JP2016040352A - Maintenance/protection film for glass, method of producing the same, maintenance/protection method, glass with maintenance/protection film, and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a maintenance/protection film for glass which is excellent in abrasion resistance, coat layer durable adhesion, appearance, and antifouling property.SOLUTION: The maintenance/protection film for glass includes a substrate film, a coat layer provided on one surface of the substrate film, and an adhesive layer provided on the opposite surface thereof. The coat layer is a cured product of a photocurable resin composition containing: (A) an aliphatic urethane (meth)acrylate; (B) polymerizable silica particles modified with a (meth)acryloyl group and having a volume average particle diameter of 10-600 nm; (C) a photocurable compound having a fluorine atom in the molecule; (D) a (meth)acrylate compound; and (E) a photopolymerization initiator. The content of (B) and the content of (C) are 5-45 mass% and 0.1-5.0 mass%, respectively, based on the total amount of (A) to (E) in the photocurable resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a maintenance protective film for glass and a production method thereof, a maintenance protection method, a glass with a maintenance protection film, and a production method thereof.

  Glass includes organic glass made of transparent resin in addition to inorganic glass. Conventionally, repair work when there is damage, contamination, or the like that impairs the appearance of the glass is often difficult, and in most cases, the glass itself is replaced with a new one. In particular, organic glass, which is a transparent resin base material, is often provided with a hard coat on the surface to prevent scratches and the like, and cannot be recoated when it is damaged or contaminated. In recent years, there has been a movement to apply a transparent resin substrate as a substitute for inorganic glass, taking advantage of the light weight and safety of plastic materials. Examples of the application include vehicles, automobiles, windows, floors, and other transparent resin panels for electronic materials. When applying a transparent resin substrate, it is necessary to protect the surface of the transparent resin substrate in order to prevent scratches. Depending on the application, the required functions and performance are various, and the levels are various, but a high level of wear resistance, chemical resistance, weather resistance and the like are often required.

In order to satisfy the above requirements, it is known to provide a wear-resistant coating on the surface of a transparent resin substrate, particularly a hard coat having an organosiloxane bond, which is known as a coating having excellent performance. Products are marketed. Moreover, it is known that the hard coat which has a specific organosiloxane bond is suitable for films, such as a car window (for example, refer patent documents 1-2). Furthermore, a method of forming a SiO ₂ film layer using plasma CVD on the hard coat having the organosiloxane bond has been reported (for example, see Patent Document 3).

  In addition, from the viewpoint of production efficiency and environmental impact, a UV curable hard coat is known that uses a small amount of solvent and requires less time and energy for curing. For example, a silica particle having a (meth) acryloyl group and a coating material having a polymerizable functional group are known (see, for example, Patent Document 4).

  In addition, an efficient method has been proposed which includes a step of forming a hard coat on a film and integrating the film at the time of transparent plastic molding such as injection molding (for example, see Patent Documents 5 to 6). Furthermore, it is also known to use a saddle type silsesquioxane resin in a hard coat to increase the hardness and improve the scratch hardness (see, for example, Patent Document 7).

JP 2002-36870 A JP 2001-354781 A US Patent Publication No. 2006/0029764 JP 2003-41148 A JP 2008-260202 A JP 2002-1759 A JP 2012-183818 A

  However, the coating material described in the cited document 4 does not necessarily have sufficient wear resistance, weather resistance, adhesion to glass, and the like. Molded products obtained by the methods described in the cited references 5 to 6 cannot be said to have sufficient wear resistance, and the appearance of smears, bubbles, etc. formed on the coated surface when a hard coat is applied to the film. There is also the possibility of deteriorating. Furthermore, the hard coat film laminate described in the cited document 7 cannot be said to have sufficient weather resistance, appearance, and the like.

  In addition, once the transparent plastic surface is protected by the above-described method for protecting the transparent plastic surface, it is difficult to remove the hard coat and recoat cannot be performed. For this reason, when the hard coat is damaged, contaminated, deteriorated, etc., it is necessary to discard the transparent plastic and reattach a new one, and there are problems such as an increase in cost and industrial waste.

  The present invention has been made in view of such a technical background, and it is an object to provide a maintenance protective film for glass excellent in abrasion resistance, coat layer durable adhesion, appearance and antifouling property, and a method for producing the same. To do. Moreover, it aims at providing the maintenance protection method which can use glass for a long term using this maintenance protection film for glass, the glass with the maintenance protection film for glass, and its manufacturing method.

  Aspects of the present invention are as follows.

<1> a base film containing a transparent resin, a coat layer provided on one side of the base film, an adhesive layer provided on the surface of the base film opposite to the side on which the coat layer is provided, With
The coat layer is
(A) an aliphatic urethane (meth) acrylate;
(B) polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm;
(C) a photocurable compound having a fluorine atom in the molecule;
(D) a (meth) acrylate compound;
(E) a photopolymerization initiator, and a cured product of a photocurable resin composition,
The content of the (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of the (A) to (E) in the photocurable resin composition, and the (C) molecule The maintenance protective film for glass whose content rate of the photocurable compound which has a fluorine atom in it is 0.1 mass%-5.0 mass%.

<2> The maintenance protective film for glass according to <1>, wherein the photocurable resin composition further includes an ultraviolet absorber and a light stabilizer.
<3> The glass protective protective film according to <1> or <2>, wherein the thickness of the base film is in the range of 30 μm to 300 μm, and the thickness of the coat layer is in the range of 3 μm to 50 μm.
<4> The maintenance protective film for glass according to any one of <1> to <3>, wherein the 180 ° peel strength with respect to the glass is 5 N / 25 mm to 40 N / 25 mm.

<5> In any one of <1> to <4>, the adhesive layer includes a copolymer including a structural unit derived from (meth) acrylic acid ester and a structural unit derived from (meth) acrylamide. The maintenance protective film for glass as described.
<6> A release film is further provided on the adhesive layer,
The maintenance protection for glass according to any one of <1> to <5>, wherein a 180 ° peel strength between the release film and the adhesive layer is 0.3 N / 25 mm to 3.0 N / 25 mm. the film.

<7> including a step of providing a coat layer on one side of a base film containing a transparent resin, and a step of providing an adhesive layer on the surface of the base film opposite to the side on which the coat layer is provided,
The coat layer is
(A) an aliphatic urethane (meth) acrylate;
(B) polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm;
(C) a photocurable compound having a fluorine atom in the molecule;
(D) a (meth) acrylate compound;
(E) a photopolymerization initiator, and a cured product of a photocurable resin composition,
The content of the (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of the (A) to (E) in the photocurable resin composition, and the (C) molecule The manufacturing method of the maintenance protective film for glass whose content rate of the photocurable compound which has a fluorine atom in it is 0.1 mass%-5.0 mass%.

<8> The step of protecting the glass by applying the maintenance protective film for glass according to any one of <1> to <6> on a glass surface, and the maintenance protective film for glass at any time The process which peels from the said glass surface, affixes the maintenance protection film for glass of any one of said <1>-<6> on the said glass surface, and protects the said glass,
Including glass maintenance protection method.

<9> A method for producing a glass with a maintenance protective film, comprising a step of bonding the glass maintenance protective film according to any one of <1> to <6> to a glass surface.
<10> A glass with a maintenance protective film produced by the production method according to <9>.

