TWI598418B - Anti-fingerprint adhesive and method for producing the same, composition for a hard coat film, base material having a hard coat layer and touch panel - Google Patents

Description

Anti-fingerprint adhesive agent, manufacturing method thereof, composition for hard coating film, substrate with hard coating layer, and touch panel Field of invention

The present invention relates to an anti-fingerprint adhesive agent, a method for producing the same, a composition for a hard coat film, a substrate having a hard coat layer, and a touch panel.

Background of the invention

Since the touch panel used in a smart phone or a tablet personal computer touches people's fingers when used, it is easy to adhere to fat dirt caused by fingerprints, sebum, sweat, and the like. Moreover, once the fat dirt adheres, it is difficult to fall off, and it is noticeable due to the degree of light, etc., which detracts from the problems of visibility and appearance. In addition, the same problem has been pointed out in display glasses, optical components, sanitary machines, and the like.

Here, as a means for solving the problem of adhesion of the grease stain, various techniques for forming an antifouling layer on the surface of the optical member have been proposed, and the antifouling layer has a property that the fat dirt is hard to adhere and is easily wiped off even if it adheres. In the optical member having the antifouling layer on the surface, the surface portion of the antifouling layer located at the outermost layer is easily damaged when it is wiped off. Therefore, when it is necessary to impart mechanical strength such as abrasion resistance to the surface of the substrate, it is necessary to provide a hard coat layer on the surface of the substrate, which has a problem that the manufacturing steps become complicated.

In order to solve the above problem, for example, it is described in Patent Document 1. A technique of applying a composition containing the following substance to a substrate and curing it to form a hard coat layer having excellent abrasion resistance and anti-fingerprint adhesion resistance, etc. An active energy ray-curable polymerizable monomer having a polyfunctional polymerizable monomer component of the above (meth) acrylonitrile group; an active energy ray-curable functional group, a water- and oil-repellent property-expressing portion, and a specific two-valent value in a molecular structure a water-based oil-repellent imparting agent; and an active energy ray polymerization initiator.

Further, Patent Document 2 describes a method for producing a fluoroorganopolysiloxane resin which is a composition for forming a film and which has a perfluoroalkyl group or a perfluoropolyether group. In the examples, a hydrofluorinated decane compound having a perfluoroalkyl group or a mixture thereof with a hydrolyzable decane compound having an organic group (having no fluorine atom) is hydrolyzed under specific conditions to obtain a fluoroorganic polyfluorene. Oxygen resin. Further, the film formed using the resin has excellent adhesion, scratch resistance, light resistance, antifouling property, water repellency, antireflection property, low refractive index, and transparency.

Prior technical literature Patent literature

Patent Document 1: International Publication No. 2004/044062

Patent Document 2: Japanese Patent No. 4711080

Summary of invention

However, in the hard coat layer obtained by using the composition described in Patent Document 1, the light resistance is insufficient for the antifouling property.

The fluoroorganopolysiloxane resin described in Patent Document 2 has a hydrolyzable decane compound having a perfluoroalkyl group having 8 carbon atoms as a raw material, and thus has a high environmental load. Further, the film obtained by the resin may have insufficient hardness. Here

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin which can be added to a photocurable hard coat film to impart sufficient hardness and antifouling property to the surface of the obtained hard coat layer. In particular, it is also capable of sufficiently protecting the appearance of the hard coat layer and the antifouling property, particularly the light resistance against fingerprint adhesion, the partial hydrolysis condensate having less environmental load, and the method for producing the same.

Still another object of the present invention is to provide a hard coat film which is blended with the above-mentioned partially hydrolyzed condensate and which can form a hard coat layer having sufficient hardness and antifouling property, particularly anti-fingerprint adhesion, light resistance and appearance. A composition, a substrate having a hard coat layer using the same, and a touch panel using the substrate having the hard coat layer.

The present invention provides an anti-fingerprint adhesive agent having the following composition [1] to [14], a method for producing the same, a composition for a hard coat film, a substrate having a hard coat layer, and a touch panel.

[1] An anti-fingerprint adhesive agent comprising a partially hydrolyzed condensate comprising a mixture of the following components: a hydrolyzable decane compound (a-1) represented by the following formula (a-1), and the following formula (a-2) The hydrolyzable decane compound (a-2) and the hydrolyzable decane compound (a-3) represented by the following formula (a-3); and the partial hydrolysis-condensation product has a fluorine atom content of 2.5 to 40% by mass.

The symbols in the formulae (a-1), (a-2) and (a-3) are as follows: R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms or represented by R ^f1 OR ^f2 - a valence group having 2 to 100 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^{f2 is a} perfluoroalkyl group having an etheric oxygen atom between carbon and carbon atoms); ¹ : a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom; Y: a group having an ethylenic double bond; Q ² : a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom; ^H1 , R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms; X ¹ , X ² , X ³ : a hydrolyzable group; p: an integer of 0 to 3; q: 1 or 2; r: 0 or 1 and q+r It is a number of 1 or 2.

However, when a plurality of X ¹ and a formula (a-2) or a formula (a-3) have a plurality of X ² , X ³ , R ^H1 , and YQ ² in the formula (a-1), they may be mutually The difference can also be the same.

[2] The anti-fingerprint adhesive agent according to [1], wherein the partial hydrolysis-condensation product has a fluorine atom content of 20 to 40% by mass, and the R ^f- based carbon number of the above formula (a-1) is 1 to 6 a perfluoroalkyl group or a valent group represented by R ^f1 OR ^f2 - and having 2 to 40 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 may have a carbon-carbon atom a perfluoroalkylene group of an etheric oxygen atom).

[3] A method for producing an anti-fingerprint adhesive agent, which is characterized in that the anti-fingerprint adhesive agent according to the above [1] or [2] is characterized in that a hydrolyzable decane compound is obtained in the presence of water, an organic solvent and an acid. The mixture is hydrolyzed and partially condensed to produce a partially hydrolyzed condensate having a fluorine atom content of 2.5 to 40% by mass; the hydrolyzable decane compound mixture is in a molar ratio with respect to the hydrolyzable decane compound represented by the above (a-1) (a-1) 100 mol, containing 1 to 23,000 mol of the above-mentioned hydrolyzable decane compound (a-2) represented by (a-2) and 20 to 11,500 mol of the foregoing (a-3) Hydrolyzable decane compound (a-3).

[4] The method for producing an anti-fingerprint adhesive agent according to [3], wherein the partially hydrolyzed condensate is a partially hydrolyzed condensate produced by hydrolyzing and partially condensing a hydrolyzable decane compound mixture, the hydrolyzable decane compound mixture being a molar The hydrolyzable decane compound (a-2) and the hydrolyzable decane compound (a) of 1 to 800 mol are contained in an amount of 1 to 800 mol per 100 mol of the hydrolyzable decane compound (a-1). -3).

[5] The method for producing an anti-fingerprint adhesive agent according to [3] or [4], wherein the water is added in an amount of 5 to 100 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture.

[6] The method for producing an anti-fingerprint adhesive agent according to [4], wherein the water is added in an amount of 5 to 40 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture.

[7] The method for producing an anti-fingerprint adhesive agent according to any one of [3] to [6], wherein The above organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C.

[8] The method for producing an anti-fingerprint adhesive according to any one of [3] to [7] wherein the acid is nitric acid.

[9] A composition for a hard coat film comprising the following partially hydrolyzed condensate and photopolymerizable component, wherein the content of the following partial hydrolyzed condensate in the total solid content of the composition is 0.01 to 20 mass Partially hydrolyzed condensate: a hydrolyzable decane compound (a-1) represented by the following formula (a-1), a hydrolyzable decane compound (a-2) represented by the following formula (a-2), and the following formula (a) -3) a partially hydrolyzed condensate of a mixture of hydrolyzable decane compounds (a-3), and a fluorine atom content of 2.5 to 40% by mass;

The symbols in the formulae (a-1), (a-2) and (a-3) are as follows: R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms or represented by R ^f1 OR ^f2 - a valence group having 2 to 100 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon and carbon atoms); ¹ : a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom; Y: a group having an ethylenic double bond; Q ² : a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom; ^H1 , R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms; X ¹ , X ² , X ³ : a hydrolyzable group; p: an integer of 0 to 3; q: 1 or 2; r: 0 or 1 and q+r It is a number of 1 or 2.

However, when a plurality of X ¹ and a formula (a-2) or a formula (a-3) have a plurality of X ² , X ³ , R ^H1 , and YQ ² in the formula (a-1), they may be mutually The difference can also be the same.

[10] The composition for a hard coating film according to [9], wherein the partial hydrolysis-condensation product has a fluorine atom content of 20 to 40% by mass, and the R ^f- based carbon number in the above formula (a-1) is 1 to 1 a perfluoroalkyl group of 6 or a valent group represented by R ^f1 OR ^f2 - and having 2 to 40 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is a carbon-carbon atom; a perfluoroalkyl group having an etheric oxygen atom).

[11] The composition for a hard coating film according to [9] or [10], wherein the photopolymerizable component contains a photopolymerizable compound and a photopolymerization initiator.

[12] The composition for a hard coat film according to any one of [9] to [11] wherein the film obtained by hardening the composition for the hard coat film is at least transparent to visible light.

[13] A substrate having a hard coat layer, comprising: a substrate; and a hard coat layer formed of the composition for a hard coat film according to any one of [9] to [11] A cured film of at least a part of the surface of the substrate.

[14] A touch panel comprising the substrate having a hard coat layer as in [13] above.

The anti-fingerprint adhesive of the present invention can be applied to a resin for a photocurable hard coat film to impart sufficient hardness and anti-fingerprint adhesion to the surface of the obtained hard coat layer. Moreover, these characteristics are excellent in light resistance and environmental load is also small.

The method for producing an anti-fingerprint adhesive of the present invention can produce an anti-fingerprint adhesion resistance which can be imparted to the surface of the obtained hard coat layer by using a resin for photocurable hard coat film. Fingerprint adhesive.

The composition for a hard coat film of the present invention can form a hard coat layer having a good appearance, sufficient hardness, antifouling property, and anti-fingerprint adhesion on a substrate.

The base material having a hard coat layer of the present invention and the touch panel using the base material having the hard coat layer have a good appearance of a hard coat layer, and have sufficient hardness, antifouling property, and excellent anti-fingerprint adhesion property. Excellent light resistance.

Form for implementing the invention

Embodiments of the present invention will be described below.

The "fingerprint" in the present specification is such that when the fingertip touches the surface of the article, the sweat and sebum components adhering to the fingertip are attached to the surface of the article in the form of a fingerprint pattern of the transfer fingertip.

The "total solid content" in the present specification is a hard coat layer forming component in the component contained in the composition for a hard coat film, and the composition of the hard coat film is heated at 140 ° C for 24 hours to remove the residue after the solvent is removed. . Specifically, it means solvent The total component other than the volatile component volatilized by heating or the like in the formation of the hard coat layer. However, the amount of total solids can also be calculated from the feed amount.

In the present specification, a film in which a composition for a hard coat film is applied is referred to as a "coating film", and a state in which it is dried is referred to as a "film", and a film obtained by curing it is referred to as a "cured film". Further, the hard coat layer formed using the composition for a hard coat film means the "cured film".

