JP5594476B2 - Laminated body, touch panel and composition - Google Patents

Description

  The present invention relates to a laminate, a touch panel, and a composition.

  Conventionally, in glass bodies such as display device screen glass panels, solar cell panels, window glass, automotive glass, and optical glass, various functions are applied to the glass body by forming a film or layer on the surface. The technology to grant is known.

  An example of such a technique is a coating for preventing scratches on the glass surface and a coating for preventing glass contamination, and the films formed on the glass surface are collectively referred to as protective films. Yes. This type of protective film is required to have performance such as transparency, hardness, adhesion to glass, and ease of molding.

  In response to such a request, for example, in Patent Document 1, a silane coupling agent is used in a composition for coating and curing to form a protective film, thereby improving the adhesion between the protective film and glass. Attempts have been disclosed. In addition, for example, Patent Document 2 discloses an attempt to improve the antireflection ability, adhesion to glass, and the like by forming a protective film of glass with an inorganic oxide fine particle-containing composition containing a cyclic monofunctional compound. ing.

JP 2004-285119 A Special table 2010-085937

  However, the protective film formed of the inorganic oxide fine particle-containing composition containing a cyclic monofunctional compound has insufficient crosslink density and has insufficient hardness depending on the application. Moreover, in order to form a protective film having high adhesion to glass using a silane coupling agent, it takes a long time or heat treatment to react the silane coupling agent with the glass surface. Productivity was not always good.

  In recent years, there has been an increasing demand for devices in which information is input by bringing a person's finger or instrument into contact with a screen of a display device called a touch panel. In addition to the traditional performance requirements, the protective film on the surface of this touch panel makes it easy to wipe off the attached fingerprint, and makes it difficult to see the fingerprint when it is attached (hereinafter referred to as fingerprint Performance such as low visibility (sometimes referred to as low visibility) is required.

  The inventors can satisfy the performance required for the touch panel by improving the adhesion of the protective film to the glass, increasing the hardness of the protective film, and containing the specific surface active component in the protective film. As a result, the present invention has been accomplished.

  The present invention has been made in view of the above-described problems, and one of the objects according to some aspects thereof is protection with good adhesion to glass and hardness, and low fingerprint visibility. It is providing the laminated body in which the film | membrane was formed, a touchscreen, and the composition for forming this protective film.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the laminate according to the present invention includes a glass substrate and a protective film formed on the glass substrate, and the protective film includes (A) a cyclic structure and a plurality of (meth) acryloyl groups. And (B) a phosphoric acid ester compound having a (meth) acryloyl group, and (C) a fatty acid ester having an HLB value of 2 or more and 15 or less.

[Application Example 2]
In Application Example 1, the component (C) may have an ethylenic double bond.

[Application Example 3]
In Application Example 1 or Application Example 2, the composition may further include (D) inorganic oxide particles having a number average particle diameter of 1 nm to 100 nm.

[Application Example 4]
One aspect of the touch panel according to the present invention includes the laminate described in any one of Application Examples 1 to 3.

[Application Example 5]
In one embodiment of the composition according to the present invention, (A) a compound having a cyclic structure and a plurality of (meth) acryloyl groups, (B) a phosphate ester compound having a (meth) acryloyl group, and (C) an HLB value is 2 to 15 fatty acid esters.

[Application Example 6]
In Application Example 5, the component (C) may have an ethylenic double bond.

[Application Example 7]
In Application Example 5 or Application Example 6,
Further, (D) inorganic oxide particles having a number average particle diameter of 1 nm to 100 nm may be contained.

  The laminate according to the present invention comprises, on a glass substrate, (A) a compound having a cyclic structure and a plurality of (meth) acryloyl groups, (B) a phosphate ester compound having (meth) acryloyl groups, and (C). A protective film is formed of a composition containing a fatty acid ester having an HLB value of 2 or more and 15 or less. The protective film has good adhesion to glass and hardness. Thereby, when a fingerprint adheres with respect to a laminated body, the low visibility of a fingerprint can be expressed. Furthermore, the laminated body concerning this invention can wipe off a fingerprint easily, when a fingerprint adheres. Since the touch panel according to the present invention includes the laminate, when the fingerprint is attached to the touch panel, low visibility of the fingerprint is exhibited, and when the fingerprint is attached, the fingerprint can be easily wiped off. Can be done. The composition according to the present invention can easily form a protective film having good adhesion and hardness on glass.

The schematic diagram of the cross section of the laminated body concerning embodiment.

  Embodiments of the present invention will be described below. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention. Note that not all the configurations described in the following embodiments are indispensable configurations of the present invention.

1. Laminated body The laminated body 10 of this embodiment includes the glass substrate 1 and the protective film 2. Drawing 1 is a mimetic diagram of the section of layered product 10 concerning an embodiment.

1.1. Glass substrate The glass substrate 1 is a substrate that serves as a base of the laminate 10. The glass substrate 1 can have shapes, such as flat form and a sheet form, for example. Although the flat glass substrate 1 is illustrated in FIG. 1, the shape of the glass substrate 1 is not limited at all. The thickness of the glass substrate 1 when making the glass substrate 1 into flat form can be 10 micrometers or more and 10 mm or less, for example.

  The glass substrate 1 may be transparent or opaque. When the laminated body 10 is used for a display device or a touch panel, the glass substrate 1 preferably has transparency. Moreover, the glass substrate 1 may be laminated with a plurality of layers. Further, a transistor (for example, TFT), a wiring layer, or the like may be formed on the glass substrate 1.

  It does not specifically limit as a material of the glass substrate 1, Boron, sodium, potassium, lead, aluminum, phosphorus, etc. may contain. Examples of such materials include quartz glass, silicate glass, borosilicate glass, soda glass, soda lime glass, potassium glass, lead glass, and the like. The glass substrate 1 may be a laminate of a plurality of layers.

