JP6762111B2 - Hard coating agent and laminated film - Google Patents

Description

The present invention relates to a hard coat agent capable of efficiently forming a hard coat layer having excellent heat resistance and scratch resistance, and a laminated film having a hard coat layer formed by using the hard coat agent.

Display devices such as various displays equipped with a touch panel and used as a data input device are operated with a finger or a pen for a touch panel during handling, so it is necessary to protect the surface from scratches. For this reason, conventionally, a cover glass (glass substrate) has been installed on the outermost surface.
However, there is a demand for further thinning and weight reduction of terminals, and in recent years, a hard coat film having a hard coat layer has been used as an alternative material for a glass substrate.
Such a hard coat film is required to have a heat resistance standard that is satisfied when a glass substrate is used. Further, when a transparent conductive material such as ITO is laminated on the hard coat film by a dry process, the hard coat film may be heated and exposed to a high temperature during the process, and better heat resistance is required. Will be done.

Conventionally, as a material (hard coating agent) for forming a hard coat layer on a resin film, for example, Patent Document 1 describes the general formula (I) in the molecule.

[In the formula, ^Ra is − (CH ₂ ) n—OC (= O) −CH = CH ₂ , − (CH ₂ ) n—OC (= O) −C (CH ₃ ) = CH. ₂ or −CH = CH ₂ (in the formula, n represents an integer of 1 to 10) represents a group, and R ^b is the above ^Ra , which has 1 to 10 carbon atoms which may have ^a substituent. Represents an aromatic group which may have an alkyl group or a substituent of 6. ], An ionizing radiation curable hard coat agent composition containing a silsesquioxane ladder oligomer having a repeating unit structure represented by [] and having a number average molecular weight of 1,000 to 30,000 is described.
In addition, this document also describes the results of evaluation tests on the scratch resistance and weather resistance of the obtained hard coat layer.
However, this document does not describe the evaluation of the pencil hardness and heat resistance of the obtained hard coat layer. Further, regarding the evaluation of scratch resistance, only the evaluation result of the test of rubbing with steel wool (# 0000) is described.

Patent No. 3389660

As described above, Patent Document 1 describes an ionizing radiation-curable hard coat agent composition containing a specific silsesquioxane ladder oligomer, which is excellent in weather resistance and scratch resistance.
However, even the hard coat layer obtained from the hard coat agent composition described in this document may have insufficient heat resistance and scratch resistance.

The present invention has been made in view of the above circumstances, and is a hard coat agent capable of efficiently forming a hard coat layer excellent in heat resistance and scratch resistance, and a hard coat agent formed by using this hard coat agent. An object of the present invention is to provide a laminated film having a coat layer.

The present inventors have diligently studied a hard coating agent in order to solve the above problems. As a result, heat resistance and scratch resistance are obtained by using a hard coat agent containing a polysilsesquioxane compound having a repeating unit containing a reactive functional group and an inorganic filler having a reactive functional group in the molecule. It has been found that an excellent hard coat layer can be efficiently formed, and the present invention has been completed.

Thus, according to the present invention, the following hard coating agents [1] and [2] and the following laminated film [3] are provided.

[1] A hard coating agent containing the following component (A) and component (B).
Component (A): A polysilsesquioxane compound having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and the repeating unit represented by the formula (1). The content ratio of the unit is 10 mol% or more and 90 mol% or less in all the repeating units, and the content ratio of the repeating unit represented by the formula (2) is 10 mol% or more and 90 mol% or less in all the repeating units. Polysilsesquioxane compound

(R ¹ represents a reactive functional group, A represents a single bond or a divalent organic group having 1 to 10 carbon atoms. R ² represents an aryl group.)
Component (B): Inorganic filler having a reactive functional group [2] The content of the component (B) is 10% by mass to 70% by mass with respect to the component (A), according to [1]. Hard coating agent.
[3] A laminated film having a base material layer and a hard coat layer.
A laminated film in which the hard coat layer is formed by using the hard coat agent according to [1] or [2].

According to the present invention, there is provided a hard coat agent capable of efficiently forming a hard coat layer having excellent heat resistance and scratch resistance, and a laminated film having a hard coat layer formed by using the hard coat agent. To.

It is an IR spectrum figure of the ladder type silane compound polymer (1). It is a ^29- Si-NMR spectrum figure of the ladder type silane compound polymer (1). It is ¹ H-NMR spectrum figure of the rudder type silane compound polymer (1).

Hereinafter, the present invention will be described in detail by dividing it into 1) a hard coating agent and 2) a laminated film.

1) Hard coating agent The first of the present invention is a hard coating agent containing the components (A) and (B).
[(A) component]
The component (A) constituting the hard coat agent of the present invention is a polysilsesquioxane compound having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) (hereinafter, It is sometimes referred to as "polysilsesquioxane compound (A)"), and the content ratio of the repeating unit represented by the formula (1) is 10 mol% or more and 90 mol% or less in all the repeating units. Yes, it is a compound in which the content ratio of the repeating unit represented by the formula (2) is 10 mol% or more and 90 mol% or less in all the repeating units.

In the above formulas (1) and (2), R ¹ represents a reactive functional group, A represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and R ² represents an aryl group.