The term "(meth)acryloxyl group" as used in the present specification means "acrylomethoxy group..." and "methacryloxy group". ..." the meaning of both. In addition, the term "(meth)acryloyl group..." which will be described later means "acryloyl group" and "methacryloyl group" in the same manner.

The compound represented by the formula (a-1) in the present specification is referred to as the compound (a-1). Other compounds are also the same.

The partially hydrolyzed condensate in the present invention is hereinafter referred to as "partial condensate (A)". In addition, the "photopolymerizable compound" in the present invention is also called "photopolymerizable compound (B)", and the "photopolymerization initiator" is also called "photopolymerization initiator (C)".

The anti-fingerprint adhesion in the present specification means the property of both the water repellency and the removability of the attached fingerprint which do not adhere to the above-mentioned fingerprint. Anti-fingerprint adhesion and antifouling properties were evaluated by the values of water contact angle and oleic acid contact angle.

However, in the case where it is not particularly described in the present specification, the symbol % indicates the mass %.

[Anti-fingerprint adhesive]

The anti-fingerprint adhesive of the present invention is composed of a partial condensate (A), In other words, the hydrolyzable decane compound (a-1) represented by the following formula (a-1) and the hydrolyzable decane compound (a-2) represented by the following formula (a-2); And the hydrolyzable decane compound (a-3) represented by the following formula (a-3); and the partial hydrolysis-condensation product has a fluorine atom content of 2.5 to 40% by mass.

The symbols in the formulas (a-1), (a-2) and (a-3) are as follows.

R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group represented by R ^f1 OR ^f2 - and having 2 to 100 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, R ^F2 is a perfluoroalkyl group having an etheric oxygen atom between carbon-carbon atoms; Q ¹ : a divalent organic group having 1 to 10 carbon atoms and no fluorine atom; Y: having an ethylenic double bond a group; Q ² : a divalent organic group having 1 to 6 carbon atoms and no fluorine atom; R ^H1 and R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms; X ¹ , X ² and X ³ : a hydrolyzable group; p: an integer from 0 to 3; q: 1 or 2; r: 0 or 1 and q+r becomes the number of 1 or 2.

However, when a plurality of X ¹ and a formula (a-2) or a formula (a-3) have a plurality of X ² , X ³ , R ^H1 , and YQ ² in the formula (a-1), they may be mutually The difference can also be the same.

The partial condensate (A) of the present invention is a compound containing a fluorine atom derived from the hydrolyzable decane compound (a-1) in the above range, and can be formed by using a composition for a hard coat film containing the same. The surface of the coating layer imparts excellent water and oil repellency. It is considered that the water and the sebum component transferred from the fingertip to the surface by the water-repellent property of the surface of the hard coat layer are not adhered to the surface of the hard coat layer. The sebum component or the like in this state can be easily wiped off. That is, it can be said that the hard coat layer is imparted with excellent anti-fingerprint adhesion by using the partial condensate (A).

Further, the fluorine atom content in the partial condensate (A) is 2.5 to 40% by mass, preferably 3 to 40% by mass, more preferably 20 to 40% by mass, particularly preferably 25 to 40% by mass, and 30% by weight. 40% by mass is the best.

When it is at most the upper limit of the above range, the compatibility with the photopolymerizable compound (B) to be described later is good, and the appearance of the cured film and the anti-fingerprint adhesion are good. Further, the fluorine atom content ratio is a ratio of the mass of the fluorine atom per unit mass of the partial condensate (A), and can be calculated by a method described later.

The partial condensate (A) in the present invention contains a unit derived from the hydrolyzable decane compound (a-2), and the solubility and film-forming property of the partial condensate (A) with respect to the hydrocarbon-based solvent are preferable.

The partial condensate (A) in the present invention is radically polymerizable by containing a group having an ethylenic double bond derived from the hydrolyzable decane compound (a-3). It is preferable to bond with all of the ethylenic double bond groups of the photopolymerizable compound (B) which is a main component of the composition for a hard coat film containing the above, and it is possible to suppress the partial condensate (A) from the hard coat film. The layer leaks.

Further, the partial condensate (A) in the present invention preferably has a stanol group. The number of stanol groups is preferably from 0.2 to 3.5 per one cesium atom, preferably from 0.2 to 2.0, and preferably from 0.5 to 1.5. When the hard coat layer is formed using the composition for a hard coat film at the lower limit or more of the above range, the partial condensate (A) is difficult to evaporate from the surface of the substrate. When it is less than the upper limit of the above range, the hard coat film composition containing the partial condensate (A) has a partial condensate (A) which is difficult to aggregate and has good storage stability.

Further, the number of decyl alcohol groups in the partial condensate (A) was calculated from the ratio of the peak areas of the Si group having a stanol group and the Si group having no stanol group measured by ²⁹ Si-NMR.

The partial condensate (A) constituting the anti-fingerprint adhesive of the present invention is a mixture of hydrolyzable decane compounds containing hydrolyzable decane compounds (a-1) to (a-3) (hereinafter also referred to as "hydrolyzable decane compound mixture" Partially hydrolyzed condensate. Hereinafter, each hydrolyzable decane compound will be described.

(hydrolyzable decane compound (a-1))

The hydrolyzable decane compound (a-1) is a fluorine-containing hydrolyzable decane compound represented by the following formula (a-1).

R ^f -Q ¹ -SiX ¹ ₃ (a-1)

In the formula (a-1), R ^f is a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group having 2 to 100 carbon atoms represented by R ^f1 OR ^f2 - (R ^f1 is a carbon atom number 1~) 6 perfluoroalkyl group, R ^f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon-carbon atoms), and Q ¹ does not contain a divalent organic group having 1 to 10 carbon atoms and no fluorine atom X ¹ is a hydrolyzable group. However, the three X ¹ may be different from each other or the same. h

Since the compound (a-1) has R ^f , the hard coat layer formed of the composition for a hard coat film containing the partial condensate (A) can exhibit excellent anti-fingerprint adhesion. Since the compound (a-1) has R ^f , when the composition for a hard coat film containing the partial condensate (A) is applied to a substrate, the R ^f group is easily formed on the opposite side to the coated substrate. (ie the air side). That is, the partial condensate (A) is easily localized on the side opposite to the substrate.

In the formula (a-1), R ^f does not contain a perfluoroalkyl group having 7 or more carbon atoms from the viewpoint of environmental load and excellent solubility in a general-purpose solvent.

The structure of R ^f may be, for example, a linear structure, a branched structure, a ring structure, or a structure having a ring partially, and a linear structure is preferred.

Specific examples of the case where R ^f is a perfluoroalkyl group having 1 to 6 carbon atoms include the following groups.

F(CF ₂ ) ₄ -, F(CF ₂ ) ₆ -.

When R ^f is a valence group having 2 to 100 carbon atoms represented by R ^f1 OR ^f2 - (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 may have an ether between carbon-carbon atoms In the case of the perfluoroalkylene group of the oxygen atom, it is preferably from 2 to 80, more preferably from 2 to 40, from the viewpoint of compatibility with other hydrolyzable decane compounds.

R ^{f2 is} preferably (R ^f3 O) _x (wherein R ^f3 is a perfluoroalkyl group having 1 to 10 carbon atoms, and x is an integer of 1 to 99). R ^f3 may be linear or branched. From the standpoint of the ease of synthesis, the number of carbon atoms of R ^f3 is preferably from 1 to 5. Specific examples of (R ^f3 O) include the following.

(CF ₂ O), (CF ₂ CF ₂ O), (CF ₂ CF ₂ CF ₂ O), (CF(CF ₃ )CF ₂ O), (CF ₂ CF ₂ CF ₂ CF ₂ O), or the like.

When x is 2 or more, the (R ^f3 O) unit may be one type or two or more types, and the bonding order is not limited. It may be any configuration of blocks, randoms or interactions composed of complex units.

Specific examples of the case where the R ^f is a monovalent group having 2 to 100 carbon atoms represented by R ^f1 OR ^f2 - may be exemplified below.

CF ₃ OCF ₃ CF ₂ CF ₂ -, CF ₃ OCF(CF ₃ )CF ₂ -, CF ₃ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-.

F(CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ -, F(CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, F(CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ -, F(CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, F(CF ₂ ) ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-.

F(CF ₂ ) ₃ OCF ₂ -, F(CF ₂ ) ₃ OCF ₂ CF ₂ -, F(CF ₂ ) ₃ OCF(CF ₃ )-, F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ -, F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ -, F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-, F(CF ₂ ) ₃ OCF(CF ₃ ) CF ₂ OCF(CF ₃ )CF ₂ -, CF ₃ O(CF ₂ CF ₂ O) _x1 CF ₂ - (x1 is an integer from 1 to 49), F(CF ₂ ) ₃ O(CF(CF ₃ )CF ₂ O) _x2 CF(CF ₃ )-(x2 is an integer from 1 to 31), F(CF ₂ ) ₂ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _x3 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -(x3 is an integer from 1 to 15), F(CF ₂ ) ₂ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _x4 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ (x4 Is an integer from 1 to 15).

In the compound (a-1), Q ¹ is a divalent organic group having 1 to 10 carbon atoms and having no fluorine atom, and is a divalent organic group linking R ^f and a hydrolyzable decyl group (-SiX ¹ ₃ ). When Q ¹ is bonded to Si on the key on the right side and R ^f is on the bond on the left side, the base represented by the following is preferably: -(CH ₂ ) _i1 -(i1 is 1~5 Integer), -CH ₂ O(CH ₂ ) _i2 - (i2 is an integer from 1 to 4), -SO ₂ NR ¹ -(CH ₂ ) _i3 - (R ¹ is a hydrogen atom, methyl or ethyl, i3 1 or more and the total number of carbon atoms of R ¹ is an integer of 4 or less), -(C=O)-NR ¹ -(CH ₂ ) _i4 - (R ¹ is the same as above, and i4 is 1 or more and R The total number of carbon atoms of ¹ is an integer of 4 or less), -(CH ₂ ) _i5 -OC(=O)-(CH ₂ ) _i6 -S-(CH ₂ ) _i7 - (i5, i6 and i7 are each independently An integer from 1 to 5), -(CH ₂ ) _i5 -OC(=O)-(CH ₂ ) _i6 -NH-(CH ₂ ) _i7 - (i5, i6 and i7 are the same as above), -(CH ₂ ) _I5 -OC(=O)-(CH ₂ ) _i6 -N(CH ₃ )-(CH ₂ ) _i7 -(i5, i6 and i7 are the same as above), -(CH ₂ ) _i5 -OC(=O)- (CH ₂ ) _i6 -N(C ₆ H ₅ )-(CH ₂ ) _i7 - (i5, i6 and i7 are the same as above). As Q ¹ , -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ - and -(CH ₂ ) ₂ -OC(=O)-(CH ₂ ) ₂ -S-(CH ₂ ) ₃ - is preferred. Further, -(CH ₂ ) ₂ - and -(CH ₂ ) ₂ -OC(=O)-(CH ₂ ) ₂ -S-(CH ₂ ) ₃ - is particularly preferred.