2. Protective film 2.1. Configuration of Protective Film The protective film 2 is provided in contact with the surface of the glass substrate 1. The protective film 2 may be provided in contact with the entire glass substrate 1 or may be provided on a part of the glass substrate 1. In the example of FIG. 1, it is formed in contact with one surface of a flat glass substrate 1. The planar shape of the protective film 2 is not limited at all. For example, when the laminated body 10 is used for a touch panel, the protective film 2 may be formed only at a portion where a human finger or the like contacts the laminated body 10. Moreover, the protective film 2 may be patterned by a general method as needed.

  Although the thickness of the protective film 2 is not specifically limited, For example, it is 10 nm or more and 500 micrometers or less. When the thickness of the protective film 2 is within the above range, sufficient adhesion to the glass substrate 1, sufficient hardness, and low fingerprint visibility can be more effectively expressed. The protective film 2 may be transparent or opaque, but when the laminate 10 is used for a display device, a touch panel, a window glass, or the like, the protective film 2 preferably has transparency.

  As a function of the protective film 2, it is formed on the surface of the glass, for example, makes it difficult to see a fingerprint (including sebum) when a human finger comes in contact, and ease of wiping when the fingerprint is wiped off For example.

2.2. Material of Protective Film Protective film 2 includes (A) a cyclic structure and a compound having a plurality of (meth) acryloyl groups, (B) a phosphate ester compound having (meth) acryloyl groups, and (C) an HLB value of 2 or more. It is formed by curing a composition containing 15 or less fatty acid esters. Hereinafter, the composition will be described.

2.2.1. Composition 2.2.1.1. (A) component The composition which forms the protective film 2 contains the compound which has a cyclic structure and several (meth) acryloyl group as (A) component.

  As used herein, the term “cyclic structure” means a cycloalkane ring such as a cyclohexane ring or cyclooctane ring, an aromatic ring such as a benzene ring or a naphthalene ring, a bicyclo ring such as a bornene ring, or a hetero atom in these ring members. It refers to the included rings, as well as the polycyclic systems of these rings, and the assembly of two or more of these rings. The cyclic structure may include a side chain.

The term “(meth) acryloyl group” as used herein refers to an acryloyl group (CH ₂ ═CH—CO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) —CO—).

  The component (A) is an organic compound having two or more (meth) acryloyl groups in the molecule and a cyclic structure. The component (A) is, for example, a compound represented by the following formula (1).

[In Formula (1), R ¹ represents each independently a monovalent group having a (meth) acryloyl group, R ² represents a divalent group having a cyclic structure, U represents NH, O ( Oxygen atom) or S (sulfur atom), and V represents O or S. ]
One of the functions of the component (A) is to reduce curl while maintaining the hardness of the protective film 2. Since the protective film 2 has a cyclic structure in the component (A), the distance between the cross-linking points is increased, and a conformational restriction is formed between the cross-linking points, thereby reducing curling. It is considered to be done. In addition, when the compound represented by the above formula (1) has an aromatic ring as a cyclic structure, it may have crystallinity. In that case, even if the distance between cross-linking points is increased, the hardness and It is considered that the balance of the above can be maintained and the mechanical strength and toughness of the protective film 2 can be improved.

In the formula (1), the cyclic structure contained in R ² is not particularly limited, but is a condensed benzene ring such as an aliphatic ring, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring, pyrene ring, thiophene ring, etc. , Heteroaromatic rings such as pyrrole ring, furan ring and pyridine ring are preferred.

The component (A) preferably has a molecular weight of 400 or less, more preferably 300 or less, of the group represented by R ² per (meth) acryloyl group of the group represented by R ¹ in the formula (1). It is. By being 400 or less, the scratch resistance of the protective film 2 can be improved.

  The component (A) can be obtained, for example, by stirring a diisocyanate having a cyclic structure and a (meth) acrylic compound having a hydroxyl group in the presence of a suitable urethanization catalyst, for example, at 60 ° C. for 6 hours. it can.

  Here, specific examples of the diisocyanate having a cyclic structure include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'- Examples include biphenylene diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diacrylate. Of these, 2,4-tolylene diisocyanate and isophorone diacrylate are particularly preferable.

  Specific examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl. (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane Di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraethylene glycol mono ( Acrylate), polyethylene glycol mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis (hydroxymethyl) tricyclodecane mono (meth) acrylate, bisphenol A polyethylene oxide or propylene oxide (Meth) acrylate was added to mono (meth) acrylate of diol as an adduct, mono (meth) acrylate of diol as an adduct of hydrogenated bisphenol A ethylene oxide or propylene oxide, and diglycidyl ether of bisphenol A An epoxy (meth) acrylate etc. can be mentioned.

  Furthermore, specific examples of the (meth) acrylic compound having a hydroxyl group include the following formula (2) or the following formula (3).

[In the formula (2), ^{R 3} represents a hydrogen atom or a methyl group, n is a number of 1 to 15. In formula (3), R ⁴ represents a hydrogen atom or a methyl group. ]
And a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate with (meth) acrylic acid.

Among these hydroxyl group-containing (meth) acrylates, in particular, pentaerythritol tri (
(Meth) acrylate is preferred.

  Specific examples of the urethanization catalyst are usually copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7- And trimethyl-1,4-diazabicyclo [2.2.2] octane. Of these, dibutyltin dilaurate is particularly preferred.

  (A) As a still more preferable aspect of a component, it is a compound represented by following formula (4) or following formula (5).

[In the formula (5), “Acryl” represents an acryloyl group. ]
The content of the component (A) in the composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass, with the total amount of the components excluding the solvent being 100% by mass. . When the content of the component (A) is within the above range, for example, the viscosity of the composition suitable for application to the glass substrate 1 can be obtained.

2.2.1.2. (B) Component The composition forming the protective film 2 contains a phosphate ester compound having a (meth) acryloyl group as the (B) component.