[Repeating unit represented by equation (1)]
In the formula (1), the reactive functional group of R ¹ is a group capable of forming a chemical bond by reacting with the reactive functional group of the inorganic filler of the component (B) described later.
Examples of the reactive functional group of R ¹ include a photoreactive functional group that reacts when irradiated with an active energy ray and a thermoreactive functional group that reacts when heated, and a photoreactive functional group is preferable. ..
Specific examples of the reactive functional group include a group having a carbon-carbon unsaturated bond such as a vinyl group, an allyl group, a styryl group, a (meth) acryloyl group, and a (meth) acryloyloxy group; an epoxy group, a glycidyl group, and a glycidyl group. Examples thereof include a group having an epoxy group such as an oxy group; an isocyanate group; a mercapto group; and the like. Here, (meth) acryloyl means acryloyl or methacryloyl.
Among these, a group having a carbon-carbon unsaturated bond is more preferable, and a vinyl group is particularly preferable.

A represents a single bond or a divalent organic group having 1 to 10 carbon atoms.
Examples of the divalent organic group of A include an alkylene group represented by the following formula (3), an arylene group represented by the following formula (4), an oxy group (-O-), an imino group (-NH-), and the like. Carbonyl group (> C = O), sulfonyl group (-SO _2- ), amide group (-NH-C (= O)-, -C (= O) -NH-), or ester group (-C (-C ()) = O) -O-, -OC (= O)-), and combinations of these groups can be mentioned.

In formulas (3) and (4), R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ar represents an arylene group. Each of a and b independently represents an integer of 1 to 10. When a and b are 2 or more, the repeating units represented by the formula: -C (R ³ ) (R ⁴ )-and the repeating units represented by the formula: -Ar- are the same. However, they may be different.

Specific examples of the alkylene group represented by the formula (3) include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and the like.
Specific examples of the arylene group represented by the formula (4) include a 1,4-phenylene group, a 1,3-phenylene group, a 1,5-naphthylene group, a 2,6-naphthylene group and the like.
The arylene group represented by the formula (4) may have a substituent at an arbitrary position. Examples of such substituents include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; and 1 to 6 carbon atoms such as methoxy group and ethoxy group. Alkoxy group; etc.

In addition, examples of the "combination of these groups" include groups represented by the following formulas (5) to (10).

In formulas (5) to (8), R ³ , R ⁴ , and Ar have the same meanings as described above.
R ⁵ and R ⁶ independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, which are the same as those of R ³ and R ⁴ , respectively.
Ar'represents an arylene group similar to Ar.
Further, the group represented by Ar'may have a substituent at an arbitrary position. Examples of such substituents include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; and 1 to 6 carbon atoms such as methoxy group and ethoxy group. Alkoxy group: and the like.
c to l each independently represent an integer of 1 to 10.
E is an oxy group (-O-), an imino group (-NH-), a carbonyl group (> C = O), a sulfonyl group (-SO _2- ), an amide group (-NH-C (= O)-, It represents −C (= O) -NH−) or an ester group (−C (= O) −O−, −OC (= O) −).
When c to l are 2 or more, the repeating units represented by the formula: -C (R ³ ) (R ⁴ )-, and the repeating units represented by the formula: -C (R ⁵ ) (R ⁶ )-. The repeating units represented by each other, the formula: -Ar-, and the repeating units represented by the formula: -Ar'-may be the same or different from each other.
Among these, in the present invention, the alkylene group represented by the formula (3) and the arylene group represented by the formula (4) are preferable, and the alkylene group represented by the formula (3) is more preferable.

The repeating unit represented by the formula (1) has a structure in which three oxygen atoms are bonded to a silicon atom and one other group (R ¹ ) is bonded [the following formula (1-a)]. ..

The repeating unit represented by the above formula (1-a) is generally collectively referred to as a T-site. Specific examples of the structure of the T-site include those represented by the following formulas (1-a1) to (1-a3).

Wherein (1-a1) ~ formula ^{(1-a3), R} 1 represents the same meaning as described above. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group and a t-butyl group. The acyl group having 2 to 10 carbon atoms R ^5, acetyl group, propionyl group, and benzoyl group. A plurality of R ⁵ together may all be different mutually be the same. Further, in the above formulas (1-a1) to (1-a3), a Si atom is bonded to *.

[Repeating unit represented by equation (2)]
In formula (2), R ² represents an aryl group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
Further, the aryl group of R ² may have a substituent at an arbitrary position. Examples of such substituents include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; and 1 to 6 carbon atoms such as methoxy group and ethoxy group. Alkoxy group; etc.

The repeating unit represented by the formula (2) has a structure [the following formula (2-a)] in which three oxygen atoms are bonded to the silicon atom and one other group (R ² ) is bonded. (following).

The repeating unit represented by the formula (2-a) is generally collectively referred to as a T-site. Specific examples of the structure of the T-site include those represented by the following formulas (2-a1) to (2-a3).