Further, when R ^f is a perfluoroalkyl group, as the above Q ¹ , the group represented by the following is preferable: -(CH ₂ ) _i1 - (i1 is the same as above), -(CH ₂ ) _i5 -OC(=O) -(CH ₂ ) _i6 -S-(CH ₂ ) _i7 - (i5, i6 and i7 are the same as described above). I1 is preferably an integer of 2 to 4, and is preferably 2. I5, i6, and i7 are preferably integers of 2 to 4, respectively, and preferably 2 or 3.

Further, when R ^f is a perfluoroalkyl group having an etheric oxygen atom, the above-mentioned Q ^{1 is} preferably represented by the following groups (i1 to 4 and R ¹ are the same as defined above): -(CH ₂ ) _i1 -, - CH ₂ O(CH ₂ ) _i2 -, -SO ₂ NR ¹ -(CH ₂ ) _i3 -, -(C=O)-NR ¹ -(CH ₂ ) _i4 -. I1 is preferably an integer of 2 to 4, and is preferably 2.

In the formula (a-1), X ¹ represents a hydrolyzable group bonded to a ruthenium atom. Examples of X ¹ include a group in which an alkoxy group, an aryloxy group, a halogen atom, a decyloxy group, an amine group, and an amine group are substituted with an alkyl group. Among them, X ¹ is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom. The methoxy group and the ethoxy group are converted into a hydroxyl group (stanol group) by a hydrolysis reaction, and a reaction in which a molecule undergoes a condensation reaction to form a Si-O-Si bond tends to progress smoothly.

Preferable specific examples of the compound (a-1) include the following compounds.

F(CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , F(CF ₂ ) ₄ CH ₂ CH ₂ SiCl ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ SiCl ₃ .

CF ₃ OCF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₂ O(CF ₂ ) ₂ O(CF ₂ ) ₂ O(CF ₂ ) ₂ OCF ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ OCF(CF ₃ )CF ₂ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

F(CF ₂ ) ₂ O(CF ₂ ) ₂ OCF ₂ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₂ O(CF ₂ ) ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

F(CF ₂ ) ₃ O(CF ₂ ) ₂ CH ₂ CH ₂ SiCl ₃ , F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ O(CF ₂ CF ₂ O) _x1 CF ₂ C(=O)NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (x1 is an integer from 1 to 49), F(CF ₂ ) ₃ O(CF(CF) ₃ ) CF ₂ O) _x2 CF(CF ₃ )CH ₂ CH ₂ Si(OCH ₃ ) ₃ (x2 is an integer from 1 to 31), F(CF ₂ ) ₂ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ ) ₂ O(CF ₂ ) ₃ C(=O)NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (x3 is an integer from 1 to 15), F(CF ₂ ) ₂ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _x4 (CF ₂ ) ₂ O(CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (x4 is an integer of 1 to 15), F (CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH(CH ₃ CH ₂ SCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , [F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH ₂ ] ₂ NCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , [F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH (CH ₃ )CH ₂ ] ₂ NCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH(CH ₃ )NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH ₂ N(CH ₃ )CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH(CH ₃ )N(CH ₃ )CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH ₂ N(C ₆ H ₅ )CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ,F (CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH ₂ CH(CH ₃ )N(C ₆ H ₅ )CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

In the present invention, as the compound (a-1), it is particularly preferable to use F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ O(CF ₂ CF ₂ O) ₈ CF ₂ C(=O)NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ and KY-108 (Commodity Name, manufactured by Shin-Etsu Chemical Co., Ltd., having the above R ^f1 OR ^f2 -Q ¹ - group and 3 alkoxy decane compounds).

In addition, as for the hydrolyzable decane compound of the raw material of the partial condensate (A) in the present invention, the compound (a-1) may be used alone or in combination of two or more.

Further, in the partial condensate (A) of the present invention, the content of the compound (a-1) in the hydrolyzable decane compound mixture is such that the fluorine atom content in the partial condensate (A) obtained from the mixture becomes The amount of the above range.

(hydrolyzable decane compound (a-2))

The hydrolyzable decane compound (a-2) is a compound represented by the following formula (a-2) which is used as the hydrolyzable decane compound which is a raw material of the partial condensate (A) in the present invention together with the above compound (a-1).

R ^H1 _p -SiX ² _(4-p) ...(a-2)

In the formula (a-2), R ^H1 is a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a methyl group or an ethyl group, and a methyl group. good. The X ² -based hydrolyzable group may be the same as the plurality of X ¹ in the above formula (a-1) and includes the desired aspect. p is an integer from 0 to 3. However, two or three R ^H1 and (4-p) X ² when p is 2 or 3 may be different from each other or may be the same.

The compound (a-2) is preferably a 4-functional compound in which p is 0 or a 3-functional compound in which p is 1, and a tetra-functional compound is particularly preferable. The compound (a-2) may be used alone or in combination of two or more. When two or more types are used together, a bifunctional compound and/or a monofunctional compound may be used together with a tetrafunctional compound and/or a trifunctional compound.

In the partial condensate (A), water repellency is exhibited by R ^{f in} the unit derived from the compound (a-1). In addition, when p is 0 in the unit derived from the compound (a-2), the partial condensate (A) has an advantage of being excellent in film formability. In the unit derived from the compound (a-2), when p is 1, 2 or 3 (i.e., when R ^H1 is present), there is an advantage that a partial condensate can be obtained by the presence of R ^H1 to some extent (A). When a coating film of a composition for a hard coating film is formed on the surface of the substrate, it is easy to dissolve in a hydrocarbon-based solvent; and a relatively low-cost solvent can be selected.

Specific examples of the compound (a-2) include the following compounds. Further, as the compound (a-2), partial hydrolysis condensation of the compound (a-2) obtained by partially hydrolyzing and condensing a plurality of them in advance may be used as required. Things. On the other hand, in the case of other hydrolyzable decane compounds, a partially hydrolyzed condensate thereof can also be used.

Si(OCH ₃ ) ₄ , Si(OCH ₂ CH ₃ ) ₄ , CH ₃ Si(OCH ₃ ) ₃ , CH ₃ Si(OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si(OCH ₃ ) ₃ , CH ₃ CH ₂ Partially hydrolyzed condensate of Si(OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si(OCH ₃ ) ₂ , (CH ₃ ) ₂ Si(OCH ₂ CH ₃ ) ₂ , Si(OCH ₃ ) ₄ (eg COLCOAT) A partially hydrolyzed condensate of methyl decanoate 51 (trade name) and Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl decanoate 40 manufactured by COLCOAT Co., Ltd., ethyl decanoate 48. manufactured by Tama Chemical Industry Co., Ltd. Phthalate 45 (all are trade names)).

Further, the compound (a-2) may be used alone or in combination of two or more.

Further, the content of the hydrolyzable decane compound (a-2) in the hydrolyzable decane compound mixture is 100 mol with respect to the hydrolyzable decane compound (a-1), and the hydrolyzable decane compound (a-2) is 1 to 23,000 mol. It is better, preferably 1~15,000 Mo, better in 1~3,000 Mo, especially in 1~800 Mo, and best in 1~400 Mo.

(hydrolyzable decane compound (a-3))

The hydrolyzable decane compound (a-3) is a hydrolyzable decane compound containing a group having an ethylenic double bond represented by the following formula (a-3), and is used together with the above compound (a-1) and compound (a-2). The partial condensate (A) raw material of the present invention is used.

[Chemical 4]

In the formula (a-3), X ³ representing a hydrolyzable group may be the same as the plurality of X ¹ in the above formula (a-1) and include a desired aspect thereof. Further, R ^H2 may be the same as R ^H1 in the above formula (a-2) and include its ideal aspect.

Y in the formula (a-3) has a group having an ethylenic double bond, and Q ² is a divalent organic group having no fluorine atom and having 1 to 6 carbon atoms. q is 1 or 2, r is 0 or 1, and q+r is 1 or 2. However, when YQ ² and X ³ are present in a plurality of the above hydrolyzable decane compounds, they may be different from each other or may be identical to each other.

Since the compound (a-3) has Y, when the hard coat film containing the obtained partial condensate (A) is photocured by the film of the composition, the partial condensate (A) can be transmitted through the base on the surface of the film. The polymerization is carried out, or the partial condensate (A) and the photopolymerizable compound (B) contained in the composition for a hard coat film are polymerized with a vinyl double bond. Therefore, after photohardening, the partial condensate (A) is easily localized on the hard coat layer, especially on the surface thereof, and can impart the water-repellent property to the surface of the hard coat layer even after long-term use. And make the anti-fingerprint adhesion last.

As Y in the formula (a-3), a (meth) acryloxy group, an ethyl phenyl group or the like is preferable, and a (meth) propylene fluorenyl group is particularly preferable.

The Q ² in the formula (a-3) is a linking group in which a hydrolyzable decyl group (-SiX ³ _(4-qr) (R ^H2 ) _r ) is bonded to Y, and specifically, a carbon number of 2 to 6 is exemplified. The alkyl group and the phenyl group. Among them, -(CH ₂ ) ₃ - is preferred.

In the formula (a-3), when q is 2, the two YQ ² may be the same or different from each other, and when q+r is 1, the three X ³ may be the same or different from each other, and q+r is 2 When two X ^3s are the same or different from each other.

In the formula (a-3), it is preferred that q is 1 and r is 0 or 1.

Specific examples of the compound (a-3) include the following compounds.

CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ , CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , CH ₂ =CHCOO(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ , [CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ ]CH ₃ Si(OCH _{3 2} , [CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ ]CH ₃ Si(OC ₂ H ₅ ) ₂ .

In addition, as the hydrolyzable decane compound which is a raw material of the partial condensate (A) of the present invention, the compound (a-3) may be used alone or in combination of two or more.

Further, in the hydrolyzable decane compound mixture, the hydrolyzable decane compound (a-3) content is preferably from 20 to 11,500, more preferably from 20 to 8,000 mol, per 100 mol of the hydrolyzable decane compound (a-1). It is better in 20~2,000, especially in 20~300 mo, and the best in 50~200 mo.

The hydrolyzable decane compound mixture of the partial condensate (A) raw material of the present invention contains the above compound (a-1), the compound (a-2) and the compound (a-3), and may be obtained by, for example, upgrading according to the demand. The partial condensate (A) contains a hydrolyzable decane compound other than the compound for the purpose of compatibility with the composition for a hard coat film, control reactivity, and the like. The content of the other hydrolyzable decane compound in the hydrolyzable decane compound mixture is in the range of 2.5 to 40% by mass of the fluorine atom content of the obtained partial condensate (A) relative to the compound. The total amount of (a-1), the compound (a-2) and the compound (a-3) is preferably 100 to 1 mol.