The (meth) acryloyl group of the component (B) is the same as that defined in the section “2.2.1.1. (A) component” above. The phosphate ester compound is a compound having a structure in which phosphoric acid (H ₃ PO ₄ ) (orthophosphoric acid) and a hydroxyl group of an organic compound are dehydrated and condensed. The phosphate ester compound of component (B) may be either a monoester or a diester.

  The organic compound that forms an ester with phosphoric acid is not particularly limited as long as it has a (meth) acryloyl group and a hydroxyl group. For example, at least one of the hydroxyl groups of a compound having a plurality of hydroxyl groups is (meth) acrylic acid and The thing which formed the ester bond is mentioned. Such an organic compound can be used as the component (B) by forming an ester bond between another hydroxyl group and phosphoric acid.

  Specific examples of the compound in which one hydroxyl group of the diol compound forms an ester bond with (meth) acrylic acid include the “hydroxyl group” exemplified in the section “2.2.1.1. Component (A)” ( And (meth) acrylic compounds ”. Moreover, as a more preferable compound of (B) component, the compound shown by following formula (6) can be illustrated.

In Formula (6), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, r represents an integer of 1 to 15, R ⁷ represents a hydroxyl group, or A in Formula (6). Represents a group.

  Specific examples of the compound represented by the above formula (6) include 2-((meth) acryloyloxy) ethyl phosphate (also known as: (2-hydroxyethyl) (meth) acrylate / acid phosphate, or ethylene glycol 1 -(Meth) acrylate 2-phosphate), 2-((meth) acryloyloxy) propyl phosphate, 2-((meth) acryloyloxy) butyl phosphate, 2-((meth) acryloyloxy) hexyl phosphate, bis (2-methacryloyloxyethyl) acid phosphate, bis (2-methacryloyloxypropyl) acid phosphate, bis (2-methacryloyloxybutyl) acid phosphate, bis (2-methacryloyloxyhexyl) acid phosphate, etc. It is done.

  Examples of these commercially available products include light esters P-1M and P-2M (manufactured by Kyoeisha Chemical Co., Ltd.).

  One of the functions of the component (B) is to improve the adhesion of the protective film 2 to the glass substrate 1. Since the protective film 2 has a structure derived from phosphoric acid in the component (B), the affinity of the interface between the protective film 2 and the glass substrate 1 is increased, and the adhesion can be improved. . Therefore, for example, when the protective film 2 has shrinkage strain (shrinkage stress), it is possible to restrain the strain (stress) and to suppress problems such as interface peeling.

  The content of the component (B) in the composition is preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 5% by mass, with the total amount of the components excluding the solvent being 100% by mass. . (B) When content of a component exists in the said range, the adhesiveness between the protective film 2 and the glass substrate 1 can fully be enlarged.

2.2.1.3. Component (C) The composition forming the protective film 2 contains a fatty acid ester having an HLB value of 2 or more and 15 or less as the component (C).

  Here, the HLB (Hydrophile-Lipophile Balance) value indicates the degree of hydrophilicity or lipophilicity. The HLB value can be obtained by the following calculation formula.

HLB = 7 + 11.7Log (M _W / M _O )
Here M _W is the molecular weight of the hydrophilic groups, M _O is the molecular weight of the lipophilic group. M _W + M _O = M (molecular weight of component (C)).

  One of the effects obtained by including the component (C) in the composition is to make the fingerprint attached to the protective film 2 less visible and improve the wiping property of the fingerprint. Here, the difficulty of conspicuous fingerprints when a fingerprint or the like is attached may hereinafter be referred to as low visibility of the fingerprints (Low Visibility). “Low fingerprint visibility” means difficulty in viewing with the naked eye when a fingerprint (sebum) is attached to the surface of the protective film 2.

  The HLB value of the fatty acid ester (C) is in the range of 2-15. Moreover, it is more preferable that the HLB value of the fatty acid ester of the component (C) is in the range of 2-4. By setting the HLB value within the above range, it is possible to sufficiently exhibit low fingerprint visibility and fingerprint wiping.

  (C) As a component, the fatty acid ester of glycerol is mentioned, As long as the HLB value is the said range, any of a monoglyceride, a diglyceride, and a triglyceride may be sufficient. The HLB value of the fatty acid ester is, for example, adjusting the molecular weight of the hydrophilic group and the hydrophobic group, introducing a hydrophilic group such as a hydroxyl group or a carboxyl group, or selecting a fatty acid having a hydroxyl group. It can be adjusted by an appropriate method.

  The fatty acid ester of component (C) can be classified as a nonionic surfactant, and hereinafter, this may be referred to as “fatty acid ester surfactant”.

  Further, the fatty acid ester preferably contains a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms. When the fatty acid ester has a hydrocarbon group having 6 to 30 carbon atoms, the low visibility of fingerprints and the wipeability of fingerprints of the cured film (protective film 2) obtained can be further improved.

  Fatty acids that esterify with glycerin include unsaturated fatty acids such as ricinoleic acid, oleic acid, and linoleic acid, and saturated fatty acids such as palmitic acid and stearic acid. In the case of diglycerides and triglycerides, different fatty acids are esterified. May be. Furthermore, the fatty acid that forms an ester bond with glycerin is not limited to a so-called higher fatty acid, and may be a lower fatty acid such as acetic acid (which becomes acetylglyceride) or propionic acid.

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

  The fatty acid ester of component (C) preferably further has a (meth) acryloyl group as an ethylenically unsaturated bond. In this case, the HLB value of the fatty acid ester of the component (C) is calculated including the (meth) acryloyl group.

  When the fatty acid ester of the component (C) has a (meth) acryloyl group, the (A) component and the component (B) contained in the composition have a (meth) acryloyl group when the composition is cured. A bond can be formed between Thereby, since (C) component is fixed in hardened | cured material, durability of the protective film 2 can be improved.