  ADVANTAGE OF THE INVENTION According to this invention, the maintenance protective film for glass excellent in abrasion resistance, a coating layer durable adhesiveness, an external appearance, and antifouling property, and its manufacturing method are provided. Moreover, the maintenance protection method which can use glass for a long term using this maintenance protection film for glass, the glass with the maintenance protection film for glass, and its manufacturing method are provided.

It is a schematic cross section which shows an example of the maintenance protection film for glass of this invention.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. To do.
In the present specification, the “layer” and the “film” include a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view.
In this specification, the “step” is not limited to an independent step, and is included in the term if the intended action of the step is achieved even when it cannot be clearly distinguished from other steps.
In the present specification, the term “(meth) acryloyl group” means at least one of acryloyl group and methacryloyl group, and the term “(meth) acrylate” means at least one of acrylate and methacrylate.

  In this specification, the term “glass” includes inorganic glass and organic glass.

<Maintenance protective film for glass>
The maintenance protective film for glass of the present invention is provided on the surface of the base film containing the transparent resin, the coating layer provided on one side of the base film, and the surface of the base film opposite to the surface on which the coating layer is provided. An adhesive layer, and a coating layer modified with (A) aliphatic urethane (meth) acrylate and (B) (meth) acryloyl group, and a volume-average particle diameter of 10 to 600 nm Cured product of photocurable resin composition comprising particles, (C) a photocurable compound having a fluorine atom in the molecule, (D) (meth) acrylate compound, and (E) a photopolymerization initiator. And
The content of (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of components (A) to (E) in the photocurable resin composition, and (C) fluorine in the molecule. The content rate of the photocurable compound which has an atom is 0.1 mass%-5.0 mass%.

The maintenance protective film for glass of the present invention has excellent wear resistance, coat layer durable adhesion, appearance and antifouling properties by having the above-described configuration.
The reason for this is not clear, but is considered as follows. In the present invention, by including a specific amount of the polymerizable silica particles, the hardness of the cured product is improved and the wear resistance is improved, and an excellent appearance and durability of the coat layer are obtained. In addition, by including a specific amount of a photocurable compound having a fluorine atom in the molecule, the surface tension of the photocurable resin composition is reduced, so that the generation of bubbles and the like is suppressed during application to the base film, An excellent appearance is obtained, and furthermore, the water repellency of the coat layer is improved, so that the antifouling property is improved. Further, since the surface of the coat layer becomes slippery, the wear resistance can be improved. Furthermore, a tough coat layer is formed when the content of the polymerizable silica particles and the photocurable compound having a fluorine atom in the molecule is within a specific range.
Moreover, the coating layer which is excellent in a weather resistance can be formed by including aliphatic urethane (meth) acrylate which is hard to deteriorate with an ultraviolet-ray. By including a (meth) acrylate compound, a coat layer having excellent adhesion can be formed. Moreover, the raise of the viscosity of a photocurable resin composition can be suppressed, generation | occurrence | production of a bubble etc. is suppressed in the case of the provision to a base film, and the outstanding external appearance is obtained.

Next, one embodiment of the maintenance protection film for glass of the present invention will be described with reference to FIG. The glass maintenance protective film shown in FIG. 1 has a base film 1 containing a transparent resin and a coat layer 2 provided on one side of the base film 1. The base film 1 may have a single layer structure or a multilayer structure composed of a plurality of layers. The coat layer 2 may have a single layer structure or a multilayer structure.
The glass maintenance protective film shown in FIG. 1 further has an adhesive layer 3 on the surface of the base film 1 opposite to the surface on which the coat layer 2 is provided, and the mold release property on the adhesive layer 3. A film (cover film) 4 is further provided.

[Base film]
The base film in this invention will not be specifically limited if it is a film containing transparent resin, The transparent resin film normally used in the said technical field can be used. For example, the base film includes a transparent resin film made of at least one resin selected from the group consisting of polycarbonate, polymethyl (meth) acrylate (PMMA) and polyethylene terephthalate (PET). The base film may have a single layer structure or a multilayer structure composed of two or more resin layers having different compositions. Each resin layer in a single layer structure or a multilayer structure is a layer containing at least one resin selected from the above.

  The thickness of the base film is not particularly limited, and is preferably in the range of 30 μm to 300 μm, and more preferably 50 μm to 300 μm from the viewpoint of workability. Here, the thickness of the base film is an average thickness, and 6 points are measured using a laser displacement meter (for example, Keyence Corporation, multilayer film thickness measuring instrument “SI-T series”), and the arithmetic average thereof. Obtained as a value. In addition, when a base film has a multilayer structure, "the thickness of a base film" means the total thickness of the resin layer which forms the multilayer structure.

[Coat layer]
The coat layer in the present invention is a cured product of a photocurable resin composition containing the following five components A to E.
Component A: Aliphatic urethane (meth) acrylate Component B: Polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm (hereinafter also referred to as “specific polymerizable silica particles”). )
Component C: a photocurable compound having a fluorine atom in the molecule (hereinafter also referred to as “specific photocurable compound”)
Component D: (Meth) acrylate compound Component E: Photopolymerization initiator In addition, the content of (B) specific polymerizable silica particles with respect to the total amount of (A) to (E) in the photocurable resin composition Is 5 mass%-45 mass%, and the content rate of (C) specific photocurable compound is 0.1 mass%-5.0 mass%.
Each component will be described sequentially.

(Component A: Aliphatic urethane (meth) acrylate)
The aliphatic urethane (meth) acrylate in the present invention is not particularly limited as long as it is a urethane (meth) acrylate having an aliphatic group. By using an aliphatic urethane (meth) acrylate, the weather resistance of the coat layer is improved, and the coat layer tends to hardly yellow.
As the aliphatic urethane (meth) acrylate, polyfunctional urethane (meth) acrylate is preferably used, more preferably urethane (meth) acrylate having 3 or more functional groups, and 6 or more functional groups. More preferably, urethane (meth) acrylate is used. When polyfunctional urethane (meth) acrylate is used, the crosslink density in the coat layer is improved, and the wear resistance, weather resistance and the like tend to be improved. In particular, by using an aliphatic urethane (meth) acrylate having 6 or more functional groups, the weather resistance is excellent and the crosslinking density is high, so that a coating layer having excellent wear resistance tends to be formed.

  The number of functional groups of the aliphatic urethane (meth) acrylate in the present invention is not particularly limited, and may be within a range of 3 to 15 in consideration of a balance of physical properties such as wear resistance, weather resistance, and coating layer adhesion durability. Preferably, it is in the range of 6-12.

  The content of the aliphatic urethane (meth) acrylate in the present invention is not particularly limited. The content of the aliphatic urethane (meth) acrylate is preferably 20% by mass to 80% by mass with respect to the total amount of the components A to E in the photocurable resin composition from the viewpoint of wear resistance. 30 mass% to 60 mass% is more preferable. If it is the range of 20 mass%-80 mass%, the more outstanding abrasion resistance will be obtained. Moreover, when the content of the aliphatic urethane (meth) acrylate is 20% by mass or more, the appearance of the coat layer becomes good, and the coat layer durability adhesion is also excellent. When the content is 80% by mass or less, warpage of the maintenance protective film due to curing shrinkage hardly occurs.