The partial condensate (A) of the present invention is a hydrolyzable decane compound (a-1), a hydrolyzable decane compound (a-2), a hydrolyzable decane compound (a-3), and other hydrolyzability which are suitably blended according to the demand. A partially hydrolyzed condensate of a mixture of hydrolyzable decane compounds composed of a decane compound. In the partial condensate (A) of the present invention, a partial condensate (A) obtained by partially hydrolyzing and condensing a mixture of the following components (a-1) to (a-3) is preferred: hydrolyzable decane Compound (a-1), hydrolyzable decane compound (a-2), and hydrolyzable decane compound (a-3). In this case, the content of the hydrolyzable decane compound (a-1), the hydrolyzable decane compound (a-2), and the hydrolyzable decane compound (a-3) in the hydrolyzable decane compound mixture may be a partial condensate which can be obtained ( A) The content of the fluorine atom content in the range of 2.5 to 40% by mass is not particularly limited. For example, the hydrolyzable decane compound (a-2) is 1 based on 100 mol of the hydrolyzable decane compound (a-1). ~23,000 moles and hydrolyzable decane compound (a-3) is preferably 20 to 11,500 moles, and is 100 moles of hydrolyzable compound (a-1), hydrolyzable decane compound (a-2) The 1 to 800 moles and the hydrolyzable decane compound (a-3) are particularly preferred at 20 to 300 moles.

The partial condensate (A) of the present invention is a partially hydrolyzed condensate of a hydrolyzable decane compound mixture of the above-mentioned raw materials, and is usually a mixture of a plurality of condensates having different degrees of polymerization. In other words, for example, a mixture of a hydrolyzable decane compound (a-1), a hydrolyzable decane compound (a-2), and a hydrolyzable decane compound (a-3) is used as a raw material hydrolyzable decane compound to produce a partial condensate ( When A), it will become the average compositional expression represented by the following formula (1) Condensate.

However, since the partial condensate (A) is a product of a hydrolyzable group or a stanol group remaining (partially hydrolyzed condensate), it is difficult to express the product in a chemical formula, and the average composition formula represented by the formula (1) is assumed to be The hydrolyzable group or the stanol group in the partially hydrolyzed condensate produced as described above is a chemical formula in which all of the hydroxyl groups are bonded.

In the formula (1), the desirable ranges of R ^f , Q ¹ , R ^H1 , Y, Q ² , R ^H2 and p, q, r are the same as described above. The average number of units in a plurality of fluorine-containing decane compound mixtures having different degrees of polymerization of s, t, and u.

As shown by the formula (1), since the partial condensate (A) of the present invention has a polyoxyalkylene bond structure having a large bond energy and is a main chain, the light resistance is good.

It is presumed that in the partial condensate (A) having the average composition formula represented by the formula (1), the units derived from the compound (a-1), the compound (a-2), and the compound (a-3), respectively. The system presents a random arrangement. In the average composition formula (1), the ratio of the compound (a-2) to the compound (a-1) in the hydrolyzable decane compound mixture is preferably in the above range. Further, the s:u system is preferably contained in the above range as the ratio of the compound (a-3) to the compound (a-1) in the mixture. If it is expressed by s:t:u, it is preferable to have a relationship of 100:1 to 23,000:20 to 11,500 (mole ratio), and it is preferably 100:1 to 800:20 to 300 (mole ratio).

The number average molecular weight (Mn) of the partial condensate (A) of the present invention is preferably 500 or more and less than 10,000, more preferably 500 or more and less than 5,000, and still more preferably 500 or more and less than 3,000. When the number average molecular weight (Mn) is at least the above lower limit value and the hard coat layer is formed using the composition for a hard coat film, the surface condensate of the partial condensate (A) is high and a good resistance can be exhibited with a small amount of addition. Fingerprint adhesion, so that the hardness of the cured film is good. When the number average molecular weight (Mn) is less than the above upper limit, the partial condensate (A) is preferably compatible with the solvent or other components in the composition for a hard coat film. Further, it is difficult to phase separate, and the composition for a hard coat film is excellent in storage stability.

The number average molecular weight (Mn) of the partial condensate (A) can be adjusted by selecting reaction conditions and the like.

[Method for producing anti-fingerprint adhesive agent]

The partial condensate (A) having a fluorine atom content of 2.5 to 40% by mass in the anti-fingerprint adhesive of the present invention can be produced by hydrolyzing and partially condensing the hydrolyzable decane compound mixture, and the hydrolyzable decane compound mixture is The hydrolyzable decane compound (a-1), the hydrolyzable decane compound (a-2), and the hydrolyzable decane compound are contained in the content of the fluorine atom in the obtained partial condensate (A) in an amount of 2.5 to 40% by mass. A-3).

Specifically, it can be produced by a method for producing a partial condensate (A) comprising the following reaction step (hereinafter referred to as "reaction step (I)").

Reaction step (I): a step of hydrolyzing and partially condensing a hydrolyzable decane compound mixture in the presence of water, an organic solvent and an acid, and the hydrolyzable decane compound mixture is in a molar ratio with respect to the hydrolyzable decane compound ( A-1) 100 moles, containing 1 to 23,000 moles of hydrolyzable decane compound (a-2) And 20 to 11,500 moles of hydrolyzable decane compound (a-3).

The reaction for hydrolyzing and partially condensing is as described above by a hydrolysis reaction of a hydrolyzable group to form a stanol group and a reaction in which a decyl alcohol group is dehydrated and condensed with each other to form a siloxane coupling.

In the partial condensate (A), the fluorine atom content thereof is 20 to 40% by mass, and the R ^f- based perfluoroalkyl group in the hydrolyzable decane compound (a-1) has a perfluoroalkyl group having 1 to 6 carbon atoms or a monovalent group represented by R ^f1 OR ^f2 - and having 2 to 40 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 may have an etheric oxygen atom between carbon-carbon atoms) In the case of a perfluoroalkylene group, the reaction step (I) is a step of hydrolyzing and partially condensing the hydrolyzable decane compound mixture in the presence of water, an organic solvent and an acid, and the hydrolyzable decane compound mixture is in the form of a mole. The hydrolyzable decane compound (a-2) and the hydrolyzable decane compound (a-3) of 1 to 800 mol are contained in an amount of 100 mol with respect to the hydrolyzable decane compound (a-1). (hereinafter also referred to as reaction step (Ia)). In the following description, various conditions and the like of the reaction step (I) include the conditions of the reaction step (Ia) and the like. In the case of having conditions which are particularly suitable for the reaction step (Ia), further description will be given for the reaction step (Ia).

The amount of water used in the reaction step (I) is preferably from 5 to 100 parts by mass, more preferably from 5 to 80 parts by mass, per 100 parts by mass of the hydrolyzable decane compound mixture. In the case of the reaction step (Ia), the amount of water used is preferably from 5 to 40 parts by mass, more preferably from 5 to 25 parts by mass, per 100 parts by mass of the hydrolyzable decane compound mixture. By allowing the amount of water to be in the above range, the control of hydrolysis and partial condensation can be easily carried out.

The acid is used as a hydrolysis and partial condensation of the hydrolyzable decane compound. Catalyst works. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as acetic acid, oxalic acid, and maleic acid. Among them, nitric acid is preferred. The amount of the acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the hydrolyzable decane compound mixture.

The organic solvent to be used in the reaction step (I) may, for example, be an organic solvent generally used in the hydrolysis and condensation reaction of a hydrolyzable decane compound. Specific examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerin, and propylene glycol; acetone and methyl groups; Ketones such as isopropyl ketone and cyclohexanone; sirolimus such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2-(2-methoxyethoxy) Carbitol such as ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, lactate B Ester, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, B 3-ethoxy propionate, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerol triacetate, etc. Ester; and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl Ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene Alcohol monobutyl ether, dipropylene glycol monomethyl ether, and the like. In the reaction step (I), a fluorine-containing solvent such as hexafluoro-m-xylene or the like may be used as the organic solvent. These organic solvents can be used alone or in combination of two The above is used together.

In the present invention, the partial condensate (A) obtained is preferably a stanol group as described above. Further, the obtained partial condensate (A) is often blended with the composition for a hard coat film together with the organic solvent used in the reaction step (I). Therefore, as the organic solvent used in the reaction step (I), an organic solvent which stabilizes the above stanol group is preferably used. The organic solvent for stabilizing the stanol group may, for example, be a compound having a hydroxyl group and having a dielectric constant (?) of 5 to 20 at 25 °C.

Specific examples thereof include a glycol monoalkyl ether acetate solvent having 2 to 8 carbon atoms, a glycol monoalkyl ether solvent, a dimethyl ether solvent, and 2 to 4 carbon atoms. Hydrocarbon alcohol or the like. More specifically, as the diol-based monoalkyl ether acetate solvent, propylene glycol monomethyl ether acetate (ε: 8.3); and the diol-based monoalkyl ether solvent may be propylene glycol monomethyl Ether (ε: 12.3); as the hydrocarbon-based alcohol, 2-propanol (ε: 19.92) or the like can be mentioned. In particular, it is preferable to have a high stabilizing effect of a decyl alcohol group of a propylene glycol monomethyl ether capable of hydrogen bonding and a protic polar solvent.

From the viewpoint of sufficiently stabilizing the stanol group, the organic solvent is preferably composed of a compound having only a hydroxyl group and a dielectric constant (?) at 25 ° C of 5 to 20. However, the organic solvent may contain a compound other than the compound in accordance with the demand, and from the viewpoint of the stabilizing effect of the stanol group, the hydroxyl group is contained in the range of 10 to 100% by mass based on the total amount of the organic solvent and is at 25 ° C. The compound having a dielectric constant (?) in the range of 5 to 20 is preferable, and it is particularly preferably in the range of 20 to 100% by mass.

The reaction step (I) is preferably carried out at a temperature ranging from room temperature to the boiling point of the solvent. It is carried out under temperature and under appropriate stirring conditions. The reaction time is specifically determined depending on the amount of the raw material component to be used, the reaction temperature, the stirring conditions, and the like, but it is preferably 0.5 to 24 hours, and particularly preferably 1 to 18 hours. After the completion of the reaction, the obtained partial condensate (A) may be contained in the composition for a hard coat film of the present invention without removing the organic solvent. After the organic solvent is removed by a usual method, the partial condensate (A) is separated and then contained in the composition for a hard coat film.

[Composition for hard coating film]

The composition for a hard coat film of the present invention contains the partial condensate (A) and the photopolymerizable component, and the content of the partial condensate (A) is 0.01 to 20% by mass based on the total solid content of the composition. A composition for a coating film.

The photopolymerizable component contains the photopolymerizable compound (B), and further preferably contains a photopolymerization initiator (C).

The composition for a hard coat film of the present invention may further contain an organic solvent (D), cerium oxide fine particles (E), and other additives as needed.

It is preferable that the cured film of the film obtained by hardening the composition for a hard coat film of the present invention is at least transparent to visible light. The cured film is preferably a colorless transparent film, and may be a colored transparent film. When a colorless transparent film or a colored transparent film is obtained, the composition for a hard coat film is not preferably contained with an additive which inhibits the transparency of the cured film. For example, a colored powder such as a pigment is not suitable for being blended into a composition for a hard coat film because it hinders transparency. On the other hand, a powder composed of a transparent material having a refractive index substantially equal to that of the cured film such as cerium oxide microparticles (E) can be used as an additive for improving the abrasion resistance of the cured film without lowering the transparency. Mix with the composition for the hard coat film.

(partial condensate (A))

The composition for a hard coat film of the present invention contains the above partial condensate (A).