  In the case where the component (C) has a (meth) acryloyl group, the compatibility with other components is improved. Therefore, compared with the case where the component (C) does not have a (meth) acryloyl group, A large amount of component (C) can be blended. for that reason. Even with spray coating, the component (C) can be present on the surface of the coating film, and the low visibility of fingerprints and the ability to wipe off fingerprints, which are one of the effects of the present invention, can be easily expressed. It becomes.

  In the case of adding a (meth) acryloyl group to the fatty acid ester of the component (C), for example, it can be synthesized as follows. In this case, for example, it is obtained by reacting an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group at a ratio such that the HLB after the reaction is 2 to 7 with respect to the surfactant having a hydroxyl group. Can do. For example, when a fatty acid ester having three hydroxyl groups is used as a raw material, when the HLB of the fatty acid ester of the raw material is 5, an isocyanate compound having a (meth) acryloyl group of 1/3 molar equivalent of the hydroxyl group or (meth) Acrylic acid may be simply reacted. When the HLB of the starting fatty acid ester is 9, it is preferable to react an isocyanate compound or (meth) acrylic acid having an equimolar equivalent of a (meth) acryloyl group of a hydroxyl group.

  Furthermore, as a method for imparting a (meth) acryloyl group to the fatty acid ester of the component (C), for example, a fatty acid having a hydroxyl group is selected at the fatty acid site of the fatty acid ester, and the hydroxyl group is converted to a (meth) acryloyl group. A method is mentioned. More specifically, the component (C) can be obtained by reacting the hydroxyl group of the fatty acid ester surfactant with a compound having a (meth) acryloyl group. Examples of such a reaction include reacting a compound having an isocyanate group and a (meth) acryloyl group with a fatty acid ester surfactant having a hydroxyl group. By using such a compound, the hydroxyl group of the fatty acid ester surfactant and the isocyanate group react to form a urethane bond, whereby a (meth) acryloyl group is introduced.

  Specific examples of the compound having an isocyanate group and a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl]. Examples thereof include ethyl isocyanate. Moreover, the compound which has a hydroxyl group and a (meth) acryloyl group can be made to react with a diisocyanate compound, and the compound which has an isocyanate group and a (meth) acryloyl group can also be obtained. Examples of such diisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

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

  Specific examples of the component (C) having a (meth) acryloyl group (fatty acid ester having an HLB value of 2 or more and 15 or less) include compounds having a structure represented by the following formula (7).

In formula (7), the meaning of each symbol is as follows. X represents an optionally substituted (m ¹ + m ² ) -valent hydrocarbon group having 3 to 10 carbon atoms. A plurality of Y ¹ and Y ² each independently represent a divalent group or a single bond containing an ether bond, an ester bond, or a urethane bond, and at least one of Y ¹ and Y ² has a structure derived from a fatty acid. . Z represents a group having one or more (meth) acryloyl groups. A plurality of R ⁸ and R ⁹ each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms. m ¹ and m ² are each an integer of 0 to 10, and n ¹ and n ² are each independently an integer of 0 to 20. However, m ¹ and m ² are not 0 at the same time.

  Specific examples of the component (C) having a (meth) acryloyl group include compounds represented by the following formula (8).

In formula (8), each R ¹⁰ is independently a hydrogen atom or a group represented by the following formula (9). a + b + c = 7.

  Furthermore, other specific examples of the component (C) having a (meth) acryloyl group include compounds represented by the following formula (10).

In formula (10), R ¹¹ is each independently a hydrogen atom or a group represented by the following formula (11). a + b + c = 7.

  The content of the component (C) in the composition is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 1 to 15% by mass, with the total amount of the components excluding the solvent being 100% by mass. It is. When the content of the component (C) is within the above range, it is possible to impart a fingerprint wiping property to the obtained protective film and to obtain a highly transparent protective film. In addition, when content of (C) component shall be 5 mass% or more, it is preferable to use the compound which has a (meth) acryloyl group as (C) component.

2.2.1.4. Other Components (D) Inorganic Oxide Particles The composition forming the protective film 2 may contain inorganic oxide particles as the component (D).

  Component (D) is a particle mainly composed of an oxide, and from the viewpoint of colorlessness of the protective film 2 of the resulting cured product, silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, Particles mainly containing an oxide of at least one element selected from the group consisting of antimony and cerium are preferred.

  Examples of these oxide particles include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can do. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more.

  Furthermore, the oxide particles may be used as a powder or a solvent-dispersed sol. When used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the oxide particles may be appropriately selected according to the use of the protective film 2 to be formed, but is preferably 1 nm to 100 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 80 nm.

  If the number average particle diameter of the inorganic oxide particles is in the above range, the transparency and the surface state of the protective film 2 can be excellent. Various surfactants and amines may be added to improve the dispersibility of the inorganic oxide particles.

  Commercially available products as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA- manufactured by Nissan Chemical Industries, Ltd. ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Moreover, as an aqueous dispersion product of alumina, Nissan Chemical Industries, Ltd. alumina sol-100, -200, -520; As an alumina isopropanol dispersion product, Sumitomo Osaka Cement Co., Ltd. AS-150I; AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; Nissan Chemical Industries, Ltd. as an aqueous dispersion of zinc antimonate powder ) Cellax: Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powders and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; Antimony-doped tin oxide water dispersion sol is Ishihara Sangyo ( SN-100D, manufactured by Mitsubishi Materials Corp .; cerium oxide The dispersion can be exemplified Taki Chemical Co., Ltd. Nidoraru like.

The inorganic oxide particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, preferably a spherical shape. The specific surface area of the oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g.

  In addition, when mix | blending an inorganic oxide particle with a composition, you may mix | blend, after coat | covering the inorganic oxide particle with the polymer of the organic compound which has polymerizability beforehand. Examples of such an organic compound include those having an ethylenically unsaturated bond ((meth) acryloyl group or the like) among the above-mentioned components (A), (B), and (C), and the following: The compound of this is mentioned.