  The aliphatic urethane (meth) acrylate in the present invention can be obtained by reacting a polyisocyanate compound, a polyol, and a (meth) acrylate having a hydroxyl group by a known method.

  Examples of the polyisocyanate compound include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate trimer, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, 1,3-bis. (Isocyanatomethyl) cyclohexane, isophorone diisocyanate trimer, and aliphatic polyisocyanate compounds thereof.

  Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol and the like.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol. Examples include penta (meth) acrylate and dipentaerythritol tri (meth) acrylate.

  Commercially available aliphatic urethane (meth) acrylates other than the aliphatic urethane (meth) acrylate obtained by reacting the above-described polyisocyanate compound, polyol, and (meth) acrylate having a hydroxyl group may be used. For example, “Hitaroid HA7902-1” (Hitachi Chemical Co., Ltd.), “Shikou 7610” (Nippon Synthetic Chemical Industry Co., Ltd.) and the like can be mentioned.

(Component B: Polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm)
Polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm (hereinafter also referred to as “specific polymerizable silica particles”) are important components for improving wear resistance. It is. The specific polymerizable silica particles can be obtained, for example, by modifying the surface of the silica particles with a compound having a (meth) acryloyl group such as methacryloxypropyltrimethoxysilane.

Further, for example, specific polymerizable silica particles can be obtained by subjecting a compound having a (meth) acryloyl group and an alkoxysilane partial condensate to a dealcoholization condensation reaction.
Examples of the compound having a (meth) acryloyl group used in the dealcoholization condensation reaction include polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, hydroxyalkyl (meth) acrylates, and hydroxyalkyl (meth) acrylate. Ε-caprolactone condensates.

Examples of the alkoxysilane partial condensate used in the dealcoholization condensation reaction include a product obtained by partially hydrolyzing and condensing an alkoxysilane compound and water using an acid or a base as a catalyst.
Examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

  As the specific polymerizable silica particles, commercially available particles may be used, and examples thereof include “Desolite Z7501” (JSR Corporation), “Compolide HUV U70DM04” (Atomics Corporation), and the like.

The volume average particle diameter of the specific polymerizable silica particles is preferably in the range of 10 nm to 600 nm. When the volume average particle diameter is 600 nm or less, it is easy to ensure the transparency of the coat layer, and the possibility of impairing the appearance is suppressed. Further, if the volume average particle diameter is 10 nm or more, it is practical because it is cheaper than those having a volume average particle diameter smaller than that.
From the viewpoint of transparency and appearance of the coat layer, the upper limit of the volume average particle diameter of the specific polymerizable silica particles is more preferably 550 nm or less, and further preferably 500 nm.
The volume average particle diameter of the specific polymerizable silica particles is measured using a laser diffraction method, a dynamic light scattering method, a centrifugal sedimentation method, a flow field separation (FFF), or the like. When measuring the volume average particle size by the laser diffraction method, it can be performed using a laser diffraction scattering particle size distribution measuring device (for example, LS230 manufactured by Beckman Coulter, Inc.).

The content of the specific polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of components A to E in the photocurable resin composition. If the content is 5% by mass or more, a coating layer having excellent wear resistance tends to be formed. On the other hand, when the content is 45% by mass or less, the adhesion of the coating layer to the base film (coating durability of the coating layer) is improved, and problems such as the coating layer being easily broken are suppressed, and excellent. Appearance tends to be obtained.
The content of the specific polymerizable silica particles is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of wear resistance, and 40% from the viewpoint of coat layer durable adhesion and appearance. It is preferable that it is below mass%.

(Component C: a photocurable compound having a fluorine atom in the molecule)
The photocurable compound having a fluorine atom in the molecule in the present invention (hereinafter also referred to as “specific photocurable compound”) is a compound having an effect of lowering the surface tension. By using the specific photocurable compound, the coating property of the photocurable resin composition of the present invention on the base film is improved, and a coating layer with few defects can be formed, and a diluent is used more than necessary. It tends to be unnecessary. Moreover, since it has the effect of making the coat layer surface slippery, the wear resistance of the coat layer can be improved. Furthermore, since the water repellency is improved, there is a tendency to improve the antifouling property and chemical resistance of the coat layer.

Specific photocurable compounds include fluorine-containing surfactants, and oligomer-type fluorine-containing surfactants or active energy ray-curable fluorine-containing surfactants are preferred.
The oligomer type fluorine-containing surfactant has a group containing a perfluoroalkyl group in the side chain of the oligomer. Specifically, “Megafac F-430”, “Megafac F-477”, “Megafac” "F-552", "Mega Fuck F-553", "Mega Fuck F-554", "Mega Fuck F-555", "Mega Fuck F-556", "Mega Fuck F-557", "Mega Fuck F-""558","MegafuckF-559","MegafuckF-561","MegafuckF-562","MegafuckR-40","MegafuckR-41","MegafuckTF-1540" , “Megafuck TF-1760” (DIC Corporation) and the like.
The active energy ray-curable fluorine-containing surfactant has a perfluoroalkyl group and a reactive double bond-containing group in the oligomer. Specifically, “Megafac RS-72-K”, “Megafac” RS-75 "," Megafuck RS-76-E "," Megafuck RS-76-NS "(DIC Corporation), and the like.

The content rate of a specific photocurable compound is 0.1 mass%-5.0 mass% with respect to the total amount of the component A-the component E in a photocurable resin composition. If the content is 0.1% by mass or more, a coating layer excellent in appearance and antifouling property tends to be obtained. When the content is 5.0% by mass or less, the coating layer durability adhesion is improved, and the yellowing degree change tends to be suppressed.
The content of the specific photocurable compound is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, from the viewpoints of appearance and antifouling property, and the coating layer durable adhesion and From the viewpoint of change in yellowing degree, it is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less.

Examples of the compound having an effect of lowering the surface tension include polyether-modified polydimethylsiloxane, which are generally marketed as an antifoaming agent, a leveling agent, a surface conditioner and the like. However, even if these compounds are used, it is difficult to lower the coefficient of friction on the surface of the coat layer or improve the water repellency as the fluorine-containing compound, and there are problems such as easy bleeding.
On the other hand, a compound having a fluorine atom in the molecule tends to sufficiently reduce the coefficient of friction on the surface of the coat layer and improve water repellency. Furthermore, a photocurable compound having a photofluorine atom is incorporated into the resin skeleton through a chemical bond, so that problems such as bleeding out can be solved.

(Component D: (meth) acrylate compound)
In the present invention, by using the (meth) acrylate compound, it is possible to suppress an excessive increase in the viscosity of the photocurable resin composition and to secure coatability. Moreover, it exists in the tendency for the adhesive force to the base film of a coating layer to improve by selecting the (meth) acrylate compound which has a certain amount of permeability to a base film.

  The content rate of a (meth) acrylate compound is not specifically limited, It is preferable that it is 5 mass%-40 mass% with respect to the total amount of component AE of a photocurable resin composition, and 10 mass%-20 mass%. % Is more preferable. When the content is 5% by mass or more, the viscosity of the photocurable resin composition does not become too high, and coating on the film substrate is easy. On the other hand, it exists in the tendency which can suppress that the effect of component AC of a photocurable resin composition is impaired as content rate is 40 mass% or less.