In formulas (2-a1) to (2-a3), R ² has the same meaning as described above. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms of R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group and the like. Examples of the acyl group having 2 to 10 carbon atoms of R ⁶ include an acetyl group, a propionyl group, a benzoyl group and the like. A plurality of R ⁶ to each other may all be different mutually be the same. Further, in the above formulas (1-b1) to (1-b3), a Si atom is bonded to *.

In the polysilsesquioxane compound (A), the content ratio of the repeating unit represented by the formula (1) is 10 mol% or more and 90 mol% or less, preferably 30 mol% or more and 70 mol% in all the repeating units. Hereinafter, it is more preferably 40 mol% or more and 60 mol% or less, and the content ratio of the repeating unit represented by the formula (2) is 10 mol% or more and 90 mol% or less, preferably 30 mol% in all the repeating units. The compound is 70 mol% or more, more preferably 40 mol% or more and 60 mol% or less.
The content ratio of the repeating unit represented by the above formulas (1) and (2) in the polysilsesquioxane compound (A) is, for example, ¹ H-NMR and ^{29 of the} polysilsesquioxane compound (A). It can be obtained by measuring Si-NMR.

The polysilsesquioxane compound (A) is a random copolymer or block as long as it has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) in the molecule. It may be any of a copolymer, a graft copolymer, an alternating copolymer and the like, but a random copolymer is preferable from the viewpoint of ease of production and the like.
Further, the structure of the polysilsesquioxane compound (A) may be any of a ladder type structure, a double decker type structure, a cage type structure, a partially cleaved cage type structure, a cyclic type structure, and a random type structure. However, a ladder type structure is preferable.

The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is usually 800 to 50,000, preferably 1,000 to 45,000, more preferably 3,000 to 40,000, particularly preferably. It is in the range of 5,000 to 35,000. By using the polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range, a cured product having excellent heat resistance and scratch resistance is given, and a hard coat having excellent workability in the coating process is provided. The agent can be easily obtained.

The molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (A) is not particularly limited, but is usually in the range of 1.0 to 10.0, preferably 1.1 to 6.0. By using the polysilsesquioxane compound (A) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easy to obtain a cured product having better adhesiveness and heat resistance.
The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, as standard polystyrene-equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

In the present invention, the polysilsesquioxane compound (A) can be used alone or in combination of two or more.

[Method for producing polysilsesquioxane compound (A)]
The method for producing the polysilsesquioxane compound (A) is not particularly limited. For example, the following equation (1-1)

(In the formula, R ¹ has the same meaning as described above. R ⁷ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, X ¹ represents a halogen atom, and p is 0. represents an -3 integer. more R ^7, and a plurality of X ¹ are each, be the same as each other, at least one may be different from each other.) a silane compound represented by (1-1) Species and the following formula (2-1)

(In the formula, R ² has the same meaning as described above. R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, X ² represents a halogen atom, and q represents 0. represents an -3 integer. plurality of R ⁸ and a plurality of X ^2, respectively, be the same as each other, at least one may be different from each other.) a silane compound represented by (2-1) The polysilsesquioxane compound (A) can be produced by polycondensing with the seed.

In the formulas (1-1) and (2-1), examples of the alkyl group having 1 to 10 carbon atoms of R ⁷ and R ⁸ include a methyl group, an ethyl group and a propyl group.
Examples of the acyl group having 2 to 10 carbon atoms of R ⁷ and R ⁸ include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the halogen atom of X ¹ and X ² include a chlorine atom and a bromine atom.

Specific examples of the silane compound (1-1) include vinyl group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, vinyltribromosilane, and vinyltriacetoxysilane;
Allyl group-containing silane compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyltriacetoxysilane, allyltrichlorosilane, allyltribromosilane, allyltriacetoxysilane;
γ-Acryloxyalkyl such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ-acryloxypropyltribromosilane, γ-acryloxypropyltriacetoxysilane Group-containing silane compound;
γ-Methyloxyalkyl groups such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, γ-methacryloxypropyltribromosilane, γ-methacryloxytriacetoxysilane Containing silane compound;
α-glycidoxyethyl trimethoxysilane, α-glycidoxyethyl triethoxysilane, β-glycidoxyethyl trimethoxysilane, β-glycidoxyethyl triethoxysilane, α-glycidoxyethyl trichlorosilane, α Epoxy group-containing silane compounds such as −glycidoxyethyltribromosilane, α-glycidoxytriacetoxysilane, β-glycidoxyethyltrichlorosilane, β-glycidoxyethyltribromosilane, β-glycidoxytriacetoxysilane ; Etc. can be mentioned.
Among these, as the silane compound (1-1), a vinyl group-containing silane compound is preferable.
The silane compound (1-1) can be used alone or in combination of two or more.