The content of the partial condensate (A) in the composition for a hard coat film of the present invention is 0.01 to 20% by mass based on the total solid content of the composition for a hard coat film, and preferably 0.1 to 10% by mass, and 0.1 to 5 mass%. % is especially good. By setting the content of the partial condensate (A) in the above range, the storage stability of the composition for a hard coat film can be improved. The surface of the hard coat layer obtained from the composition for a hard coat film is excellent in antifouling property or anti-fingerprint adhesion, and a hard coat layer having a surface having a good appearance can be obtained.

(Photopolymerizable compound (B))

The photopolymerizable compound (B) in the composition for a hard coat film of the present invention is a general term for a compound which is started by a polymerization reaction by irradiation with light and hardened by polymerization in the presence of a photopolymerization initiator (C) to be described later. Photopolymerization may be carried out only by the photopolymerizable compound (B) depending on the conditions or the kind, and it is usually used together with the photopolymerization initiator (C).

The photopolymerizable compound (B) preferably contains a polyfunctional monomer having two or more ethylenic double bonds in one molecule (hereinafter also referred to as "monomer (b-1)"). Further, it is preferable to contain a monofunctional monomer having one ethylenic double bond in one molecule (hereinafter also referred to as "monomer (b-2)"). The photopolymerizable compound (B) can be cured by irradiation with light such as ultraviolet rays, electron beams, X-rays, radiation, and high-frequency rays by containing the monomer (b-1). Further, the partial condensate (A) is a compound having an ethylenic double bond, and the photopolymerizable compound (B) does not contain a compound corresponding to the partial condensate (A).

As the monomer (b-1), it has two or more B in one molecule. The compound of the group of the ethylenic double bond (hereinafter also referred to as "polymerizable functional group") is not particularly limited. The polymerizable functional group is preferably an α,β-unsaturated group such as a (meth)acryl fluorenyl group, a vinyl group or an allyl group, and particularly preferably a (meth) acrylonitrile group. Among them, it is preferred to use an acrylonitrile group which is more easily polymerized by ultraviolet light. In addition, the monomer (b-1) may be a compound having two or more polymerizable functional groups in total in one molecule, or a compound having two or more identical polymerizable functional groups in total.

The number of the polymerizable functional groups in the molecule of the monomer (b-1) is two or more, and more preferably three or more. The upper limit of the number of the polymerizable functional groups of the monomer (b-1) molecule is not particularly limited, and is usually about 50 and preferably 30. Further, as the monomer (b-1), from the viewpoint of exhibiting high abrasion resistance, a compound having three or more polymerizable functional groups per molecule and having a molecular weight of 120 or less per one functional group is preferable. . The monomer (b-1) which satisfies the above conditions may, for example, be the following compounds.

A polyfunctional compound which is a polyester of neopentyl alcohol or a reaction product of polytetramethylenetetraol and (meth)acrylic acid, and has 3 or more and more preferably 4 to 20 (meth) acrylonitrile. base. Specifically, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI are exemplified. (Meth) acrylate, etc.

Further, a (meth)acryloyl group-containing compound having an urethane bond in the molecule (hereinafter also referred to as "ethyl urethane acrylate") has an urethane bond which functions as a hydrogen bond. At the cross-linking point, even if the molecular weight per one functional group is not as small as described above, a sufficient height of wear resistance can be exhibited. Consumable, quite ideal. As the monomer (b-1) satisfying the above conditions, the following compounds are preferred.

a polyfunctional compound which is a urethane urethane which is a reaction product of pentaerythritol or polytetramethylene glycol, a polyisocyanate and a hydroxyalkyl (meth) acrylate, and has 3 or more and more preferably 4 ~20 (meth)acrylonitrile groups.

a polyfunctional compound which is an urethane urethane which is a reaction product of a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate of pentaerythritol or polytetramethylene glycol, and has 3 or more and more preferably 4 ~20 (meth)acrylonitrile groups.

The monomer (b-1) may be used alone or in combination of two or more.

The monomer (b-2) is not particularly limited as long as it is a compound having one polymerizable functional group in one molecule. As the polymerizable functional group of the monomer (b-2), a (meth) acrylonitrile group is preferred.

Specific examples of the monomer (b-2) include CH ₂ =C(R ⁴ )COOC _z H _2z+1 (R ⁴ -based hydrogen atom or methyl group, z-system 1 to 13 integer. C _z H _2z+1 may be a linear structure or a branched structure represented by an alkyl (meth)acrylate. Further, as the monomer (b-2), allyl mono(meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, butanediol mono(methyl) may be mentioned. Acrylate, butoxy triethylene glycol (meth) acrylate, tributyl butyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, (methyl) 2-cyanoethyl acrylate, cyclohexyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-(meth)acrylate Diethylamine ethyl ester, N,N-dimethylaminoethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxylated) (meth)acrylate Oxy)ethyl ester, 2-ethylhexyl (meth)acrylate, glycerol mono(meth)acrylate, glycidyl (meth)acrylate, heptafluorodecyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-hydroxy-3-(methyl)propenyloxybutyltrimethylammonium chloride, 2-hydroxypropyl (meth)acrylate, 3-(methyl) ) acryloxypropyltrimethoxy decane, 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethyl Alcohol (meth) acrylate, methoxy tetraethylene glycol (meth) acrylate, dipropylene glycol methoxy (meth) acrylate, methyl ten ring carbon leukotriene oxide (meth) acrylate, Porphyrin (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, (A) Phenoxy butyl acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, benzene Ethoxy hexaethylene glycol (meth) acrylate, phenoxy (meth) acrylate, polypropylene glycol (meth) acrylate, sodium ethoxylate (meth) acrylate, (meth) acrylate Tetrafluorobutyl ester, tetrahydrofuran methyl (meth)acrylate, trifluoroethyl (meth)acrylate, vinyl acetate, N-vinyl caprolactam, N-vinylpyrrolidone, bicyclo(meth)acrylate Pentadienyl ester, isodecyl acrylate, and the like.

The monomer (b-2) may be used alone or in combination of two or more.

The content of the monomer (b-1) in the photopolymerizable compound (B) is preferably from 20 to 100% by mass based on the total amount of the photopolymerizable compound (B). When the ratio of the monomer (b-1) in the photopolymerizable compound (B) is in the above range, the hard coat layer composed of the cured film of the composition for a hard coat film is excellent in abrasion resistance. The ratio of the monomer (b-1) is preferably from 50 to 100% by mass, and particularly preferably from 70 to 100% by mass.

The content of the monomer (b-2) in the photopolymerizable compound (B) is preferably from 0 to 80% by mass based on the total amount of the photopolymerizable compound (B). When the ratio of the monomer (b-2) in the photopolymerizable compound (B) is in the above range, the hardness of the cured film is good and the film shrinkage ratio is appropriate, so that the substrate having the hard coat layer does not warp. The ratio of the monomer (b-2) is preferably 0 to 50% by mass, and more preferably 0 to 30% by mass.

Here, the monomer (b-1) and the monomer (b-2) may also be a plurality of monomers (b-1) or a plurality of monomers (b-1) and monomers (b-2) depending on the requirements. The form of (co)oligomer or pre (co)polymer obtained by (co)polymerization is used in advance. At this time, in terms of the content of the (co)oligomer or the pre-copolymer in the photopolymerizable compound (B), the content of the repeating unit derived from the monomer (b-1) is relative to the photopolymerization. The total amount of the compound (B) is from 20 to 100% by mass, and the content of the repeating unit derived from the monomer (b-2) is preferably from 0 to 80% by mass based on the total amount of the photopolymerizable compound (B). . Further, the ratio of the repeating unit derived from the monomer (b-1) is preferably from 50 to 100% by mass, and particularly preferably from 70 to 100% by mass. The ratio of the repeating unit derived from the monomer (b-2) is preferably from 0 to 50% by mass, and particularly preferably from 0 to 30% by mass.

The content of the photopolymerizable compound (B) in the total solid content of the composition for a hard coat film is preferably from 40 to 98.99% by mass, more preferably from 50 to 95% by mass, particularly preferably from 55 to 90% by mass.

(Photopolymerization initiator (C))

The photopolymerization initiator (C) used in the composition for a hard coat film of the present invention is not particularly limited as long as it has a function as a photopolymerization initiator, and is preferably a compound which generates a radical by light.

As the photopolymerization initiator (C), specifically, aryl ketone photopolymerization is exemplified. Initiators (for example, acetophenones, diphenylketones, alkylaminodiphenyl ketones, benzyls, benzoins, benzoin ethers, benzyldimethylketal) , benzoyl benzoic acid esters, α-mercapto oxime esters, etc.), sulfur-containing photopolymerization initiators (for example, sulfides, squalenes, etc.), mercaptophosphine oxides (for example) For example, mercaptodiarylphosphine oxides, and the like, and other photopolymerization initiators.

One type of the photopolymerization initiator (C) may be used alone or two or more types may be used in combination. Further, the photopolymerization initiator (C) may be used in combination with a photo sensitizer such as an amine.

The photopolymerization initiator may, for example, be the following compounds.

4-phenoxydichloroacetophenone, 4-tributyl-dichloroacetophenone, 4-tributyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2 -methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl) -2-methylpropan-1-one, 1-{4-(2-hydroxyethoxy)phenyl}-2-hydroxy-2-methyl-propan-1-one, 1-hydroxycyclohexylbenzene Ketone, 2-methyl-1-{4-(methylthio)phenyl}-2- Lolinylpropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, diphenyl Ketone, benzamidine benzoic acid, methyl benzoyl benzoate, 4-phenyldiphenyl ketone, hydroxydiphenyl ketone, propylene diphenyl ketone, 3,3'-dimethyl- 4-methoxydiphenyl ketone, 3,3',4,4'-fluorene (tertiary butylperoxycarbonyl)diphenyl ketone, 9,10-phenanthrenequinone, camphorquinone, dibenzocycloheptane Ketone, 2-ethylhydrazine, 4',4"-diethyliso-diphenylphthalic lactone, (1-phenyl-1,2-propanedione-2 (o-ethoxycarbonyl) ))), α-mercaptodecyl ester, methylphenylglyoxylate.

4-Benzylmercapto-4'-methyldiphenyl sulfide, thiazolone, 2-chlorothianicone, 2-methylthiane, 2,4-dimethylthio onion Ketone, isopropyl sulforaphane, 2,4-dichlorothiazepine, 2,4-diethylthiane, 2,4-diisopropylthione, 2,4, 6-trimethylbenzimidyl diphenylphosphine oxide, benzamidine diphenylphosphine oxide, 2,6-dimethylbenzimidyl diphenylphosphine oxide, double (2,6 -Dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide.

The content of the photopolymerization initiator (C) in the total solid content of the composition for a hard coat film is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, and particularly preferably from 3 to 10% by mass. In the above range, the compatibility with the photopolymerizable compound (B) in the composition for a hard coat film and the curability are good, and the hardness of the cured film formed is good.

(organic solvent (D))

The composition for a hard coat film of the present invention may further contain an organic solvent (D). By containing an organic solvent (D), the coating property of the composition to the substrate can be improved. Further, in the composition for a hard coat film, the partial condensate (A) can be stably present. The organic solvent (D) is further a part of the condensate (A), the photopolymerizable compound (B), and the photopolymerization initiator (C) which can be contained as a component of the hard coat film as an essential component. The cerium oxide fine particles (E) or other additives contained in the composition are uniformly dissolved or dispersed, and are not reactive with the respective components contained in the composition for a hard coating film, and are not particularly limited.