  Examples of the (meth) acrylate compound in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, ethoxyethyl ( (Meth) acrylate, butoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate 2- (meth) acryloyloxyethyl acid phosphate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedi (meth) acrylate , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (acryloxyethyl) isocyanurate, etc. And the like. These may be used alone or in combination of two or more.

(Component E: Photopolymerization initiator)
The photocurable resin composition of the present invention contains a photopolymerization initiator. Content of a photoinitiator is not specifically limited, When the total amount of component AE in a photocurable resin composition is 100 mass parts, it is preferable that it is 3 mass parts-10 mass parts, and 3 masses. It is more preferable that it is 7 parts by mass. When the content of the photopolymerization initiator is within the above range, a sufficient crosslinking density is obtained, and a coating layer that is superior in wear resistance tends to be obtained.

The photopolymerization initiator is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other benzoins, benzoin alkyl ethers, benzophenone, benzoylbenzoic acid and other aromatics Ketones, α-dicarbonyls such as benzyl, benzyl ketals such as benzyldimethyl ketal and benzyldiethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-hydroxy 2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2- Methyl-1- (4- Acetophenones such as methylthio) phenyl) -2-morpholinopropanone, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 2, Thioxanthones such as 4-diisopropylthioxanthone, α-acyloximes such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoate And amines such as isoamyl acid.
A commercially available photopolymerization initiator may be used. As a commercial item, "Irgacure 184", "Irgacure 149" etc. (BASF Japan Co., Ltd.), "Kayacure DETX-S", "Kayacure EPA" etc. (Nippon Kayaku Co., Ltd.) are mentioned, for example.
These photopolymerization initiators may be used alone or in combination of two or more. Moreover, you may use together with a sensitizer, an accelerator, etc.

(Other components and composition)
The photocurable resin composition in the present invention may further contain components other than the above components A to E. When the maintenance protective film for glass of the present invention is used in applications where it is exposed to light such as sunlight, the photocurable resin composition preferably contains an ultraviolet absorber, a light stabilizer, etc., and is photocurable. More preferably, the resin composition further contains an ultraviolet absorber and a light stabilizer.

  Although it does not specifically limit as a ultraviolet absorber, The compound which has an unsaturated double bond is preferable. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, formamidine compounds, oxanilide compounds, salicylate compounds, and the like. Commercially available products include “Tinuvin 327”, “Tinuvin 328”, “Tinuvin 400”, “Tinuvin 479”, “Tinuvin 900”, “Tinuvin 928”, “Yubinar 3035” (above, BASF Japan Ltd.), “ Seasorb 100 "," Seasorb 101 "," Seesorb 103 "," Seesorb 151 "," Seesorb UV-1 "(above, Sipro Kasei Co., Ltd.) and the like. These ultraviolet absorbers may be used alone or in combination of two or more.

  The content of the ultraviolet absorber is preferably 2 parts by mass to 10 parts by mass, preferably 3 parts by mass to 7 parts by mass when the total amount of components A to E in the photocurable resin composition is 100 parts by mass. It is more preferable that If it is in the said range, it exists in the tendency for the coat layer excellent in the weather resistance to be obtained, maintaining abrasion resistance.

  Although it does not specifically limit as a light stabilizer, It is preferable to use a hindered amine compound. Commercially available products include “Tinuvin 770”, “Tinubin 765”, “Tinubin 123”, “Tinubin 622” (above, BASF Japan Ltd.), “Adeka Stub LA57”, “Adeka Stub LA94”, “Adeka Stub LA87”, “ ADEKA STAB LA-52 "," ADEKA STAB LA-81 "(above, ADEKA Corporation) and the like. These light stabilizers may be used alone or in combination of two or more.

  The content of the light stabilizer is preferably 2 parts by mass to 10 parts by mass, preferably 3 parts by mass to 7 parts by mass when the total amount of components A to E in the photocurable resin composition is 100 parts by mass. It is more preferable that If it is in the said range, the coating layer excellent in weather resistance is obtained, maintaining abrasion resistance.

  The photocurable resin composition may contain various solvents as necessary. Examples of the solvent include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, toluene, xylene, methylcyclohexane, ethylcyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like. These solvents may be used alone or in combination of two or more.

  Moreover, the photocurable resin composition may contain appropriate amounts of various additives such as an antioxidant, a radical scavenger, and a plasticizer.

  Moreover, the photocurable resin composition may contain an appropriate amount of a thermoplastic resin. Examples of the thermoplastic resin include homopolymers such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, and 2-ethylhexyl polymethacrylate, and (meth) acrylic resins such as copolymers thereof.

The thickness of the coat layer is preferably 3 μm to 50 μm. When the thickness of the coat layer is 3 μm or more, weather resistance and scratch resistance tend to be sufficiently obtained, and workability tends to be excellent. Here, the thickness of the coat layer is an average thickness, and 6 points are measured using a laser displacement meter (for example, Keyence Corporation, multilayer film thickness measuring instrument “SI-T series”), and the arithmetic average value thereof. As obtained.
Moreover, in the maintenance protective film for glass of this invention, it is preferable that the thickness of a base film exists in the range of 30 micrometers-300 micrometers, and the thickness of a coating layer exists in the range of 3 micrometers-50 micrometers.

  When the coating layer in the present invention has a multilayer structure, two or more types of photocurable resin compositions having different compounding ratios of the respective components in the photocurable resin composition of the present invention are prepared, and the multilayer structure of two or more layers is prepared. A coat layer may be formed. As a specific example, two types of photo-curable resin compositions having different blending amounts of specific polymerizable silica particles (component B) are prepared, and the blending amount of the specific polymerizable silica particles is smaller on the base film side. A first coat layer is provided using the photo-curable resin composition, and the photo-curable resin composition having the larger amount of the specific polymerizable silica particles is used as the outermost layer on the first coat layer. A second coat layer may be provided. Thereby, the coating layer excellent in weather resistance and abrasion resistance is formed.

[Adhesive layer]
The maintenance protective film for glass of the present invention has an adhesive layer provided on the surface of the base film opposite to the surface on which the coat layer is provided. The definition of the adhesive in the present invention is that an object can be bonded, and a pressure-sensitive adhesive is also included in the adhesive.

  The adhesive layer in the present invention is required to have high transparency, wet heat whitening resistance, blister resistance, tackiness that does not peel, re-peelability, and the like. In order to satisfy these characteristics, the adhesive layer preferably contains a copolymer (component F) containing a structural unit derived from (meth) acrylic acid ester and a structural unit derived from (meth) acrylamide. And an isocyanate compound (component G).

(Component F: a copolymer containing a structural unit derived from (meth) acrylic acid ester and a structural unit derived from (meth) acrylamide)
The structural unit derived from (meth) acrylic acid ester in the copolymer containing the structural unit derived from (meth) acrylic acid ester in the adhesive used in the present invention and the structural unit derived from (meth) acrylamide. The content is preferably 50% by weight to 90% by weight, and the content of the structural unit derived from (meth) acrylamide is preferably 0.5% by weight to 20% by weight.

  The (meth) acrylic acid ester is not particularly limited, and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms, an (meth) acrylic acid alkoxyalkyl ester having an alkyl group having 1 to 18 carbon atoms. Etc. These may be used alone or in combination of two or more.