  Preferable examples of the organic compound that covers the inorganic oxide particles include a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound to be generated include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom and the like are bonded to a silicon atom, but a compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, That is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.

  The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the inorganic oxide particles by a condensation reaction that occurs following a condensation reaction or hydrolysis.

  Preferable specific examples of such a compound include compounds represented by the following formula (12).

In the formula (12), R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ¹² O) _j R ¹³ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ¹⁴ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.

R ¹⁵ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.

R ¹⁶ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.

  K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  The content of the component (D) in the composition is preferably in the range of 0 to 80% by mass, more preferably in the range of 5 to 75% by mass, with the total amount of the components excluding the solvent being 100% by mass. . (D) When content of a component exists in the said range, the hardness of the protective film obtained can be raised.

(E) Radical polymerization initiator In the composition which forms the protective film 2, you may mix | blend (E) radical polymerization initiator.

  Examples of such (E) radical polymerization initiator include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation (light ) Polymerization initiator) and the like can be mentioned, and among these, a radiation (photo) polymerization initiator is preferred.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1- Methyl vinyl) phenyl) propanone) and the like.

  Examples of commercially available radiation (photo) polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, manufactured by BASF. Examples include Lucillin TPO, LR8883, Ubekril P36 manufactured by UCB, Ezacure KIP150, KIP65LT, KIP100F manufactured by Lamberti, KT37, KT55, KTO46, KIP75 / B, and the like.

  The thermal polymerization initiator is not particularly limited as long as it is decomposed by heating and generates radicals to initiate polymerization, and examples thereof include peroxides and azo compounds. Specific examples include benzoyl Examples include peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  In the composition for forming the protective film 2, the blending amount of the (E) radical polymerization initiator used as needed is 0.01 when the total of the components excluding the solvent of the composition is 100% by mass. It is preferable to be in the range of ˜20 mass%, and it is more preferable to be in the range of 0.1 to 10 mass%.

(F) Organic solvent The composition for forming the protective film 2 can be diluted with an organic solvent for the purpose of adjusting the thickness of the protective film 2 or the like. Since the viscosity of the composition can be adjusted with an organic solvent, the thickness of the protective film 2 can be adjusted. The viscosity of the composition to be adjusted by adding an organic solvent to the composition is, for example, 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec. / 25 ° C.

  Examples of the organic solvent (F) include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, Esters such as γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

  In the composition for forming the protective film 2, the blending amount of the organic solvent (F) used as necessary is 50 to 10,000% by mass when the total of components excluding the solvent is 100% by mass. It is preferable to be within the range. The blending amount of the organic solvent can be appropriately determined in consideration of the viscosity of the composition.

(G) Polyfunctional polymerizable compound The composition for forming the protective film 2 contains, as necessary, a polyfunctional polymerizable compound having two or more (meth) acryloyl groups as the component (G). You may mix | blend. Hereinafter, the component (G) is also referred to as “polyfunctional (meth) acrylate compound (G)”. One effect of blending the component (G) is to improve the strength of the protective film 2. Moreover, it is preferable that (G) component has 3 or more (meth) acryloyl groups from a viewpoint of the film forming property of a composition, and the hardness of hardened | cured material.

  Specific examples of polyfunctional polymerizable compounds include (meth) acrylic esters such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Opentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meta) ) Acrylates, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meta ) Acrylates and oligoepoxy (meth) acrylates. Among them, dipentaerythritol hexa (meth) acrylate (hereinafter also referred to as DPHA), pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate are used because the obtained protective film has high hardness. preferable.

Commercially available products of the polyfunctional (meth) acrylate compound (G) include: Sanwa Chemical Co., Ltd., trade name: Nicalak MX-302, Toagosei Co., Ltd .: trade names: Aronix: M-400, M-402, M-403, M-404, M-408, M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-326, M- 327, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO- 1343, TO-138 , TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd .: Trade name KAYARAD: D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60 , DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR -492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344 SR-349, SR-368, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, G O-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., Ltd .: Trade name: Light acrylate PE-4A, DPE -6A, DTMP-4A, and the like. Said compound can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, as a commercial item of a polyfunctional monomer, for example, Iupimer UV: SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation), Biscoat: # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate: 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA , TMP-A, PE-3A (above, manufactured by Kyoeisha Chemical Co., Ltd.), Aronix: M210, M220, M240, M305, M309, M310, M325, M400 (above, manufactured by Toagosei Co., Ltd.), Lipoxy: VR -77, VR-60, VR-90 (manufactured by Showa Polymer Co., Ltd.) and the like.

  The content of the component (G) in the composition for forming the protective film 2 is preferably 0 to 40% by mass, more preferably 100% by mass based on the total amount of the composition other than the component (E) (organic solvent). Is in the range of 0 to 35% by weight. When the content of the component (G) is within the above range, a composition viscosity suitable for spray coating properties can be obtained, and the scratch resistance and hardness of the protective film 2 can be further improved.

(H) Curable oligomer In the composition for forming the protective film 2, a curable oligomer or polymer may be blended as a component (H) as long as the properties of the composition are not impaired. . Examples of the curable oligomer or polymer include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane polymer having a (meth) acryloyloxy group, and glycidyl methacrylate. Examples thereof include reactive polymers obtained by reacting copolymers with other polymerizable monomers and (meth) acrylic acid.

(I) Monofunctional polymerizable compound In the composition for forming the protective film 2, a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional polymerizable” as component (I), if necessary. Compound ")) may be blended.

  Examples of the component (I) (monofunctional polymerizable compound) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, alicyclic structure-containing (meth) acrylate such as dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso Propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylamino Ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and compounds represented by the following formulas (13) to (16).

(In the formula (13), R ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ¹⁹ represents a hydrogen atom or 1 to 12 carbon atoms. Preferably an alkyl group of 1 to 9 is shown, and m is a number of 0 to 12, preferably 1 to 8.)

