,

The said aliphatic urethane (meth)acrylate (A) is contained in 10 mass parts or more and 80 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.

[Annex 12]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 11, preferably,

The (meth)acrylate monomer (B) has three or more photopolymerizable unsaturated groups in one molecule.

[Annex 13]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 12, preferably,

The said (meth)acrylate monomer (B) is contained in 10 mass parts or more and 80 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.

[Annex 14]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 13, preferably,

The compounding ratio of the said (meth)acrylate monomer (B) with respect to the said aliphatic urethane (meth)acrylate (A) is 0.5 or more and 10 or less.

[Annex 15]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 14, preferably,

The said ultraviolet absorber (D) is contained in 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.

[Annex 16]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 15, preferably,

The said ultraviolet absorber (D) contains at least 1 of the ultraviolet absorber (d1) which has a triazine skeleton, and the ultraviolet absorber (d2) which has a benzotriazole skeleton.

[Annex 17]

In the photocurable resin composition of Supplementary Note 16, preferably,

The ultraviolet absorber (d2) having the benzotriazole skeleton has a photopolymerizable unsaturated group.

[Annex 18]

In the photocurable resin composition of Appendix 16 or 17, preferably,

The ultraviolet absorber (d1) having a triazine skeleton and the ultraviolet absorber (d2) having a benzotriazole skeleton are contained in a ratio of 99:1 to 1:99.

[Annex 19]

In any one of the photocurable resin compositions of Supplementary Notes 16 to 18, preferably,

The ultraviolet absorber (d1) having a triazine skeleton and the ultraviolet absorber (d2) having a benzotriazole skeleton are contained in a ratio of 90:10 to 50:50.

[Annex 20]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 19, preferably,

The fluorine-based compound (E) having a photopolymerizable unsaturated group has a perfluoropolyether skeleton.

[Annex 21]

In any one of the photocurable resin compositions of Supplementary Notes 1 to 20, preferably,

The fluorine-type compound (E) which has the said photopolymerizable unsaturated group is contained in 0.1 mass part or more and 20 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.

[Annex 22]

In any one of the photocurable resin compositions of Supplementary Notes 1-21, preferably,

It further contains a light stabilizer (G).

[Annex 23]

According to another aspect of the present invention,

A cured film formed of any one of the photocurable resin compositions of Supplementary Notes 1-22 is provided.

[Annex 24]

According to another aspect of the present invention,

There is provided a substrate having a substrate and a coating having a cured coating according to Supplementary Note 23 provided on the substrate.

[Annex 25]

According to another aspect of the present invention,

A method for producing a cured film having a curing step of curing any one of the photocurable resin compositions of Supplementary Notes 1-22 by irradiation with light is provided.

[Annex 26]

According to another aspect of the present invention,

A coating step of applying any one of the photocurable resin compositions of Supplementary Notes 1-22 to at least one main surface of the substrate;

There is provided a method for manufacturing a base material having a coating film, comprising a curing step of curing the photocurable resin composition by light irradiation after the coating step to form a cured coating film.

Claims (17)

An aliphatic urethane (meth)acrylate (A),
(meth) acrylate monomer (B) and,
Spherical silica particles (C);
UV absorber (D) and
A fluorine-based compound (E) having a photopolymerizable unsaturated group, and
It contains a photoinitiator (F),
The spherical silica particles (C) have a D90/D10 of 2.0 or less when the particle diameters of 10% and 90% of the cumulative particles in the volume-based particle size distribution are D10 and D90, respectively.
The method of claim 1,
The photocurable resin composition whose average particle diameter of the said spherical silica particle (C) is 1 micrometer or more and 10 micrometers or less.
3. The method of claim 1 or 2,
The photocurable resin composition which contains the said spherical silica particle (C) in 0.5 mass part or more and 15 mass parts or less with respect to 100 mass parts of solid content of a photocurable resin composition.
3. The method of claim 1 or 2,
The photocurable resin composition in which the said aliphatic urethane (meth)acrylate (A) has an alicyclic skeleton.
5. The method of claim 4,
The aliphatic urethane (meth)acrylate (A) is formed by polymerizing an isocyanate compound (a1) and a (meth)acrylate monomer (a2) having a hydroxyl group, wherein the isocyanate compound (a1) is an isocyanate in an alicyclic skeleton The photocurable resin composition is an alicyclic isocyanate in which at least two reactive groups having a group are bonded and the reactive groups have the same chemical structure.
6. The method of claim 5,
The photocurable resin composition whose said isocyanate compound (a1) is hydrogenated diphenylmethane diisocyanate. 3. The method of claim 1 or 2,
The photocurable resin composition whose weight average molecular weight of the said aliphatic urethane (meth)acrylate (A) is 800 or more and 30,000 or less.
3. The method of claim 1 or 2,
The photocurable resin composition in which the said (meth)acrylate monomer (B) has 3 or more photopolymerizable unsaturated groups in 1 molecule.
3. The method of claim 1 or 2,
The photocurable resin composition in which the mixing ratio of the said (meth)acrylate monomer (B) with respect to the said aliphatic urethane (meth)acrylate (A) is 0.5 or more and 10 or less.
3. The method of claim 1 or 2,
The photocurable resin composition in which the said ultraviolet absorber (D) contains at least 1 of the ultraviolet absorber (d1) which has a triazine skeleton, and the ultraviolet absorber (d2) which has a benzotriazole skeleton. 11. The method of claim 10,
The photocurable resin composition wherein the ultraviolet absorber (d2) having a benzotriazole skeleton has a photopolymerizable unsaturated group.
3. The method of claim 1 or 2,
The photocurable resin composition in which the said fluorine-type compound (E) has a perfluoro polyether skeleton.
A cured film formed from the photocurable resin composition according to claim 1 or 2.
A base material having a base material and a film provided with the cured film according to claim 13 provided on the base material.
A method for producing a cured coating film comprising a curing step of curing the photocurable resin composition according to claim 1 or 2 by light irradiation. An application step of applying the photocurable resin composition according to claim 1 or 2 to at least one main surface of the substrate;
The manufacturing method of the base material with a film which has a hardening process of hardening the said photocurable resin composition by light irradiation after the said application|coating process, and forming a cured film. delete