  It does not specifically limit as (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N-isopropyl (meth) acrylamide, N -Methylol (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. are mentioned. These may be used alone or in combination of two or more.

  The (meth) acrylamide is more preferably a tertiary amino group-containing (meth) acrylamide. By using tertiary amino group-containing (meth) acrylamide, it is possible to realize a better balance between adhesiveness and removability.

  The copolymer containing a structural unit derived from a (meth) acrylic acid ester and a structural unit derived from (meth) acrylamide may contain a structural unit derived from another monomer, if necessary. Examples of other monomers include hydroxyl group-containing (meth) acrylic acid esters.

  It does not specifically limit as a hydroxyl-containing (meth) acrylic acid ester, (meth) acrylic-acid 2-hydroxyethyl, (meth) acrylic-acid 2-hydroxypropyl, (meth) acrylic-acid 4-hydroxybutyl, (meth) acrylic Examples include 6-hydroxyhexyl acid, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, [4- (hydroxymethyl) cyclohexyl] methyl acrylate, and the like. It is done. These may be used individually by 1 type, or may use 2 or more types.

(Component G: Isocyanate compound)
The adhesive in the present invention may further contain an isocyanate compound. Isocyanate compound is not particularly limited, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate trimer, And polyisocyanates such as hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane.

  The isocyanate compound of component G also includes a high molecular weight isocyanate compound obtained by reacting the above polyisocyanate compound with an alcohol or an amine compound.

(Other ingredients)
The adhesive in the present invention may contain other components as necessary. Examples of other components include various additives such as a polymer compound other than components F and G, a crosslinking agent, an antioxidant, a radical scavenger, and an ultraviolet absorber.

  Examples of the crosslinking agent include epoxy compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, metal chelate compounds, and the like. These may be used alone or in combination of two or more.

  Moreover, as long as the effect of this invention is not inhibited, you may use a commercially available adhesive agent. In particular, adhesives used for OCA (Optically Clear Adhesive) tapes such as tablets and smartphones are preferable because of their high transparency. Among them, an adhesive for blister-resistant transparent plastic panels is suitable. Examples of the commercially available products include “Acrybase LKG-1007”, “Acrybase LKG-1010”, “Acrybase LKG-1011”, “Acrybase LKG-1012” (hereinafter, Fujikura Kasei Co., Ltd.) and the like.

  The adhesive in the present invention is preferably adjusted as appropriate so that the 180 ° peel strength with respect to glass is 5 N / 25 mm to 40 N / 25 mm. When the 180 ° peel strength is 5 N / 25 mm or more, problems such as peeling from the glass hardly occur, and when the 180 ° peel strength is 40 N / 25 mm or less, it becomes easy to peel the maintenance protective film from the glass, It can function as a maintenance film. By adjusting the adhesive force within the above range, the maintenance protective film of the present invention can be easily replaced.

  In addition, the 180 ° peel strength between the adhesive layer and the release film in the present invention is preferably 0.3 N / 25 mm to 3.0 N / 25 mm. When the 180 ° peel strength between the adhesive layer and the releasable film is within this range, the releasable film is easily peeled off from the adhesive layer, and when the maintenance protective film for glass of the present invention is bonded to glass. There is a tendency to improve workability.

[Releasable film]
The maintenance protective film for glass of the present invention may further have a releasable film provided on the adhesive layer. The releasable film in the present invention is not particularly limited as long as it is used as a cover film in the technical field. The glass maintenance protective film further includes a release film on the adhesive layer, and the 180 ° peel strength between the release film and the adhesive layer is 0.3 N / 25 mm to 3.0 N / 25 mm. preferable.

  It does not specifically limit as a film in this invention, The releaseable film, release paper, etc. which are marketed can be used. Examples of commercially available products include the “Purex” series (Teijin DuPont Films Co., Ltd.) and the “Separator SP-PET” series (Mitsui Chemicals Tosero Co., Ltd.).

<Method for producing maintenance protective film for glass>
Next, the manufacturing method of the maintenance protection film for glass of this invention is demonstrated.
The method for producing a maintenance protective film for glass according to the present invention includes a step of providing a coat layer on one side of a base film containing a transparent resin (hereinafter also referred to as “coat layer forming step”), and a surface on which the coat layer is provided. Including a step of providing an adhesive layer on the surface of the opposite substrate film (hereinafter also referred to as “adhesive layer forming step”),
The coating layer is (A) an aliphatic urethane (meth) acrylate, (B) a polymerizable silica particle modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm, and (C) an intramolecular Is a cured product of a photocurable resin composition containing a photocurable compound having a fluorine atom, (D) (meth) acrylate compound, and (E) a photopolymerization initiator,
The content of (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of components (A) to (E) in the photocurable resin composition, and (C) fluorine in the molecule. The content rate of the photocurable compound which has an atom is 0.1 mass%-5.0 mass%.
The order of the coat layer forming step and the adhesive layer forming step is not particularly limited.

[Coat layer forming step]
In the coating layer forming step, after applying the photocurable resin composition of the present invention to one surface of the base film, the coating layer is a cured product of the photocurable resin composition of the present invention by irradiating with actinic rays. Form.

  The preparation method of a photocurable resin composition is not specifically limited, The above-mentioned component AE and other components can be mixed by a well-known method as needed.

  The method for applying the photocurable resin composition to the base film is not particularly limited, and a known method can be used. For example, dip method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, spin coating method, slit coating method, micro gravure coating method, etc. Can be used. In particular, from the viewpoint of productivity and coating accuracy, it is preferable to use a slit coat method or a micro gravure coat method in a roll-to-roll manner.

  When applying a photocurable resin composition by the said coating method, it is more preferable to provide so that the thickness of the coat layer after hardening may be in the range of 3 micrometers-50 micrometers. When the thickness of the coat layer is 3 μm or more, the weather resistance and wear resistance tend to be improved. Moreover, it is preferable that it is 50 micrometers or less from a viewpoint of workability | operativity.

  When the photocurable resin composition contains a solvent, the solvent may be removed by drying after applying the photocurable resin composition and before irradiation with actinic rays.

  Subsequently, an actinic ray is irradiated and a photocurable resin composition is hardened, and a coat layer is formed. Examples of the actinic rays include ultraviolet rays, electron beams, and gamma rays.

  In the case of ultraviolet irradiation, the conditions are not particularly limited, and it is preferable to irradiate about 500 mJ to 3000 mJ using a high pressure mercury lamp, a metal halide lamp, a fusion lamp or the like. In addition, "UVR-T1" (Topcon Co., Ltd.) can be used as an apparatus for measuring the amount of light.

[Adhesive layer forming step]
In the adhesive layer forming step, the adhesive layer is formed by applying the adhesive to the surface of the base film opposite to the surface on which the coat layer is formed.
The method for producing the adhesive is not particularly limited, and materials can be mixed by a known method. Moreover, you may use a commercial item.

  The adhesive layer is preferably formed by a roll-to-roll method, as in the coating layer forming step. The means for applying the adhesive is not particularly limited, and can be appropriately selected from the above methods in consideration of material properties, coating thickness, and coating accuracy.