(In the formulas (14) and (15), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, and R ²² each independently represents a hydrogen atom. Or a methyl group, and p preferably represents a number of 1 to 4.)

(In the formula, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group, and q represents an integer of 1 to 5.)
Of these monofunctional polymerizable compounds, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, and lauryl acrylate are more preferable.

  These monofunctional polymerizable compounds are commercially available products IBXA (isobornyl acrylate) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-111, M-113, M114, M-117, TO-1210 (above, Available from Toagosei Co., Ltd.).

  When the monofunctional polymerizable compound (I) is contained in the composition for forming the protective film 2, the total amount of the composition other than the organic solvent is 100% by mass, preferably 0 to 10% by mass. More preferably, it is 0-5 mass%. When the composition contains the component (I), the residual stress in the protective film 2 can be reduced. However, if the composition exceeds the above range, the hardness of the protective film 2 may be reduced.

<Other ingredients>
In addition to the above components, the composition for forming the protective film 2 may further include various additives as required, such as sensitizers, antioxidants, ultraviolet absorbers, light stabilizers, and silane couplings. Blending agent, coating surface improver, thermal polymerization inhibitor, leveling agent, surfactant, colorant, storage stabilizer, plasticizer, lubricant, solvent, filler, anti-aging agent, wettability improver, etc. as required May be.

  Here, as the sensitizer, for example, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Examples thereof include ethyl and isoamyl 4-dimethylaminobenzoate. Examples of commercially available products of this sensitizer include Nippon Kayaku Co., Ltd. trade name: KAYACURE: DMBI, EPA, and the like.

  Examples of the antioxidant include Irganox 1010, 1035, 1076, 1222 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Antigen P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), and the like. Examples of the ultraviolet absorber include Tinuvin: P, 234, 320, 326, 327, 328, 329, 213 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 110, 501, 202, 712. 704 (above, manufactured by Sipro Kasei Co., Ltd.) and the like. Examples of the light stabilizer include Tinuvin: 292, 144, 622LD (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (Sankyo (Sankyo)). Manufactured by SumisorbTM-061 (Sumitomo Chemical Co., Ltd.) As the silane coupling agent, for example, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, commercially available products such as SH6062, 6030 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KBE903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of the coating surface improver include dimethylsiloxane polyether and the like. Examples of commercially available products include DC-57, DC-190 (above, manufactured by Dow Corning), SH-28PA, SH-29PA, SH-30PA, SH-190 (above, Toray Dow Corning).・ Silicone Co., Ltd.), KF351, KF352, KF353, KF354 ( Moreover, Shin-Etsu Chemical Co., Ltd.), L-700, L-7002, L-7500, FK-024-90 (or, Nippon Unicar Co., Ltd.).

  The composition for forming the protective film 2 can be produced by mixing the above-mentioned components by a conventional method. Thus, the viscosity of the resin composition of this invention prepared is 200-50,000 mPa * s / 25 degreeC normally, Preferably it is 500-30,000 mPa * s / 25 degreeC. If the viscosity is within this range, uneven coating or undulation may occur, or a target thickness can be easily obtained, and the performance as a protective film can be sufficiently exhibited.

2.2.2. Curing of composition The above-mentioned composition is applied to the glass substrate 1 and can be cured, for example, as follows.

The compositions described above can be heat cured and / or radiation cured. Specifically, the composition is coated on the glass substrate 1, and after the volatile component is dried preferably at 0 to 200 ° C., a curing treatment is performed with heat or / and radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 001 to 10 J / cm ² , more preferably 01 to ² J / cm ² . Further, preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 002 to 030 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad. In the present invention, “radiation” means infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like.

  When the composition is cured, a polymer compound in which at least a part of the (meth) acryloyl group of the compounded compound is condensed is generated in the protective film 2.

2.3. Formation of protective film The protective film 2 is formed, for example, by applying the above composition to a spin coating method, a dip coating method, a roll coating method, a spray coating method, an ink jet method, etc., and then thermosetting and / or radiation curing. can do. Moreover, the protective film 2 can be patterned by a general method as needed.

  The protective film 2 is formed of a cured product obtained by reacting the above composition. That is, the protective film 2 is made of, for example, a polymer (cured product) having a structure in which at least a part of (meth) acryloyl groups contained in the composition is polymerized.

3. Touch Panel The touch panel according to the present embodiment is a device to which information is input when a human finger, an instrument, or the like comes into contact. The touch panel of the present embodiment has the above-described laminated body 10 at a site where a person's finger or instrument comes into contact, and the person's finger or instrument comes into contact with the protective film 2 when information is input. Are arranged as follows.

  In addition, the laminated body 10 of this embodiment is not only suitable for a touch panel, but also has a wide range of uses such as various display devices, window glass for houses and automobiles, other glass panels, and casings in addition to the touch panel. It will be readily understood that this is applicable.

4). Action The laminated body 10 of the present embodiment has, on the glass substrate 1, (A) a compound having a cyclic structure and a plurality of (meth) acryloyl groups, (B) a phosphate ester compound having a (meth) acryloyl group, The protective film 2 is formed by a composition containing (C) a fatty acid ester having an HLB value of 2 or more and 15 or less. The protective film 2 has high hardness and good adhesion to the surface of the glass substrate 1. Thereby, when the fingerprint adheres to the laminated body 10, the low visibility of the fingerprint can be expressed by the action of the protective film 2. Furthermore, since the laminate 10 according to the present embodiment has high hardness of the protective film 2 and high adhesion to glass, the fingerprint can be easily wiped off when the fingerprint is attached. Since the touch panel according to the present embodiment includes the laminated body 10, when the fingerprint is attached to the touch panel, the low visibility of the fingerprint is exhibited, and when the fingerprint is attached, the fingerprint is wiped off. It can be done easily. According to the composition concerning this embodiment, the said protective film 2 with favorable adhesiveness and hardness can be formed easily on glass.