Specific examples of the silane compound (2-1) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, and 3-chlorophenyltrimethoxy. Aryltrialkoxysilane compounds such as silane, 3-chlorophenyltriethoxysilane, 3,5-dimethoxyphenyltrimethoxysilane, 1-naphthyllimethoxysilane, 2-naphthyllimethoxysilane;
Aryltriacyloxysilane compounds such as phenyltriacetoxysilane, 4-methylphenyltriacetoxysilane, 3-chlorophenyltriacetoxysilane, 3,5-dimethoxytriacetoxysilane, 1-naphthylriacetoxysilane, 2-naphthylriacetoxysilane ;
Phenylchlorodimethoxysilane, phenylchlorodiethoxysilane, phenyldichloromethoxysilane, phenylbromodimethoxysilane, 4-methylphenylchlorodimethoxysilane, 4-methylphenylchlorodiethoxysilane, 1-naphthyldichloromethoxysilane, 2-naphthylbromodimethoxy Arylhalogenoalkoxysilane compounds such as silane;
Examples thereof include aryltrihalogenosilane compounds such as phenyltrichlorosilane, phenyltribromosilane, 4-methylphenyltrichlorosilane, 4-methylphenyltribromosilane, 1-naphthyllichlorosilane, and 2-naphthyllibromosilane.
Among these, as the silane compound (2-1), aryltrialkoxysilane compounds are preferable because a hard coating agent that gives a cured product having better heat resistance and scratch resistance can be obtained.
The silane compound (2-1) can be used alone or in combination of two or more.

The method for polycondensing the silane compound (1-1) and the silane compound (2-1) is not particularly limited. For example, a predetermined amount of polycondensation catalyst is added to a mixture of a silane compound (1-1) and a silane compound (2-1) (hereinafter, may be referred to as a "mixture of a silane compound") in a solvent or without a solvent. Is added, and the mixture is stirred at a predetermined temperature.
More specifically, (a) a method of adding a predetermined amount of an acid catalyst to the mixture of the silane compounds and stirring at a predetermined temperature, and (b) adding a predetermined amount of a base catalyst to the mixture of the silane compounds. Method of stirring at a predetermined temperature, (c) A predetermined amount of an acid catalyst is added to the mixture of the silane compounds, and after stirring at a predetermined temperature, an excess amount of a base catalyst is added to make the reaction system basic. Method of stirring at a predetermined temperature, (d) A predetermined amount of polycondensation catalyst is added to the silane compound (1-1) in a solvent or without a solvent, and the mixture is stirred at a predetermined temperature and then the silane compound (2-1). ) Is added and the whole volume is stirred at a predetermined temperature. (E) A predetermined amount of polycondensation catalyst is added to the silane compound (2-1) in a solvent or without a solvent to obtain a predetermined temperature. After stirring with, a predetermined amount of the silane compound (1-1) is added, and the whole volume is stirred at a predetermined temperature;
Among these, the method (a) or (c) is preferable because the desired polysilsesquioxane compound (A) can be efficiently obtained.

The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Further, two or more polycondensation catalysts may be used in combination.
Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; Can be mentioned. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferable.

As the base catalyst, aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picolin, 1,4- Diazabicyclo [2.2.2] Organic bases such as octane and imidazole; Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxydone, sodium alkoxide, sodium t-butoxide, potassium t-butoxide Metal alkoxides such as; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; Metallic hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and the like.

The amount of the polycondensation catalyst used is usually in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, based on the total molar amount of the mixture of the silane compounds.

When a solvent is used, the solvent to be used can be appropriately selected depending on the types of the silane compound (1-1) and the silane compound (2-1) and the like. For example, water; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. ; Alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol; and the like. These solvents can be used alone or in combination of two or more. When the method (c) above is adopted, a polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, and then an organic solvent and an excessive amount of a base catalyst (ammonia water, etc.) are added to the reaction solution. The polycondensation reaction may be further carried out under basic conditions.

The amount of the solvent used is 0.1 to 10 liters, preferably 0.1 to 2 liters, per 1 mol of the total molar amount of the mixture of the silane compounds.

The temperature at which the mixture of the silane compounds is polycondensed is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 20 to 100 ° C. If the reaction temperature is too low, the progress of the polycondensation reaction may be insufficient. On the other hand, if the reaction temperature becomes too high, it becomes difficult to suppress gelation. The reaction is usually complete in 30 minutes to 20 hours.

After completion of the reaction, when an acid catalyst is used, an alkaline aqueous solution such as sodium hydrogen carbonate is added to the reaction solution, and when a base catalyst is used, an acid such as hydrochloric acid is added to the reaction solution. The sum is performed, and the salt generated at that time is removed by filtration, washing with water, or the like to obtain the desired polysilsesquioxane compound (A).

When the polysilsesquioxane compound (A) is produced by the above method, dealcoholization is performed among OR ⁷ or X ^{1 of} the silane compound (1-1) and OR ⁸ or X ² of the silane compound (2-1). The portion where the above did not occur remains in the polysilsesquioxane compound (A). Therefore, in the polysilsesquioxane compound (A), in addition to the repeating units represented by the formulas (1-a) and (2-a), the formulas (1-a1) and (1-a2) are included. ), Formula (1-a3), formula (2-a1), formula (2-a2), and repeating units represented by formula (2-a3) may be included.

Component (B) The hard coat agent of the present invention contains an inorganic filler having a reactive functional group as the component (B) (hereinafter, the component (B) may be referred to as "inorganic filler (B)"). To do.
The hard coating agent containing the component (B) is excellent in workability in the coating process.