  For example, a release film may be laminated after forming an adhesive layer by applying an adhesive to the surface of the base material layer opposite to the surface on which the coat layer is formed. Alternatively, the adhesive layer may be formed by applying an adhesive on the releasable film and then attaching the adhesive to the base film. In any case, when the adhesive contains a solvent, it is dried and then laminated after removing the solvent.

  The thickness of the adhesive layer is not particularly limited, and is preferably in the range of 25 μm to 200 μm in consideration of the performance of the entire product, ease of sticking, appearance, and the like. When it is 25 μm or more, defects are unlikely to occur when the glass maintenance protective film is bonded to organic glass or the like, and when it is 200 μm or less, the performance deterioration of the glass maintenance protective film is suppressed and the appearance tends to be excellent. The thickness of the adhesive layer is an average thickness, and 6 points are measured using a laser displacement meter (for example, Keyence Co., Ltd., multilayer film thickness measuring instrument “SI-T series”), and obtained as an arithmetic average value thereof. It is done.

<Maintenance protection method>
The maintenance protective film for glass according to the present invention can be used for the purpose of protecting glass by bonding with glass through an adhesive layer. Thereby, damage, contamination, etc. of glass can be suppressed. Moreover, when damage, contamination, etc. arise in the maintenance protection film for glass of this invention, it can peel from a glass and can be easily replaced by a new maintenance protection film. Accordingly, the glass can be used for a long time without replacing the glass itself, and the cost and industrial waste can be reduced.

  More specifically, the method for protecting and maintaining glass according to the present invention comprises the steps of protecting the glass by applying the glass maintenance protective film according to the present invention to the glass surface, and the glass maintenance protective film at any time. And a step of protecting the glass by newly applying the glass maintenance protective film of the present invention to the glass surface.

  “Glass” in the present invention includes inorganic glass and organic glass. Examples of the organic glass include a transparent resin substrate.

  The method for bonding the maintenance protective film for glass to glass is not particularly limited, and a known method can be used. From the viewpoint of simplicity, it is preferable to carry out by water sticking. When bonding to a three-dimensional glass, it is preferable to select a method of bonding by TOM molding. The TOM molding in the present invention means molding by the Three Dimension Overlay Method, and indicates a three-dimensional surface decoration molding method developed by Fuse Vacuum Co., Ltd.

<Glass with maintenance protective film and manufacturing method>
The manufacturing method of the glass with a maintenance protective film of this invention includes the process of bonding the maintenance protective film for glass of this invention to the glass surface. Thereby, the glass with a maintenance protective film provided with the maintenance protective film of the present invention on the glass surface is obtained.
As a method of sticking the glass maintenance protective film on the glass surface, the same method as the method of bonding the glass maintenance protective film to glass in the maintenance protection method of the present invention, the adhesive layer of the glass maintenance protective film is applied to the glass surface. Can be bonded together by bringing them into contact with each other.

<Application>
There is no restriction | limiting in particular in the use of the maintenance protection film for glass of this invention, The protection and maintenance of glass, such as a transparent resin panel for vehicles, a motor vehicle, a window, a floor, and other electronic materials, can be illustrated.
By using the maintenance protective film for glass of the present invention, it is possible to efficiently form a protective layer excellent in abrasion resistance, coating layer durable adhesion, appearance and antifouling property on the glass surface, and any maintenance protective film can be used. It is possible to use the glass for a long period of time by peeling it off from the glass surface at this time and attaching it to a new maintenance protective film. Further, it can function as an anti-scattering film when subjected to a large impact that breaks the glass.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples without departing from the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Main component of photocurable resin composition>
[Aliphatic urethane (meth) acrylate: Component A]
(1) “Hitaroid HA7902-1” (Hitachi Chemical Co., Ltd.)
[Polymerizable silica particles: Component B]
(2) “Compolide HUV U70DM04” (Atomics Co., Ltd .; volume average particle size: about 30 nm)
[Photocurable compound having fluorine atom in molecule: Component C]
(3) "Megafuck RS-75" (DIC Corporation)
[(Meth) acrylate: Component D]
(4) “HDDA” (Daicel Ornics Co., Ltd .; 1,6-hexanediol diacrylate)
[Photopolymerization initiator: Component E]
(5) "Ilquagua 184" (BASF Japan K.K.)

<Other ingredients>
(6) Ultraviolet absorber: “Tinuvin 400” (BASF Japan Ltd.)
(7) Light stabilizer: “Tinuvin 144” (BASF Japan K.K.)

<Examples 1-8 and Comparative Examples 1-9>
[Evaluation 1: Appearance of coating]
Each component of the photocurable resin composition was blended at a solid content ratio shown in Tables 1 to 4 below to prepare a liquid photocurable resin composition. In addition, all the numerical values shown in the following Tables 1 to 4 are “parts by mass”.
The prepared liquid photocurable resin composition was put into a liquid feed pump of a roll-to-roll coating machine. In addition, “Iupilon film DF02U” (Mitsubishi Gas Chemical Co., Ltd .: coextruded sheet of polycarbonate resin and acrylic resin: thickness 125 μm) as a base film is wound from the unwinding part of the roll-to-roll coating machine. Passed through. Next, a liquid photocurable resin composition is applied to the acrylic resin layer side of the base film by a slit die method so that the dry film thickness is about 10 μm, and after undergoing drying and exposure processes, the base film A transparent film (hereinafter also referred to as “transparent film with coat layer”) having a cured product layer (hereinafter also referred to as “coat layer”) of the photocurable resin composition was obtained. The drying conditions at this time were 80 ° C. for 2 minutes, and the exposure conditions were 200 mW / cm ² and 3000 mJ / cm ² .
In Comparative Example 9, a compound having no fluorine atom in its molecule (“BYK-347”: Big Chemie Japan Co., Ltd.) was used in place of Component C of the photocurable resin composition in the present invention. That is, “BYK-347” described in Tables 3 and 4 below is not a photocurable compound having a fluorine atom in the molecule.

(1) Evaluation method of coating appearance The appearance after coating of the protective film with a coating layer obtained above was visually observed and evaluated according to the following criteria.
A: There are no coating streaks and coating unevenness, no bubbles exceeding a diameter of 1 mm, and the number of bubbles having a diameter of 0.5 mm to 1.0 mm is within 6 per 1 m ² .
B: There are no coating streaks and coating unevenness, no bubbles exceeding 1 mm in diameter and 3 mm in diameter, and the number of bubbles having a diameter of 0.5 mm to 3.0 mm is within 6 per 1 m ² .
D: Other than the above.

[Evaluation 2: Performance evaluation]
(Preparation of test piece)
“Purex A43” (Teijin DuPont Films, Inc.): A thickness of 38 μm was passed from the unwinding part to the winding part of the roll-to-roll coating machine.
Next, “Acrybase LKG-1012” (Fujikura Kasei Co., Ltd.), an aluminum chelate curing agent and an epoxy curing agent, a stirrer capable of vacuum degassing (Sinky Corp., “Awatori Rentaro ARV-3000TWIN”) And the mixture was stirred to produce an adhesive. In addition, each hardening | curing agent was thrown in in the ratio of 0.08 weight part with respect to 100 weight part of solid content of the said acrylic base LKG-1012.
Thereafter, the vacuum defoamed adhesive is put into the liquid feed pump of the roll-to-roll coating machine, and applied to one side of the Purex A43 by a slit die method so that the dry film thickness is 25 μm, and then dried. (Drying temperature: 100 ° C., drying time: 3 minutes).