4). Examples and Comparative Examples The laminates of Examples and Comparative Examples were prepared and evaluated as follows.

4.1. Glass substrate Blue plate glass (soda lime glass plate) was used as the glass substrate of each Example and each Comparative Example. The surface of the blue plate glass was used after being washed with pure water and sufficiently dried.

4.2. Protective film In each Example and each comparative example, the protective film was created on the surface of the glass substrate. The composition (solid content concentration 25%) was applied onto the glass substrate using a # 20 bar, and this was placed in an oven at 80 ° C. for 5 minutes for drying. Thereafter, the coating film is irradiated with 350 mW / cm ² and 1000 mJ / cm ² using an electrodeless lamp (H bulb) manufactured by Fusion UV Systems in an air atmosphere, and cured to form a protective film having a film thickness of 6 μm. The laminated body of each Example which has this, and each comparative example was obtained.

4.2.1. Composition The protective film of the laminated body of each Example and each comparative example was created using the following compositions. The composition of the composition used is shown in Table 1. The unit of the formulation described in Table 1 is mass%.

4.2.1.1. Component (A) (compound having a cyclic structure and a plurality of (meth) acryloyl groups)
As the component (A), the following three synthetic products or commercially available products were used.

  (A-1) To a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer, NK ester A-TMM-3LM-N (pentaerythritol tris) manufactured by Shin-Nakamura Chemical It is a mixture of acrylate and pentaerythritol tetraacrylate, and it is only pentaerythritol triacrylate having a hydroxyl group that is involved in the reaction.) After 93 parts were added dropwise at 10 ° C. for 1 hour, The mixture was stirred for 6 hours. Thus, a mixed solution of 75 parts of compound (A-1) (abbreviated as PIP) having a cyclic structure and an acryloyl group and 37 parts of pentaerythritol tetraacrylate was obtained.

  (A-2) 57.1 parts of hydroxyethyl acrylate was added to a solution consisting of 42.8 parts of tolylene diisocyanate and 0.08 part of dibutyltin dilaurate in a container equipped with a stirrer at 10 ° C. for 1 hour. Then, the mixture was stirred at 60 ° C. for 6 hours to obtain a compound (A-2) (abbreviated as HTH) having a cyclic structure and an acryloyl group.

  (A-3) Toagosei Co., Ltd., trade name: Aronix M-315 was used as a compound (A-3) (abbreviated as M315) having a cyclic structure and an acryloyl group. M315 is a mixture of isocyanuric acid EO-modified di and triacrylate.

4.2.2.2. (B) component (phosphate ester compound having a (meth) acryloyl group)
2-((Meth) acryloyloxy) ethyl phosphate (abbreviated as PPME) was purchased from Toho Chemical Co., Ltd. and used as the component (B).

4.2.2.3. (C) component (fatty acid ester whose HLB value is 2-15)
As the component (C), the following three synthetic products or commercially available products were used.

(C-1) To a three-necked flask equipped with a stirrer, 0.030 g of 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT), pentaerythritol triacrylate (Shin Nakamura Chemical) Manufactured, NK ester A-TMM-3LM-N) 21.05 g, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur I) 9.10 g, and methyl isobutyl ketone 50.00 g (Mitsubishi Chemical Co., Ltd.) was charged, and after adding 0.31 g of dioctyltin dilaurate (Kyodo Pharmaceutical Co., Ltd., KS-1200-A), the mixture was stirred at room temperature for 2 hours. Next, 19.52 g of polyoxyethylene hydrogenated castor oil (manufactured by Nippon Emulsion Co., Ltd., EMALEX HC-7; HLB value 6) was added. The reaction solution was heated to 60 ° C. and stirred for 2 hours to obtain compound (C-1). In this reaction, since the acrylation reaction proceeds almost quantitatively, the HLB of the compound (C-1) determined from the charged amount is 3. The compound (C-1) corresponds to a compound having a structure in which R ^{10 of the} compound represented by the formula (8) among the components (C) described in the above embodiment is represented by the formula (9).

(C-2) To a three-necked flask equipped with a stirrer, 0.041 g of 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT), pentaerythritol triacrylate (Shin Nakamura Chemical) NK ester A-TMM-3LM-N) 12.92 g, tolylene diisocyanate 4.82 g, and methyl isobutyl ketone (Mitsubishi Chemical Co., Ltd.) 50 g are charged, and dioctyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., KS). After adding 0.349 g of -1200-A), the mixture was stirred at room temperature for 2 hours. Subsequently, 31.88 g of polyoxyethylene hydrogenated castor oil (Nippon Emulsion, EMALEX HC-5; HLB value 4) was added. The reaction solution was heated to 60 ° C. and stirred for 2 hours to obtain compound (C-2). In this reaction, since the acrylation reaction proceeds almost quantitatively, the HLB of the compound (C-2) obtained from the charged amount is 3. The compound (C-2) corresponds to a compound having a structure in which R ^{11 of the} compound represented by the formula (10) is represented by the formula (11) among the components (C) described in the above embodiment.

4.2.2.4. Other components (D) Component: As the inorganic oxide particles, the following two types (D-1 and D-2) in which the inorganic oxide particles were coated with a polymer of an organic compound having polymerizability were used.

  (D-1) is Toray Dow Corning Z6030 (γ-methacryloxypropyltrimethoxysilane) 0.71 part, silica particle dispersion (MEK solvent, silica concentration 32%, Adeka AT20 solvent-substituted) After stirring a mixed solution of 89.1 parts, 0.12 parts of ion-exchanged water, and 0.01 parts of p-hydroxyphenyl monomethyl ether at 60 ° C. for 4 hours, 1.36 parts of orthoformate methyl ester was added, and Obtained by heating and stirring at 60 ° C. for 1 hour. The average particle diameter of the inorganic oxide particles (D-1) measured with a transmission electron microscope was 13 nm. 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 32.3%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 98%.