The reactive functional group contained in the inorganic filler (B) refers to a group capable of reacting with the reactive functional group of the component (A) to form a chemical bond. Examples of this reactive functional group include those similar to those shown as the reactive functional group of the polysilsesquioxane compound (A). Of these, a group having a carbon-carbon unsaturated bond is preferable, and a (meth) acryloyloxy group is more preferable.

The inorganic filler (B) is an inorganic filler in which a reactive functional group is introduced into the surface by a modification treatment.
Examples of the inorganic component (constituent component of the inorganic filler before the modification treatment) constituting the inorganic filler (B) include metal oxides, metal hydroxides, metal salts and the like.

Examples of the metal oxide include silica, titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide and the like.
Examples of the metal hydroxide include aluminum hydroxide.
Examples of the metal salt include metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and metal silicates such as aluminum silicate, calcium silicate and magnesium silicate; and the like.
Among these, as the inorganic component constituting the inorganic filler (B), a metal oxide is preferable, and silica is more preferable.

The shape of the inorganic filler (B) may be spherical, chain-shaped, needle-shaped, plate-shaped, flaky, rod-shaped, fibrous, or the like, but is preferably spherical. Here, the spherical shape means a substantially spherical shape including a polyhedral shape that can be approximated to a spheroid, an oval shape, a konpeito shape, an eyebrows shape, and the like, in addition to a true sphere.

The size of the inorganic filler (B) is not particularly limited. The average particle size of the inorganic filler (B) is usually 5 to 1000 nm, preferably 10 to 500 nm, and more preferably 20 to 100 nm.
When the average particle size of the inorganic filler (B) is within the above range, a hard coat layer having excellent transparency and scratch resistance can be efficiently formed.
The average particle size of the inorganic filler (B) can be calculated by using the specific surface area obtained by the BET method.

Most of the inorganic fillers (B) used in the present invention are known substances. This can be obtained by a known method such as a method of dispersing inorganic fine particles in an appropriate dispersion medium (water, organic solvent, etc.) in the presence of a surface modifier. The surface modifiers used include saturated or unsaturated carboxylic acids, acid anhydrides, acidified products, esters and acid amides corresponding to the carboxylic acids, amino acids, imines, nitriles, isonitriles, epoxy compounds, amines, and β-dicarbonyl. Examples thereof include one or more compounds selected from the group consisting of compounds, silanes, and metal compounds having a functional group.
Further, in the present invention, a commercially available product can be used as it is as the inorganic filler (B).

In the hard coating agent of the present invention, the inorganic filler (B) can be used alone or in combination of two or more.

The content of the inorganic filler (B) in the hard coating agent of the present invention is not particularly limited. The content of the inorganic filler (B) is usually 10 to 70% by mass, preferably 15 to 65% by mass, and more preferably 18 to 60% by mass with respect to the component (A).
In particular, when a hard coat agent having an inorganic filler (B) content of 10 to 70% by mass with respect to the component (A) is used, a hard coat layer having a high hardness is easily formed.
Further, when a hard coat agent having an inorganic filler (B) content of 10 to 70% by mass with respect to the component (A) is used, it becomes easy to form a hard coat layer having excellent scratch resistance.

The hard coat agent of the present invention may contain other components in addition to the components (A) and (B) as long as the effects of the present invention are not impaired. Other components include solvents and photopolymerization initiators.

Since the hard coat agent containing a solvent is excellent in coatability, a thin hard coat layer can be efficiently formed by using the hard coat agent containing a solvent.
Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride and ethylene chloride; methanol, ethanol and propanol. Alcohol-based solvents such as butanol and 1-methoxy-2-propanol; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone and isophorone; ester solvents such as ethyl acetate and butyl acetate; cellosolves such as ethyl cellosolve Examples include system solvents and the like.
The solvent may be used alone or in combination of two or more.

When the hard coat agent of the present invention contains a solvent, the content of the solvent is preferably an amount such that the solid content concentration of the hard coat agent of the present invention is 30 to 95% by mass or more, and is an amount of 35 to 90% by mass. Is more preferable, and an amount of 40 to 85% by mass is further preferable.

By using a hard coating agent containing a photopolymerization initiator, the obtained coating film can be efficiently cured after the hard coating agent is applied.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like. 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2- Methylanthraquinone, 2-ethylanthraquinone, 2-tershary-butylantraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl Examples thereof include dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester and the like.
The photopolymerization initiator may be used alone or in combination of two or more.

When the hard coat agent of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is usually 0.01 to 10% by mass, preferably 0.%, based on the total solid content of the hard coat agent. It is 5 to 10% by mass.

The hard coat agent of the present invention is preferably a mixture of a polysilsesquioxane compound having a small amount of low molecular weight components and a small amount of residual silanol groups and alkoxy groups that cause dehydration and dealcohol, and an inorganic filler. By forming a hard coat layer using such a hard coat agent, a laminated film having excellent heat resistance and scratch resistance can be obtained.

2) Laminated film The laminated film of the present invention is a laminated film having a base material layer and a hard coat layer, and the hard coat layer is formed by using the hard coat agent of the present invention. And.

The base material layer constituting the laminated film of the present invention is used to hold the hard coat layer.
The type of the base material layer is not particularly limited. For example, a synthetic resin film can be used as a base material layer.
Examples of the synthetic resin film include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polymethacrylic acid. Examples thereof include films of methyl, methyl polyacrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, polycarbonate and the like.