  Next, the substrate surface on which the coating layer of the transparent film with a coating layer prepared in the above [Evaluation 1: Coating appearance] set in another unwinder is not formed, and the substrate is removed from the drying furnace. The adhesive surface of the purex A43 with adhesive was bonded to obtain a maintenance protective film for glass. The glass maintenance film thus obtained was affixed to an acrylic plate with water to obtain a test piece for evaluation.

(2) Visible light transmittance evaluation method The visible light transmittance of JIS R3106 (1998) or ISO 9050 (1990) is the initial, after the heat resistance test, after the moisture resistance test and after the thermal cycle test of the obtained test specimen for evaluation. Measurements were made in accordance with the following criteria.
A: The visible light transmittance is 85% or more in any of the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test.
D: The visible light transmittance in at least one of the initial stage, the heat resistance test, the moisture resistance test, and the thermal cycle test is less than 85%.

The heat resistance test, moisture resistance test and thermal cycle test are as follows.
(Heat resistance test)
The test specimen for evaluation was left in a 90 ° C. atmosphere for 1000 hours.
(Moisture resistance test)
The test specimen for evaluation was left for 1000 hours in an atmosphere of 70 ° C. and 95% RH.
(Thermal cycle test)
The test piece for evaluation was put into a thermal cycle test tank, held at 80 ° C. for 2 hours, and then held at −40 ° C. for 2 hours. This was repeated 50 times.

(3) Evaluation method of yellowing degree change The yellowing degree (ΔYI) after the initial stage, after the heat resistance test, after the moisture resistance test and after the thermal cycle test of the obtained test piece for evaluation was measured using a spectroscope (Spectra Corp., “ Solid Lambda UV-NIR ”. More specifically, since the test specimen for evaluation is transparent, the optical fiber for light reception is installed in the spectroscopic device so that transmission measurement can be performed. It was evaluated with.
A: The degree of yellowing (ΔYI) is less than 5.0 after the heat test, after the moisture test and after the heat cycle test.
D: The yellowing degree (ΔYI) in at least one of the heat resistance test, the humidity resistance test, and the heat cycle test is 5.0 or more.

(4) Haze change evaluation method The haze change (ΔH) after the initial, after the heat resistance test, after the moisture resistance test and after the thermal cycle test of the obtained test piece for evaluation was measured using ISO 13468, ISO 14782, JIS K7361 and JIS K7136. The measurement was performed using a satisfactory haze meter (Murakami Color Research Laboratory, "HM-150"), and evaluation was performed according to the following criteria.
A: The haze change (ΔH) is less than 5.0 after the heat test, after the moisture test and after the heat cycle test.
D: The haze change (ΔH) in at least one of the heat resistance test, the humidity resistance test, and the heat cycle test is 5.0 or more.

(5) Coat layer durability adhesion evaluation method The adhesion of the obtained test piece for evaluation after the initial stage, after the heat resistance test, after the moisture resistance test and after the thermal cycle test was evaluated. Various tests were performed under the same conditions as the measurement of the visible light transmittance.
(Adhesion evaluation method)
The obtained test specimen for evaluation was cut from the surface of the coat layer with a cutter knife until it reached the molding resin, and 100 grids with an interval of 1 mm were made. Adhesive tape (Cellotape (registered trademark), Nichiban Co., Ltd.) is pressure-bonded from the top of the grid, and it is quickly peeled off at an angle of about 60 ° with respect to the surface of the coating layer. The number of eyes was evaluated (based on JIS K5600-5-6 (1999) or ISO 2409 (1992)). The determination method is as follows.
A: No peeling at any of the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test.
B: 1 or more and 5 or less exfoliation in any of the initial stage, after the heat resistance test, after the moisture resistance test and after the heat cycle test.
D: There are 6 or more peels in the initial stage, after the heat resistance test, after the moisture resistance test, and after the heat cycle test.

(6) Evaluation method of blister resistance The initial state of the obtained test piece for evaluation, after the heat resistance test, after the moisture resistance test and after the thermal cycle test, the state of blister generation was confirmed. Various tests were performed under the same conditions as the measurement of the visible light transmittance described above, and the determination was performed as follows.
A: No blisters at the initial stage, after the heat resistance test, after the moisture resistance test and after the heat cycle test.
B: There are no blisters that can be visually confirmed in the initial stage, after the heat resistance test, after the moisture resistance test, and after the heat cycle test.
C: In at least one of the initial stage, after the heat resistance test, after the moisture resistance test and after the thermal cycle test, there are 3 or less blisters that can be visually confirmed within a 100 mm square.
D: At least one after the heat resistance test, after the heat resistance test, and after the heat cycle test, there are four or more blisters that can be visually confirmed within a 100 mm square.

(7) 180 ° Peel Strength Evaluation Method for Transparent Plastic of Adhesive The 180 ° peel strength of the obtained test piece for evaluation was measured after the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test. Various tests were performed under the same conditions as the measurement of the visible light transmittance described above, and the determination was performed as follows.
A test piece for evaluation was attached to a peel tester “SHIMAZU EZ-S” (Shimadzu Corporation), and the peel strength at 180 ° peel was measured.
A: The strength is 5 to 40 N / 25 mm in the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test, and within a range of ± 5% of the initial strength.
B: The strength is 5 to 40 N / 25 mm in the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test, and within a range of ± 10% of the initial strength.
C: The strength is 5 to 40 N / 25 mm in the initial stage, after the heat resistance test, after the moisture resistance test, and after the thermal cycle test, and within a range of ± 15% of the initial strength.
D: The strength in at least one of the initial stage, the heat resistance test, the moisture resistance test, and the thermal cycle test is not in the range of 5 to 40 N / 25 mm.

(8) Evaluation method of wear resistance The wear resistance of the test specimen for evaluation was evaluated according to ASTM D1044. First, the test specimen for evaluation was cut into a 100 mm square. A Taber abrasion test was conducted with a load of 500 g using CS-10F (Calibrase) as an abrasion wheel. The difference ΔH between the haze after the Taber abrasion and the haze before the Taber abrasion test was measured and evaluated as abrasion resistance. The wear wheel was refaced at 25 revolutions using an ST-11 Refacing stone. Each haze value can be calculated by the following formula.
Haze value = Td / Tt × 100
(Here, Td indicates the scattered light transmittance, and Tt indicates the visible light transmittance.)
The visible light transmittance Tt is measured by (2) above. The determination method is as follows.
A: ΔH after 1000 revolutions is 5 or less, and ΔH after 500 revolutions is 3 or less.
B: ΔH after 1000 revolutions is greater than 5 and 10 or less.
C: ΔH after 500 rotations is greater than 3 and less than 10.
D: ΔH after 500 rotations is 10 or more.

(9) Chemical resistance evaluation method A chemical resistance test was performed on acetone, toluene, 2-propanol (IPA), 3% sodium hydroxide, 3% sulfuric acid and 3% albumin. Each of these solutions was dropped on the coating layer of the test specimen for evaluation and allowed to stand for 4 hours. Thereafter, the solution was washed away with tap water, the dropping surface was wiped off, and it was visually confirmed whether there was any abnormality in appearance. The evaluation criteria were as follows.
A: No change in appearance.
D: Dissolution, peeling, cracking, clouding, etc.