  In the production of (D-2), the organic compound to be coated was first synthesized as follows.

To a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate in dry air, 60.0 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour, and then at 70 ° C. The mixture was heated and stirred for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is pentaerythritol having a hydroxyl group that is involved in the reaction. (Only triacrylate.) After dropping 202.0 parts at 30 ° C. over 1 hour, the mixture was heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Db) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was not more than 01%, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto groups in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. Thus, 285 parts of a compound (including 80.8 parts of pentaerythritol tetraacrylate which was not involved in the reaction) for synthesizing the inorganic oxide particles was synthesized.

  8.7 parts of the obtained compound (Db), methyl ethyl ketone (MEK) silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number average particle diameter 22 nm, silica concentration 30%)) 91.3 Parts of solid (27.4 parts solids), 0.2 parts of isopropanol and 0.1 parts of ion-exchanged water were stirred at 80 ° C. for 3 hours, and then 1.4 parts of orthoformate methyl ester was added. A dispersion of colorless and transparent inorganic oxide particles (D-2) was obtained by heating and stirring at the same temperature for 1 hour. 2 g of the dispersion was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 35% by mass. The average particle diameter of the inorganic oxide particles (D-2) covered with the polymer of the organic compound having polymerizability was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

  As the polymerization initiator (E) component, IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone manufactured by BASF Corporation was used.

  As the polyfunctional polymerizable compound, KAYARAD DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. was used.

  As the monofunctional polymerizable compound, IBXA: isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was used.

  As the organic solvent, methyl isobutyl ketone (MIBK) and propylene glycol monomethyl ether acetate (PGMEA) purchased as reagents were used.

4.3. Evaluation method 4.3.1. Cross-cut test Put a 5mm square cross-cut with a cutter knife on the surface on which the protective film of the laminate of each Example and each Comparative Example was formed, and attach the Nichiban cellophane tape and peel it off. It was investigated whether it adhered, and in Table 1, what did not peel was described as favorable, and what produced peeling was described as defect.

4.3.2. Fingerprint Low Visibility Evaluation was performed by attaching an evaluator's fingerprint to the surface on which the protective film of the laminate of each Example and each Comparative Example was formed. For each sample, the evaluator's finger was washed with soap for each sample, and then the hand cream was applied under the same conditions before the fingerprint was attached. The attached fingerprint was evaluated by visual observation and listed in Table 1 as ◯ when it was hardly visible, Δ when it was thinly visible, and x when it was clearly confirmed.

4.3.3. Fingerprint wipeability Fingerprint wipeability was evaluated as the wipeability of a fingerprint attached. A fingerprint is attached to the surface of the laminate of each Example and each Comparative Example on which the protective film is formed, and the evaluator's hand wipes it with a tissue paper 5 times. The defects are listed in Table 1.

4.3.4. Hardness test The hardness of the protective film was determined by a scratch test using a pencil in accordance with JIS K5600-5-4. Measurements were performed on the protective films of the laminates of each Example and each Comparative Example with a pencil of H to 4H and a weight of 750 gf. The results are shown in Table 1.

4.4. Evaluation result When Table 1 is seen, in the laminated body of each Example in which the protective film was formed with the composition containing (A) component, (B) component, and (C) component, adhesiveness and low visibility of fingerprint Good results were obtained for all of the fingerprint wiping property and the hardness of the protective film. On the other hand, in the laminates of Comparative Examples 1 and 2 in which the protective film was formed by the composition containing no component (B), the adhesion was insufficient. Moreover, in the laminated body of the comparative example 3 in which the protective film was formed with the composition which does not contain (C) component, the low visibility and wiping property of a fingerprint, and the hardness of the protective film were inadequate. Furthermore, in the laminated body of the comparative example 4 in which the protective film was formed with the composition containing no component (A), the hardness of the protective film was insufficient.

The composition of Example 1 was applied to the glass substrate with a spray coating machine, and this was placed in an oven at 80 ° C. for 5 minutes for drying. Thereafter, the coating film is irradiated with 350 mW / cm ² and 1000 mJ / cm ² using an electrodeless lamp (H bulb) manufactured by Fusion UV Systems in an air atmosphere, and cured to be a protective film having a thickness of 1 μm. Formed. The obtained protective film showed good fingerprint wiping properties.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

  The laminate of the present invention is suitable for, for example, a touch panel because a protective film having good adhesion and hardness with glass and low fingerprint visibility is formed.

DESCRIPTION OF SYMBOLS 10 ... Laminated body, 1 ... Glass substrate, 2 ... Protective film

Claims (5)

A glass substrate, and a protective film formed on the glass substrate,
The protective film is
(A) a compound having a cyclic structure and a plurality of (meth) acryloyl groups,
(B) a phosphate ester compound having a (meth) acryloyl group , and (C) a fatty acid ester having a (meth) acryloyl group and having an HLB value of 2 or more and 15 or less,
The laminated body formed by hardening the composition containing this. Oite to claim 1,
The laminate, wherein the composition further comprises (D) inorganic oxide particles having a number average particle diameter of 1 nm to 100 nm. A touch panel comprising the laminate according to claim 1 . (A) a compound having a cyclic structure and a plurality of (meth) acryloyl groups,
(B) a phosphate ester compound having a (meth) acryloyl group , and (C) a fatty acid ester having a (meth) acryloyl group and having an HLB value of 2 or more and 15 or less,
Contain,
100% by mass of the entire component excluding the solvent, 10 to 90% by mass of the component (A), 1 to 10% by mass of the component (B), and 0.1 to 20% by mass of the component (C). A composition for forming a protective film . In claim 4 ,
Further, (D) a composition containing inorganic oxide particles having a number average particle diameter of 1 nm to 100 nm.

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