The thickness of the base material layer (synthetic resin film) is not particularly limited, and can be appropriately determined depending on the use of the laminated film and the like.
The thickness of the base material layer is usually 10 to 500 μm, preferably 20 to 200 μm.

The hard coat layer constituting the laminated film of the present invention is formed by using the hard coat agent of the present invention.
The thickness of the hard coat layer is usually 0.1 to 50 μm, preferably 0.5 to 20 μm.

The hard coat layer can be formed by applying the hard coat agent of the present invention on a synthetic resin film for a base material layer and curing the obtained coating film.

The method of applying the hard coating agent on the synthetic resin film is not particularly limited, and a known method can be adopted. For example, roll coat method, curtain flow coat method, mayer bar coat method, reverse coat method, gravure coat method, gravure reverse coat method, air knife coat method, kiss coat method, blade coat method, smooth coat method, roll knife coat method, etc. Can be mentioned.

The method for curing the coating film is not particularly limited. For example, the coating film can be cured by irradiating the coating film with active energy rays such as ultraviolet rays and electron beams.
Ultraviolet irradiation can be performed by a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. The dose of ultraviolet rays, illuminance 50~1000mW / cm ^2, about the amount of light 50~1000mJ / cm ² is preferred. On the other hand, electron beam irradiation can be performed by an electron beam accelerator or the like. The irradiation amount of the electron beam is preferably about 10 to 1000 grad.

When forming the hard coat layer, if necessary, the drying treatment may be performed before the coating film is cured or after the coating film is cured.
The drying treatment conditions are not particularly limited. The drying temperature is, for example, 40 to 150 ° C., preferably 60 to 140 ° C., and the drying time is, for example, 30 seconds to 1 hour, preferably 1 to 30 minutes.

The hard coat layer of the laminated film of the present invention is formed by using the hard coat agent of the present invention, and is excellent in heat resistance and scratch resistance.

The excellent heat resistance of the hard coat layer of the laminated film of the present invention means that the hard coat layer obtained from the hard coat agent of the present invention can be subjected to a 5% weight loss temperature using, for example, a thermogravimetric analyzer (TGA). When measured, it can be confirmed from the high 5% weight loss temperature.
The 5% weight loss temperature of the hard coat layer obtained from the hard coat agent of the present invention is usually 350 ° C. or higher, preferably 360 ° C. or higher, and more preferably 370 ° C. or higher.
The hard coat layer of the laminated film of the present invention is excellent in abrasion resistance, for example, by using a steel wool # 0000, the surface of the hard coat layer of the laminated film of the present invention, at 250 g / cm ² load, 50 mm It can be confirmed that there is no scratch on the surface even after rubbing 10 times.

The hard coat layer of the laminated film of the present invention has high hardness and excellent scratch resistance.
The hard coat layer constituting the laminated film of the present invention usually shows a hardness of F or more when a pencil hardness test is performed according to the method described in Examples, and H or more is preferable.
When the scratch resistance of the hard coat layer constituting the laminated film of the present invention is evaluated according to the method described in Examples, no scratches are usually observed.

The laminated film of the present invention has excellent optical characteristics.
The total light transmittance of the laminated film of the present invention is usually 89% or more, preferably 90% or more.
The haze of the laminated film of the present invention is usually 0.75 or less, preferably 0.72 or less.
The b ^* of the laminated film of the present invention is usually 0.3 or less, preferably 0.25 or less.

The laminated film of the present invention has a hard coat layer having excellent heat resistance and scratch resistance and high hardness, and is suitably used as a material for manufacturing a touch panel.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise specified, parts and% in each example are based on mass.

[Production Example 1] Production of silane compound polymer (1) To a 500 ml eggplant-shaped flask, 0.12 g (0.86 mmol) of potassium carbonate, 14.4 g of purified water, and 24.0 g of tetrahydrofuran were added, and the whole volume was adjusted to room temperature (24.0 g). The mixture was stirred at 25 ° C. (same below) for 5 minutes. There, 29.86 g (120 mmol) of 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-503), and phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-103). 23.78 g (120 mmol) was added dropwise using a dropping funnel. After completion of the dropping, the mixture was further stirred at room temperature for 96 hours. After completion of the reaction, ethyl acetate was added to the reaction solution to separate the layers, and the ethyl acetate layer was separated. The organic layer was repeatedly washed with purified water until pH = 7, and the organic layer was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated on an evaporator. The obtained concentrate was added to a large amount of methanol to reprecipitate the desired product. The obtained precipitate was vacuum dried to obtain 24.0 g of a ladder-type silane compound polymer (1).
The mass average molecular weight was 31,600 and the molecular weight distribution (PDI) was 1.87.
The IR spectrum diagram of the obtained ladder-type silane compound polymer (1) is shown in FIG. 1, the ²⁹ Si-NMR spectrum diagram is shown in FIG. 2, and the ¹ H-NMR spectrum diagram is shown in FIG. 3, respectively. In FIG. 1, the horizontal axis represents cm ^-1 , the vertical axis represents the transmittance (MT%), and in FIGS. 2 and 3, the horizontal axis represents the chemical shift (ppm) and the vertical axis represents the peak intensity.