The organic solvent (D) may be used alone or in combination of two or more. The amount of the organic solvent (D) to be used is preferably 10,000 parts by mass or less based on 100 parts by mass of the photopolymerizable compound (B), and more preferably 5,000 parts by mass or less.

The organic solvent (D) is preferably a lower alcohol such as ethanol, butanol or isopropanol; a ketone such as methyl isopropyl ketone, methyl ethyl ketone or acetone; Ethers such as alkane, diethylene glycol dimethyl ether, tetrahydrofuran, methyl-tertiary butyl ether; and methyl stilbene, ethyl siroli, butyl siroli, propylene glycol monomethyl ether, etc. An organic solvent such as a glycol ether. Further, esters such as n-butyl acetate, isoamyl acetate, diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate; polyfluorohexane, polyfluoromethylcyclohexane, and polyfluoride can be used. a polyfluoroaliphatic hydrocarbon having 5 to 12 carbon atoms such as 1,3-dimethylcyclohexane; a polyfluorinated aromatic hydrocarbon such as bis(trifluoromethyl)benzene; and halogenation of a polyfluorinated aliphatic hydrocarbon Hydrocarbons; and hydrocarbons such as toluene, xylene, and hexane. From the viewpoint of good coatability of the composition for a hard coat film, n-butyl acetate which is suitable for the solubility and evaporation rate of the photopolymerizable compound (B) is particularly preferable.

Further, as described above, from the viewpoint that the partial condensate (A) can be stably present in the composition for a hard coating film, the dielectric constant (?) having a hydroxyl group at 25 ° C is in the range of 5 to 20 The compound is preferred. In particular, it is preferable that the stanol group of propylene glycol monomethyl ether which can be hydrogen-bonded to a protic polar solvent has a high stabilizing effect.

From the point of view of the stabilizing effect of the stanol group, it is preferred to contain a compound having a hydroxyl group in the range of 10 to 100% by mass and a dielectric constant (?) in the range of 5 to 20 at 25 ° C with respect to the total amount of the organic solvent. It is particularly preferably in the range of 20 to 100% by mass.

When the composition for a hard coat film contains an organic solvent (D), it is preferable to select an appropriate organic solvent (D) depending on the type of the substrate on which the hard coat layer is formed. For example, when the substrate is an aromatic polycarbonate resin having low solvent resistance, it is preferred to An organic solvent (D) having a low solubility with respect to the aromatic polycarbonate resin is used, and a mixture of a lower alcohol, a glycol ether, an ester, an ether, and the like is suitably used.

(cerium oxide microparticles (E))

The composition for a hard coat film of the present invention may contain cerium oxide microparticles (E) as needed. The wear resistance of the hard coat layer can be improved by containing cerium oxide microparticles (E).

As the cerium oxide microparticles (E), colloidal cerium oxide is preferred. The colloidal cerium oxide is an ultrafine particle of phthalic anhydride which is dispersed in a colloidal state in a dispersion medium, and the dispersion medium is not particularly limited, and water, a lower alcohol, and a serotonin are preferable. Specific examples of the dispersion medium include water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, methyl stilbene, ethyl serosol, butyl siroli, propylene glycol monomethyl ether B. Acid ester, dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, amyl acetate, acetone, and the like.

The average particle diameter of the cerium oxide fine particles (E) is not particularly limited, and is preferably 1 to 1,000 nm, more preferably 1 to 200 nm, and 1 to 1 in order to exhibit high transparency in a hard coating film which is a cured film after curing. 50nm is especially good.

In order to improve the dispersion stability of the cerium oxide microparticles (E), the hydrolyzate of the hydrolyzable decane compound may be used to modify the surface of the microparticles. Here, "the surface modified with a hydrolyzate" means a state in which a hydrolyzate of a hydrolyzable decane compound is physically or chemically bonded to a part or all of a stanol group on the surface of the cerium oxide microparticle (E), and thereby the surface is made The characteristics are modified. Further, cerium oxide microparticles bonded by a partial condensate of the hydrolyzate are also included. Surface modification, for example, by making water in the presence of cerium oxide microparticles The partial or total hydrolysis of the hydrolyzable group of the decane compound may be carried out by hydrolysis or condensation reaction.

The hydrolyzable decane compound is a hydrolyzable group such as an organic group having a functional group such as a (meth)acryl fluorenyl group, an amine group, an epoxy group or a decyl group, or a hydrazine compound having a hydroxyl group bonded to a ruthenium atom. good.

When the cerium oxide fine particles (E) are contained, the content thereof is preferably 0.1 to 500 parts by mass, more preferably 1 to 300 parts by mass, and particularly preferably 10 to 200 parts by mass, per 100 parts by mass of the photopolymerizable compound (B). . In the above range, abrasion resistance is sufficient in the hard coat layer which is a cured film after curing, and it is easy to maintain high transparency, and it is difficult to cause cracks or the like due to an external force.

(other additives)

The composition for a hard coat film of the present invention may be selected from the group consisting of ultraviolet absorbers, light stabilizers, antioxidants, and thermal polymerizations as needed in addition to the above-described additives without damaging the effects of the present invention. Inhibitor, leveling agent, antifoaming agent, tackifier, anti-settling agent, pigment (organic coloring pigment, inorganic pigment), coloring dye, infrared absorbing agent, fluorescent whitening agent, dispersing agent, conductive microparticle, anti-resistance One or more additives selected from the group consisting of an electrostatic agent, an antifogging agent, and a coupling agent.

In addition, the composition for a hard coat film of the present invention may be a photocurable resin composition for forming a commercially available hard coat film (hereinafter also referred to as "resin composition (Y)"), with respect to the resin composition. (Y) The total mass of the total solid content and the partial condensate (A), and the partial condensate (A) is contained in a ratio of 0.01 to 20% by mass. The commercially available resin composition for forming a hard coat film (Y) usually contains a photopolymerizable compound (B) as a photopolymerizable component, and more often contains a photopolymerizable component. The initiator (C) is contained in the same manner as described above in accordance with the demand.

Specific examples of the commercially available resin composition for forming a hard coat film (Y) include a hard coat film HC162 (trade name, manufactured by Yokohama Rubber Co., Ltd.) and a hard coat film BEAMSET 575 (CB) (trade name, Arakawa Chemical Co., Ltd.). Industrial company system).

[Substrate with hard coating layer]

The substrate having a hard coat layer of the present invention comprises: a base material; and a hard coat layer formed of a cured film formed on the surface of at least a part of the base material by the composition for a hard coat film of the present invention.

The base material for forming the hard coat layer is generally not particularly limited as long as it is composed of a material having a hard coat layer which is required to form antifouling properties, particularly anti-fingerprint adhesion, and is preferably used as a metal. A substrate composed of glass, resin, ceramic, or a combination thereof (composite material, laminated material, etc.). In particular, a transparent substrate such as glass or resin is preferred.

Examples of the glass include ordinary soda lime glass, borosilicate glass, alkali-free glass, and quartz glass.

In the present invention, when a resin substrate which is a transparent resin and which has antifouling properties, particularly anti-fingerprint adhesion and abrasion resistance, is used as a substrate capable of forming a hard coat layer, a remarkable effect can be exerted. Quite ideal.

Specific examples of the resin include an aromatic polycarbonate resin, a polymethyl methacrylate resin, a polymethacrylimide resin, a polystyrene resin, a polyvinyl chloride resin, and an unsaturated polyester resin. Polyolefin resin, ABS resin, and MS (methyl methacrylate styrene) resin.

The shape of the substrate or the surface on which the hard coat layer is formed is not particularly limited and may be appropriately selected depending on the application. When the substrate is in the form of a plate, it can be a flat plate. The entire surface or a portion may have a curvature. The thickness of the substrate can be appropriately selected in accordance with the use of the substrate having the hard coat layer, and is generally preferably 0.5 to 10 mm.

For the substrate used in the present invention, it may also be subjected to acid treatment on the surface (using diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.) or alkali treatment (using aqueous sodium hydroxide solution, etc.) for the purpose. ) or discharge treatment (plasma irradiation, corona irradiation, electron beam irradiation, etc.).

As a method of forming a hard coat layer on the surface of the substrate, a method similar to the method of forming a hard coat layer on a substrate using a composition for a hard coat film mainly composed of a photopolymerizable compound (B) can be suitably used. Specifically, it can be produced by the following method: (1) a coating film forming step of applying a composition for a hard coating film onto a predetermined surface of a substrate to form a coating film (however, the composition for a hard coating film contains no solvent) In this case, the obtained coating film becomes a "film" containing no solvent); (2) a solvent removing step, removing the solvent from the coating film on the substrate according to the demand and forming a film; (3) a photohardening step to the substrate The upper film is irradiated with light to form a hard coat layer which is a cured film.

(coating film (film) forming step)

The method of applying the composition for a hard coat film to the surface of the substrate is not particularly limited, and a known method can be applied. Specifically, methods such as dip coating, spin coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, and air knife coating may be mentioned. Here, the thickness of the coating film or the film can be adjusted so that the thickness of the hard coat film which is the hardened film after photohardening becomes the thickness mentioned later.

(Solvent removal step)

When a coating film containing a solvent is formed on a substrate, it is usually used for The drying of the solvent is removed. Although the drying conditions depend on the composition for the hard coat film to be used, it is generally carried out at 40 to 120 ° C for about 0.5 to 5 minutes.

(photohardening step)

Next, the film on the substrate is irradiated with light, and the photohardenable component in the film is reactively cured to form a cured film to form a hard coat layer. As the light used for light irradiation, ultraviolet rays, electron beams, X-rays, radiation, and high-frequency rays are preferable, and ultraviolet rays having a wavelength of 180 to 500 nm are economically preferable. As the light source, an ultraviolet irradiation device such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp, an electron beam irradiation device, an X-ray irradiation device, and a high frequency generating device can be used.

The conditions of the light irradiation can be appropriately changed depending on the kind of the photopolymerizable compound (B), the kind of the photopolymerization initiator (C), the film thickness, the type of the light source, and the like. The condition as the exposure amount to the film is usually preferably from 100 to 5,000 mJ/cm ^{2 and more} preferably from 100 to 1,000 mJ/cm ² . In terms of exposure time, it is preferably 0.1 to 60 seconds, and preferably 0.5 to 30 seconds. Further, heat treatment may be performed after the light irradiation for the purpose of completing the hardening reaction.

The thickness of the cured film, that is, the hard coat layer, can be various thicknesses as desired. The thickness of the hard coat layer is preferably 0.1 to 50 μm, more preferably 0.2 to 20 μm, and particularly preferably 0.3 to 10 μm. When the thickness of the hard coat layer is in the above range, the abrasion resistance is sufficient and the hardening of the deep portion of the hard coat layer is sufficient, which is preferable.

The hard coat layer formed on the surface of the substrate in this manner is excellent in transparency, and has a sufficient hardness on the surface thereof, and is excellent in water repellency and oil repellency. Excellent anti-fingerprint adhesion. The water-repellent property associated with the surface of the hard coat layer of the substrate having the hard coat layer of the present invention depends on the function of the partial condensate (A) contained in the composition for a hard coat film.