(10) Weather resistance evaluation method The test piece for evaluation was cut into a size of 75 mm x 100 mm, chamfered, washed with IPA and pure water, and the end was covered with aluminum tape. Next, the cut test piece was put into a strong energy xenon weather meter XEL-1WN (Suga Test Instruments Co., Ltd.) and operated with a cycle of irradiation intensity of 180 W / m ² , watering for 18 minutes and no watering for 102 minutes. . The test specimen for evaluation was taken out at regular intervals, and confirmation of adhesion and appearance change of each layer was performed over 1000 hours.

By observing the appearance change of the test specimen for evaluation (base film, yellowing degree of coat layer, haze, crack of coat layer, etc.), adhesion of coat layer and 180 ° peel strength of adhesive, weather resistance Evaluated. The evaluation criteria were as follows.
A: Yellowing degree (ΔYI), haze change (ΔH) and visible light transmittance change (ΔTt) after 1000 hours are less than 5, and appearance abnormality such as cracks in the coating layer is not observed. There is no peeling in the adhesion test, and the strength of the adhesive is 5 to 40 N / 25 mm, and is within a range of ± 10% of the initial strength.
D: Before 1000 hours elapse, any of yellowing degree (ΔYI), haze change (ΔH), and visible light transmittance change (ΔTt) exceeds 5, or an appearance abnormality such as a crack in the coating layer is observed. Or peeling is observed in the adhesion test of the coating layer, the strength of the adhesive is not 5 to 40 N / 25 mm, or the strength of the adhesive is not within the range of ± 10% of the initial strength.

(11) Evaluation method of antifouling property As an index of antifouling property, the contact angle of water and the repellency and wiping property of magic ink were evaluated by the following methods.

(11-1) Method for evaluating water contact angle The water contact angle was measured, and the evaluation criteria were as follows.
A: It is 100 degrees or more.
B: 95 ° or more and less than 100 °.
C: 90 ° or more and less than 95 °.
D: It is less than 90 degrees.

(11-2) Evaluation method of repellent property and wiping property of magic ink With “Mackey MO-150-MC-BK” (Zebra Co., Ltd.), which is a magic ink, 30 mm is applied to the surface of the coating layer of the test piece for evaluation. I wrote three lines. The repellency of the magic ink was confirmed and left for 3 minutes. Thereafter, the surface of the coating layer was rubbed 30 times with a waste cloth, and then the wiping property was confirmed. The judgment criteria were as follows.
A: Magic ink is repelled and lines cannot be written, and magic ink can be wiped off by 30 reciprocating rubbing.
B: A line can be written or magic ink cannot be wiped off even after 30 reciprocating rubs.
D: A line can be written and the magic ink cannot be wiped even after 30 reciprocating rubs.

  The glass maintenance protective films of Examples 1 to 8 in the present invention were excellent in various durability and excellent in antifouling properties, transparency, appearance and the like. Moreover, even when bonded to a resin substrate, no blister due to outgas or the like was generated, and the 180 ° peel strength did not change over a long period of time, so that it had a sufficient function as a maintenance protective film for glass.

  On the other hand, as shown in Comparative Examples 1 to 9, sufficient performance is obtained when any of the components A to E of the photocurable resin composition in the present invention is missing or outside the specified range. It was not obtained.

  In Comparative Example 1 that does not contain polymerizable silica particles and Comparative Example 2 in which the content of polymerizable silica particles is less than the specified range, sufficient wear resistance cannot be obtained, and the content of polymerizable silica particles is specified. In Comparative Example 3 and Comparative Example 4 exceeding the range, the adhesion durability of the coat layer was not sufficiently obtained.

  When a photocurable compound other than that is used instead of the photocurable compound having a fluorine atom in the molecule (Comparative Example 9), or when no photocurable compound having a fluorine atom is contained in the molecule (Comparative Example 5) ) And when the content of the photocurable compound having a fluorine atom in the molecule is less than the specified range (Comparative Example 6), sufficient performance was not obtained. Similarly, sufficient performance was not obtained in Comparative Examples 7 and 8 in which the content of the photocurable compound having a fluorine atom in the molecule exceeded the specified range.

1 base film 2 coat layer 3 adhesive layer 4 releasable film

Claims (10)

A base film containing a transparent resin, a coat layer provided on one side of the base film, and an adhesive layer provided on the surface of the base film opposite to the side on which the coat layer is provided,
The coat layer is
(A) an aliphatic urethane (meth) acrylate;
(B) polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm;
(C) a photocurable compound having a fluorine atom in the molecule;
(D) a (meth) acrylate compound;
(E) a photopolymerization initiator, and a cured product of a photocurable resin composition,
The content of the (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of the (A) to (E) in the photocurable resin composition, and the (C) molecule The maintenance protective film for glass whose content rate of the photocurable compound which has a fluorine atom in it is 0.1 mass%-5.0 mass%.   The glass protective protective film according to claim 1, wherein the photocurable resin composition further comprises an ultraviolet absorber and a light stabilizer.   The maintenance protective film for glass according to claim 1 or 2, wherein the thickness of the base film is in the range of 30 µm to 300 µm, and the thickness of the coat layer is in the range of 3 µm to 50 µm.   The 180 degree peel strength with respect to glass is 5N / 25mm-40N / 25mm, The maintenance protection film for glass of any one of Claims 1-3.   The glass according to any one of claims 1 to 4, wherein the adhesive layer includes a copolymer including a structural unit derived from (meth) acrylic acid ester and a structural unit derived from (meth) acrylamide. Maintenance protection film. Further comprising a releasable film on the adhesive layer,
The glass protective protective film according to any one of claims 1 to 5, wherein a 180 ° peel strength between the release film and the adhesive layer is 0.3 N / 25 mm to 3.0 N / 25 mm. . Including a step of providing a coat layer on one side of a base film containing a transparent resin, and a step of providing an adhesive layer on the surface of the base film opposite to the side on which the coat layer is provided,
The coat layer is
(A) an aliphatic urethane (meth) acrylate;
(B) polymerizable silica particles modified with a (meth) acryloyl group and having a volume average particle diameter of 10 nm to 600 nm;
(C) a photocurable compound having a fluorine atom in the molecule;
(D) a (meth) acrylate compound;
(E) a photopolymerization initiator, and a cured product of a photocurable resin composition,
The content of the (B) polymerizable silica particles is 5% by mass to 45% by mass with respect to the total amount of the (A) to (E) in the photocurable resin composition, and the (C) molecule The manufacturing method of the maintenance protective film for glass whose content rate of the photocurable compound which has a fluorine atom in it is 0.1 mass%-5.0 mass%. The process for protecting the glass by applying the glass maintenance protective film according to any one of claims 1 to 6 on the glass surface, and the glass maintenance protective film from the glass surface at an arbitrary time. The process of peeling and protecting the said glass by affixing the maintenance protection film for glass of any one of Claims 1-6 on the said glass surface newly,
Including glass maintenance protection method.   The manufacturing method of the glass with a maintenance protective film including the process of bonding the maintenance protective film for glass of any one of Claims 1-6 on the glass surface.   A glass with a maintenance protective film produced by the production method according to claim 9.