[Production Example 2] Preparation of hard coat coating liquid 1
100 parts by mass of methyl ethyl ketone diluent (concentration 50% by mass) of the ladder type silane compound polymer (1), acryloyloxy group-modified silica nanofiller [manufactured by Nissan Chemical Industries, Ltd., "AC-4130Y", concentration 30% by mass, average particle size 40 to 50 nm] 30 parts by mass, photopolymerization initiator [BASF, "IRGACURE184", concentration 100% by mass] 2.5 parts by mass of the mixed solution diluted with methyl ethyl ketone, hard coat coating with a concentration of 40% by mass Liquid 1 was prepared.

[Production Examples 3 to 5] Preparation of Hard Coat Coating Liquids 2 to 4 Addition of acryloyloxy group-modified silica nanofiller [manufactured by Nissan Chemical Industries, Ltd., "AC-4130Y", concentration 30% by mass, average particle size 40 to 50 nm] Hard coat coating liquids 2 to 4 were prepared in the same manner as in [Production Example 2] except that the amounts were 50 parts by mass, 70 parts by mass, and 100 parts by mass.

[Production Example 6] Preparation of hard coat coating liquid 5 100 parts by mass of methyl ethyl ketone diluted solution (concentration 50% by mass) of rudder type silane compound polymer (1), photopolymerization initiator [BASF, "IRGACURE 184", concentration [100% by mass] 5 parts by mass of the mixed solution was diluted with methyl ethyl ketone to prepare a hard coat coating solution 5 having a concentration of 40% by mass.

[Example 1]
Apply hard coat coating liquid 1 to a PET film with a single-sided easy-adhesive layer [manufactured by Toyobo Co., Ltd., "PET50A4100", film thickness 50 μm] using Meyerbar # 10 so that the film thickness after curing is 5 μm. Then, it was dried at 100 ° C. for 1 minute to form a coating film of the hard coat coating liquid 1.
Next, the coating film was irradiated with ultraviolet rays (light intensity: 500 mJ / cm ² ) and cured to form a hard coat layer 1 to obtain a hard coat film 1 of Example 1.
Further, by forming a hard coat layer on a PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] in the same manner using the coating liquid 1, the PET film with a release layer is peeled off and removed. , The cured layer was recovered. This was used as the heat resistance evaluation sample 1.

[Examples 2 to 4]
In Example 1, hard coat films 2 to 4 of Examples 2 to 4 were obtained in the same manner as in Example 1 except that hard coat coating liquids 2 to 4 were used instead of hard coat coating liquid 1. It was.
Further, after forming a hard coat layer on a PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] in the same manner using coating solutions 2 to 4, the PET film with a release layer is peeled off and removed. As a result, the cured layer was recovered. This was used as heat resistance evaluation samples 2 to 4.

[Comparative Example 1]
A hard coat film 5 of Comparative Example 1 was obtained in the same manner as in Example 1 except that the hard coat coating liquid 5 was used instead of the hard coat coating liquid 1 in Example 1.
Further, by forming a hard coat layer on a PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] in the same manner using the coating liquid 5, the PET film with a release layer is peeled off and removed. , The cured layer was recovered. This was used as the heat resistance evaluation sample 5.

[Comparative Example 2]
In Example 1, the organically modified silica fine particles were changed to 100 parts by mass of a mixture of polyfunctional acrylates [Taisei Fine Chemicals Co., Ltd., "Acryt 8RX-012", concentration 40% by mass], and a photopolymerization initiator [BASF Co., Ltd., " IRGACURE 184 ”, concentration 100% by mass] A hard coat coating solution 6 was prepared in the same manner as in Example 1 except that a mixed solution of 5 parts by mass was used. Using the obtained hard coat coating liquid 6, the hard coat film 6 of Comparative Example 2 was obtained in the same manner as in Example 1.
Further, the hard coat layer is similarly formed on the PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] using the hard coat coating liquid 6, and then the PET film with a release layer is peeled off and removed. As a result, the cured layer was recovered. This was used as a heat resistance evaluation sample 6.

[Comparative Example 3]
In Example 1, an acrylate resin solution having a cage-shaped silane compound in the side chain [manufactured by JNC Corporation, "HC-6114-001", concentration 40% by mass, containing a photopolymerization initiator] (hard coat coating solution 7) was applied. A hard coat film 7 of Comparative Example 3 was obtained in the same manner as in Example 1 except that it was used.
Further, the hard coat layer is similarly formed on the PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] using the hard coat coating liquid 7, and then the PET film with a release layer is peeled off and removed. As a result, the cured layer was recovered. This was used as a heat resistance evaluation sample 7.

[Comparative Example 4]
In Example 1, a mixture of organically modified silica fine particles and a polyfunctional acrylate [manufactured by JSR, "Opstar Z7530", concentration 73% by mass, containing a photopolymerization initiator] was diluted with propylene glycol monomethyl ether to a concentration of 40% by mass. The hard coat film 8 of Comparative Example 4 was obtained in the same manner as in Example 1 except that the solution adjusted to (Hard Coat Coating Solution 8) was used.
Further, by forming a hard coat layer on a PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] in the same manner using the coating liquid 8, the PET film with a release layer is peeled off and removed. , The cured layer was recovered. This was used as a heat resistance evaluation sample 8.