When the partial condensate (A) is blended into the composition for a hard coat film and the hard coat layer is formed by the above method, the partial condensate (A) is bonded to the main constituent component of the hard coat layer, that is, photopolymerizability. Compound (B). The hard coat layer, particularly on the surface, exhibits excellent water repellency and oil repellency obtained by the fluorine-containing organic group of the partial condensate (A). Further, when the partial condensate (A) and the photopolymerizable compound (B) are bonded to each other, leakage from the hard coat layer is hardly generated, and excellent water repellency and oil repellency can be exhibited for a long period of time. Therefore, the surface of the hard coat layer of the substrate having the hard coat layer of the present invention has excellent antifouling properties, particularly anti-fingerprint adhesion, and is difficult to adhere to grease stains, even if there is grease stain such as sebum, sweat, and cosmetics. The attachment can also be easily removed.

From the point of view of the above-described characteristics of the substrate having the hard coat layer of the present invention, it can be effectively used as a touch panel for smart phones and tablet personal computers, etc., which are effective for viewing grease stains, especially fingerprints. Components such as display glass, optical components, and sanitary machines. In particular, a remarkable effect can be obtained when used in a touch panel.

<Touch Panel>

The touch panel of the present invention has the above-described substrate having a hard coat layer of the present invention. The touch panel is provided with a substrate having a hard coat layer so that the hard coat layer is exposed on the touch surface, and can be designed in the same manner as a normal touch panel.

Example

The invention is further illustrated in the following examples, but the invention is not limited by the examples. Examples 1 to 3, 9 to 11, 18, 19, 21 to 24, and 26 are examples, and examples 4 to 8, 12 to 16, 20, and 25 are comparative examples, and example 17 is a reference example.

Each measurement system was carried out in the following manner.

[Number average molecular weight (Mn)]

Gel permeation chromatography (GPC) of several monodisperse polystyrene polymers having different commercial polymerization degrees as standard samples for molecular weight measurement was measured using a commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC) ), and the detection line is prepared based on the relationship between the molecular weight of polystyrene and the retention time (residence time).

After the sample was diluted to 1.0% by mass in tetrahydrofuran and passed through a filter of 0.5 μm, the GPC of the sample was measured using the GPC measuring apparatus.

The number average molecular weight (Mn) of the sample was determined by analyzing the GPC spectrum of the sample by a computer using the above-mentioned detection line.

[Fluorine content]

The fluorine atom content was determined by ¹⁹ F NMR measurement using 1,4-bistrifluoromethylbenzene as a standard material.

[water contact angle]

Water droplets were dripped on the measurement surface 3 on the substrate in accordance with JIS R 3257 "Test method for wettability of the surface of the substrate glass" by the non-drop method, and the water droplets were measured. The droplet system was about 2 μL/drop and the assay was carried out at 20 °C. The contact angle is expressed as the average of 3 measured values (n=3). And, from anti-fingerprint attachment From the point of view of sex, the water contact angle can be used as long as it is about 90 degrees or more, and preferably about 95 degrees or more.

[oleic acid contact angle]

The oleic acid droplets were dropped on the measurement surface 3 of the substrate in accordance with JIS R 3257 "Test method for wettability of the surface of the substrate glass" by the non-drop method, and each oleic acid droplet was measured. The droplet system was about 2 μL/drop and the assay was carried out at 20 °C. The contact angle is expressed as the average of 3 measured values (n=3). Further, from the viewpoint of anti-fingerprint adhesion, the oleic acid contact angle can be used as long as it is approximately 55 degrees or more, and preferably about 60 degrees or more.

[The appearance of the cured film]

The appearance of the cured film was evaluated by visual inspection in accordance with the following criteria.

○ (good): Foreign matter could not be confirmed and the film thickness was uniform.

△ (may): Although the foreign matter could not be confirmed, the film thickness was uneven.

× (defect): Foreign matter can be confirmed.

[Ink repellency]

The ink repellency after the initial and following light resistance tests was evaluated. The ink repellency was evaluated by scribing the surface of the obtained cured film with a crayon (manufactured by ZEBRA, product name: MACKEE very fine black) and visually observing the adhesion state of the ink. The evaluation criteria are as follows.

◎ (Excellent): The ink repellency is good and the ink can be plucked into a bead shape.

○ (good): The ink cartridge cannot be made into a bead shape and a linear plucking is generated (the line width is less than 50% of the width of the tip of the stylus pen).

△ (may): A linear plucking of the ink is produced and the line width is 50% or more and less than 100% of the width of the tip of the stylus pen.

× (bad): There is no way to print the ink and draw a complete line on the surface.

[Light resistance test]

The obtained cured film was exposed to a cycle of rain at 12 minutes and dried for 48 minutes at a blackboard temperature of 63 ° C for 500 hours using a sunshine weather tester.

[pencil hardness]

The measurement was carried out in accordance with JIS K 5600.

The compounds used in the examples of the composition for a hard coat film and the substrate having a hard coat layer are as follows.

(partial condensate (A))

The partial condensate solutions (A1-1) to (A6-1), (A8-1) to (A11-1), (X1-1) obtained in the following Examples 1 to 6, 8 and 18 to 21 were used. And a partial condensate (A7) obtained in Example 7.

(Photopolymerizable compound (B))

B-1: dipentaerythritol hexaacrylate.

B-2: ginseng (propylene oxyethyl) iso-cyanate.

(Photopolymerization initiator (C))

C-1: 2-methyl-1-(4-methylthiophenyl)-2- Lolinyl-propan-1-one

(organic solvent (D))

D-1: n-butyl acetate.

D-2: propylene glycol monomethyl ether (hereinafter also referred to as "PGME").

(cerium oxide microparticles (E))

Addition of 3-methylpropenyloxypropane to E-1: isopropanol-dispersed colloidal cerium oxide (cerium oxide content: 30% by mass, average particle diameter: 11 nm), 100 parts by mass 2.5 parts by mass of methoxytrioxane and stirred at 50 ° C for 3 hours, and then aged at room temperature for 12 hours to obtain a cerium oxide cerium having a hydrolyzed condensate of a decane compound having a methacryl oxime group on the surface.

[Example 1: Production of partial condensate (A1) and partial condensate liquid (A1-1)]

Into a 2 liter flask equipped with a stirrer, 46.75 g of CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (manufactured by Asahi Glass Co., Ltd.) of the above compound (a-1) and the above compound (a-2) were placed. 12.45 g of Si(OCH ₂ H ₅ ) ₄ (manufactured by COLCOAT Co., Ltd.) and 40.8 g of CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) of the above compound (a-3). Next, 607 g of PGME and 12.02 g of water were placed to prepare a mixture.

While stirring the mixture at room temperature, 0.20 g of a 60% aqueous solution of nitric acid was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 5 hours. A PGME solution containing 10% by mass of the obtained partial condensate (A1) was used as a partial condensate liquid (A1-1). The partial condensate (A1) had a fluorine atom content of 34.3% by mass and a number average molecular weight (Mn) of 740.

In Table 1, the raw material composition of the partial condensate (A1) and the amount of each component used in the production are indicated by mass (g). Further, the relevant raw material composition will be expressed by combining the molar numbers of the compound (a-1) at 100 mol. The amount of each component used for the production is a combination of the mass parts when the total amount of the compounds (a-1) to (a-3) is 100 parts by mass. Further, the fluorine atom content ratio and the number average molecular weight (Mn) are combined and expressed.

[Examples 2 to 6: Preparation of partial condensate (A2) to (A6) and partial condensate (A2-1) to (A6-1)]

The partial condensates (A2) to (A6) and the partial condensate solutions (A2-1) to (A6-1) were obtained in the same manner as in Example 1 except that the raw materials were blended and changed as shown in Table 1.

[Example 7: Production of partial condensate (A7)]

The raw material blending was changed to as shown in Table 1. Upon completion of the reaction, a white oily ester precipitated. The white oil ester was filtered and washed with ion-exchanged water until the pH became 6 to 7, and dried under reduced pressure at 60 ° C for 3 hours to obtain a slightly viscous white solid resin. The obtained resin was used as a partial condensate (A7).

[Example 8: Production of partial condensate (A8) and partial condensate liquid (A8-1)]

40 mg of tetraisobutylene titanate and C ₃ F ₇ (OCF ₂ CF ₂ CF ₂ ) ₂₀ O(CF ₂ ) ₂ CH ₂ OH (manufactured by Daikin Industries Co., Ltd.) in a 300 mL four-necked flask equipped with a stirrer and a cooling tube. Product name: DEMNUM SA, number average molecular weight (Mn): 4,000) 100 g and ε-caprolactone 10 g, and heated at 150 ° C for 5 hours. A white waxy compound obtained by ring-opening addition of ε-caprolactone to one end of C ₃ F ₇ (OCF ₂ CF ₂ CF ₂ ) ₂₀ O(CF ₂ ) ₂ CH ₂ OH was obtained. The compound has a number average molecular weight (Mn) of 4,400 and a caprolactone polymerization degree of about 3.5.

Next, the compound was cooled to room temperature, and 50 g of hexafluorom-xylene and 60 mg of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred for 30 minutes. 6.0 g of 2-methylpropenylmethoxyethyl isocyanate was added, and further stirred at room temperature for 24 hours to obtain a hexafluorom-xylene solution containing a partial condensate (A8) modified with a methacryl oxime group (containing A partial condensate liquid (A8-1) of 70% by mass of the partial condensate (A8)). Table 1 shows partial condensate solution The composition of (A8-1) and the fluorine atom content and the number average molecular weight (Mn) of the partial condensate (A8).

[Example 9: Composition of a hard coating film and production of a substrate having a hard coating layer]

Into a 300-mL four-necked flask equipped with a stirrer and a cooling tube, 10 g of the liquid (A1-1) produced in Example 1, 80 g of a photopolymerizable compound (B-1), and 4 g of a photopolymerization initiator (C-1) were placed. 100 g of an organic solvent (D-1) was stirred for 1 hour at normal temperature and in a state of being shielded from light. Next, slowly add the glue while stirring 75 g of cerium oxide (E-1) was further stirred at normal temperature and in a state of being shielded for 1 hour to obtain a composition 1 for a hard coating film.

Next, the composition 1 of the hard coat film was applied onto the surface of the PET substrate by a bar coating method, and dried on a hot plate at 50 ° C for 1 minute to form a film on the surface of the substrate. Next, light irradiation was performed using a high pressure mercury lamp (light quantity: 300 mJ/cm ² , ultraviolet integral energy of wavelength 365 nm). As a result, a cured film having a thickness of 5 μm was formed on the surface of the substrate. The cured film (hard coat layer) was evaluated in the above manner. The results are shown in Table 2 together with the composition of the composition for a hard coat film.

[Examples 10 to 17: Composition of a hard coating film and production of a substrate having a hard coating layer]

The partial condensate solutions (A1-1) to (A6-1), (A8-1) obtained in Examples 1 to 6 and 8, and the partial condensate (A7) obtained in Example 7, and a photopolymerizable compound (B) The composition for a hard coat film 2-2 was produced in the same manner as in Example 9 except that the photopolymerization initiator (C), the organic solvent (D), and the colloidal cerium oxide (E) were changed as shown in Table 2. 9. A cured film (hard coat layer) was formed on the PET substrate in the same manner as in Example 9 and evaluated. The results are shown in Table 2 together with the composition of the composition for a hard coat film.