[Comparative Example 5]
In Example 1, polysilsesquioxane having an ultraviolet curable group [manufactured by Toa Synthetic Co., Ltd., "MAC-SQ TM100", concentration 100% by mass], photopolymerization initiator [manufactured by BASF, "IRGACURE 184", concentration 100). Mass%] 5 parts by mass was diluted with methyl ethyl ketone, and a solution adjusted to a concentration of 40% by mass (hard coat coating solution 9) was applied using Meyerbar # 10, dried at 100 ° C. for 1 minute, and then dried. A hard coat film 9 of Comparative Example 6 was obtained in the same manner as in Example 1 except that the obtained coating film was irradiated with ultraviolet rays (light intensity: 1700 mJ / cm ² ).
Further, by forming a hard coat layer on a PET film with a release layer [Lintec Corporation, "PET381130", thickness 38 μm] in the same manner using the coating liquid 9, the PET film with a release layer is peeled off and removed. , The cured layer was recovered. This was used as a heat resistance evaluation sample 9.

With respect to the hard coat films 1 to 9 obtained above, the film thickness, the total light transmittance, and the pencil hardness were measured as follows, and the scratch resistance was evaluated.
(1) Measurement of the film thickness of the hard coat layer: According to JIS K 7130, the film thickness was measured with a thickness meter ["MH-15" manufactured by Nikon Corporation.
(2) Measurement of total light transmittance and haze: Measurement was performed using a haze meter [N-DH-2000, manufactured by Nippon Denshoku Co., Ltd.] according to JIS K 7361-1 (1997).
(3) Measurement of pencil hardness: According to JIS K5600-5-4, the measurement was performed using a pencil scratch hardness tester ["No. 553-M" manufactured by Yasuda Seiki Seisakusho Co., Ltd.].
The measurement conditions were a load of 750 g and a scratching speed of 0.5 mm / sec. (4) Scratch resistance evaluation test: Using steel wool # 0000, the surface of the hard coat layer was 50 mm with a load of 250 g / cm ² . After rubbing 10 times back and forth, the presence or absence of scratches was visually confirmed. As a result, the case without scratches was evaluated as "○", and the case with scratches was evaluated as "x".
(5) Measurement of b ^* : CIE1976L * a * b * Color value b ^* defined by the color system,
The measurement was performed using a spectrophotometer (MPC3100 manufactured by Shimadzu Corporation) in accordance with JIS Z 8729-1994.

In addition, the following heat resistance evaluation test was carried out using the heat resistance evaluation samples 1 to 9 obtained above.
(6) Heat resistance evaluation: A 5% weight loss temperature under a nitrogen atmosphere was measured using a thermogravimetric analyzer (TGA).
In Table 1, Td1 (° C.) indicates the temperature when the weight is reduced by 1%, and Td5 (° C.) indicates the temperature when the weight is reduced by 5%.

From Table 1, the hard coat film having a hard coat layer obtained by using the hard coat agent containing the silsesquioxane compound (A) and the inorganic filler (B) has optical properties (transparency, haze, b ^*. ), Heat resistance, pencil hardness and scratch resistance are all excellent.
On the other hand, a hard coat film having a hard coat layer obtained from a hard coat agent containing only the polysilsesquioxane compound (A) and not containing the inorganic filler (B) is excellent in optical properties and pencil hardness, but heat resistant. It is inferior in properties and scratch resistance.
A hard coat film having a hard coat layer obtained from a silicon polymer other than the polysilsesquioxane compound (A) or a hard coat agent containing an organic polymer and an inorganic filler (B) is excellent in optical properties. , Pencil hardness, heat resistance and scratch resistance, or all are inferior.

Claims (3)

Below, (A) component, contains the component (B) and a photopolymerization initiator,
The content of the component (B) is 10% by mass to 70% by mass with respect to the component (A) .
The content of the photopolymerization initiator is 0.01 to 10% by weight based on the total solid content of the hard coating agent.
Is a hard coat agent.
Component (A): A polysilsesquioxane compound having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and the repeating unit represented by the formula (1). The content ratio of the unit is 10 mol% or more and 90 mol% or less in all the repeating units, and the content ratio of the repeating unit represented by the formula (2) is 10 mol% or more and 90 mol% or less in all the repeating units. And
Polysilsesquioxane compound

(R ¹ represents a reactive functional group, A represents a single bond or a divalent organic group having 1 to 10 carbon atoms. R ² represents an aryl group.)
Component (B): Inorganic filler having a reactive functional group
Photopolymerization initiators: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propane-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2 -Ethylanthraquinone, 2-tershari-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone One or more selected from dimethyl ketal and p-dimethylaminobenzoic acid ester A laminated film having a base material layer and a hard coat layer.
A laminated film in which the hard coat layer is formed by using the hard coat agent according to claim 1 . The laminated film according to claim 2, wherein the 5% weight loss temperature of the hard coat layer is 350 ° C. or higher.

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