[Example 18: Production of partial condensate (A9) and partial condensate liquid (A9-1)]

CF ₃ O(CF ₂ CF ₂ O) ₈ CF ₂ C(=O)NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) _{3 of the} above compound (a-1) was added to a 2 liter flask equipped with a stirrer (according to international disclosure) Example 2 of the No. 2009/008380) 3.3 g of Si(OC ₂ H ₅ ) ₄ (manufactured by COLCOAT Co., Ltd.) of the above compound (a-2) and CH ₂ =CHCOO of the above compound (a-3) ( CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) 34.6 g. Next, 530 g of hexafluorom-xylene and 227 g of 2-propanol were added to prepare a mixture.

While the mixture was stirred at room temperature, 59.7 g of a 1% aqueous solution of nitric acid was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 5 hours. The obtained solution containing the 5% by mass of the partial condensate (A9) was used as a partial condensate liquid (A9-1). The fluorine atom content of the partial condensate (A9) is 3.9% by mass and the number The average molecular weight (Mn) was 1,160.

[Example 19: Production of partial condensate (A10) and partial condensate liquid (A10-1)]

To a 2 liter flask equipped with a stirrer, KY-108 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) of the above compound (a-1), 5.2 g of the compound (a-2), and Si(OC ₂ H ₅ ) ₄ (COLCOAT) of the above compound (a-2) were added. 60.7 g of the compound (a) and 34.1 g of CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) of the above compound (a-3). Next, 537 g of hexafluoro-m-xylene and 230 g of 2-propanol were added to prepare a mixture.

While the mixture was stirred at room temperature, 57.6 g of a 1% aqueous solution of nitric acid was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 5 hours. The resulting solution containing 7 mass% of the partial condensate (A10) was used as a partial condensate liquid (A10-1). The partial condensate (A10) had a fluorine atom content of 7.4% by mass and a number average molecular weight (Mn) of 1,230.

[Example 20: Production of partial condensate (X1) and partial condensate liquid (X1-1)]

In a 2 liter flask equipped with a stirrer, CF ₃ O(CF ₂ CF ₂ O) ₈ CF ₂ C(=O)NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) _{3 of the} above compound (a-1) was placed (according to international Manufactured in Example 2 of the publication No. 2009/008380), 1.7 g of the compound (a-2), Si (OC ₂ H ₅ ) ₄ (manufactured by COLCOAT Co., Ltd.), 62.8 g, and the compound (a-3), CH ₂ =CHCOO (CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) 35.5 g. Next, 526 g of hexafluoro-m-xylene and 226 g of 2-propanol were added to prepare a mixture.

While the mixture was stirred at room temperature, 61.3 g of a 1% aqueous solution of nitric acid was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 5 hours. The obtained solution containing the 5% by mass of the partial condensate (X1) is a partial condensate solution (X1-1). The partial condensate (X1) had a fluorine atom content of 2.1% by mass and a number average molecular weight (Mn) of 1,150.

[Example 21: Production of partial condensate (A11) and partial condensate liquid (A11-1)]

In a 2 liter flask equipped with a stirrer, F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)C(CH ₃ )=CH ₂ 88.0 g, HSCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) was added under a nitrogen atmosphere. ₃ 40.0 g and 2,2'-azobisisobutyronitrile (AIBN) 0.33 g. Next, 710 g of hexafluorom-xylene and 304 g of 2-propanol were added to prepare a mixture.

The mixture was stirred at 70 ° C for 12 hours to obtain 10% by mass of F(CF ₂ ) ₆ CH ₂ CH ₂ OC(=O)CH(CH ₃ )CH ₂ SCH ₂ CH ₂ CH. ₂ Si(OCH ₃ ) ₃ (compound (a-1-11)).

In a 1 liter flask equipped with a stirrer, 162 g of a 10% solution of the compound (a-1-11) of the above compound (a-1) and Si(OC ₂ H ₅ ) _{4 of} the compound (a-2) (manufactured by COLCOAT Co., Ltd.) were added. 53.6 g and 30.2 g of CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) of the above compound (a-3). Next, 149 g of hexafluoro-m-xylene and 64 g of 2-propanol were added to prepare a mixture.

The mixture was stirred while stirring at room temperature with 53.8 g of a 1% aqueous solution of nitric acid. After the completion of the dropwise addition, the mixture was further stirred for 5 hours. The resulting solution containing 10% by mass of the partial condensate (A11) was used as a partial condensate solution (A11-1). The partial condensate (A11) had a fluorine atom content of 12.4% by mass and a number average molecular weight (Mn) of 990.

The raw material compositions of the partial condensates (A9), (A10), (X1) and (A11) and the amounts of the respective components used for the production are shown in Table 3 in terms of mass (g). Further, in terms of the raw material composition, the molar ratio of the compound (a-1) to 100 mol And display. The amount of each component used for the production is shown by combining the mass parts when the total amount of the compounds (a-1) to (a-3) is 100 parts by mass. Further, the fluorine atom content rate and the number average molecular weight (Mn) were combined and displayed.

[Examples 22 to 26: Composition of a hard coating film and production of a substrate having a hard coating layer]

In the resin composition (Y) for forming a commercially available hard coating film shown in Table 4, the partial condensate (A9), (A10) was used as the total mass of the total solid content and the partial condensate of the resin composition (Y). The ratio of (X1) and (A11) to the ratio (% by mass) shown in Table 4 includes the partial condensate solutions (A9-1), (A10-1), (X1-1) obtained in Examples 18 to 21 and (A11-1), compositions 10 to 14 for hard coat films were produced. In addition, as a photocurable resin composition (Y) of each of the examples, a hard coat film HC162 (trade name, manufactured by Yokohama Rubber Co., Ltd.) and a hard coat film BEAMSET 575 (CB) (trade name, manufactured by Arakawa Chemical Industries, Ltd.) can be used. Any of them. Each of these was used, and a cured film (hard coat layer) was formed on the PET substrate in the same manner as in Example 11 and evaluated. The results are shown in Table 4 together with the composition of the hard coating film composition.

The hard coat layers of Examples 9 and 10 formed by using the partial condensates (A1) and (A2) of the present invention respectively exhibit anti-fingerprint adhesion, light resistance, and cured film appearance of water repellency and ink repellency. The pencil is of good hardness.

The hard coat layer layer of Example 11 formed using the partial condensate (A3) of the present invention has anti-fingerprint adhesion properties and a cured film having a good appearance.

The hard coat layers of Examples 22 to 24 and 26 formed by using the partial condensates (A9), (A10) and (A11) of the present invention are respectively resistant to fingerprint adhesion and hardening of water repellency and ink repellency. The film looks good.

The hard coat layer of Example 12 of the partial condensate (A4) having a fluorine atom content of the partial condensate of more than 40% is insufficient in the appearance of the cured film.

The hard coat layer of Example 13 using the partial condensate (A5) containing no compound (a-2) unit was insufficient in ink repellency. It is presumed that the film-forming property of the partially hydrolyzed condensate is impaired by the absence of the compound (a-2) unit.

The hard coat layer of Example 14 using the partial condensate (A6) containing no compound (a-3) unit was insufficient in ink repellency. It is presumed that the partial hydrolysis condensate and the photopolymerizable compound (B) cannot be polymerized because the compound (a-3) unit is not contained, and it is difficult to form a coating layer, especially a surface.

The hard coat layer of Example 15 using a partial condensate (A7) having a hydrolyzable decane compound having a perfluoroalkyl group having 8 carbon atoms has a large environmental load. Moreover, the appearance of the cured film is insufficient. This estimation is because the number average molecular weight of the partially hydrolyzed condensate is large and the compatibility with the photopolymerizable compound (B) is insufficient.

The hard coat layer of Example 16 using the partial condensate (A8) composed of a hydrocarbon in the main chain was insufficient in light resistance. Presumed because the main chain is composed of hydrocarbons and It is degraded by ultraviolet rays.

In Example 17, the partially hydrolyzed condensate of the Example obtained in Example 1 was used to produce a composition for a hard coat film, and a substrate having a hard coat layer was produced using the same. However, from the viewpoint of producing a composition for a hard coat film having a composition in which the content of the partially hydrolyzed condensate in the total solid content exceeds 20% by mass, the ink-repellent property in the hard coat layer of Example 17 is insufficient. The partially hydrolyzed condensate having a low surface energy has characteristics of segregation on the surface. It is presumed that a partially hydrolyzed condensation property layer is formed in the hard coat layer of Example 17 to partially crosslink the partial condensate (A) and the photopolymerizable compound (B). When the composition contains the partially hydrolyzed condensate of the present invention, it is possible to appropriately adjust the appropriate composition by using the range of characteristics of the composition and the like.

The hard coat layer of Example 25 using the partial condensate (X1) having a fluorine atom content of less than 2.5% was insufficient in ink repellency. The presumption is because the surface cannot be fully covered by Rf.

Industrial availability

The composition for a hard coat film containing the partially hydrolyzed condensate of the present invention can form a hard coat layer which has sufficient hardness to the substrate and has excellent antifouling properties, particularly excellent in anti-fingerprint adhesion. In addition, the environmental load is small. Further, the substrate having the hard coat layer has excellent abrasion resistance and transparency, and the surface thereof has sufficient hardness, and the antifouling property, particularly the anti-fingerprint adhesion, is also excellent in light resistance. Therefore, it can be effectively used as a member of a touch panel, a display glass, an optical element, a sanitary machine, or the like which is used for a fat-type dirt, in particular, a smart phone or an input tablet personal computer to which a fingerprint is attached.

However, this is a reference to the Japanese application that was filed on January 31, 2012. The entire contents of the specification, the patent application, and the abstract of the Japanese Patent Application No. 2012- 245 498 filed on Nov.

Claims (21)

A method for producing an anti-fingerprint adhesive agent, characterized in that a mixture of hydrolyzable decane compounds is hydrolyzed and partially condensed in the presence of water, an organic solvent and an acid to produce a partial hydrolysis of a fluorine atom content of 2.5 to 40% by mass. a condensate; the hydrolyzable decane compound is a mixture of 1 to 23,000 moles per mole of the hydrolyzable decane compound (a-1) represented by the following formula (a-1) in terms of a molar ratio ( a hydrolyzable decane compound (a-2) represented by a-2) and a hydrolyzable decane compound (a-3) represented by the following formula (a-3): 20 to 11,500 mol; The symbols in the formulas (a-1), (a-2) and (a-3) are as follows: R ^f : F(CF ₂ ) ₄ -, F(CF ₂ ) ₆ - or R ^f1 OR ^F2 - represents a monovalent group having 2 to 100 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is a perfluoroalkylene having an etheric oxygen atom between carbon atoms and carbon atoms) Base); Q ¹ : a divalent organic group having 1 to 10 carbon atoms and no fluorine atom; Y: a group having an ethylenic double bond; Q ² : a carbon number of 1 to 6 and not containing a fluorine atom Organic group; R ^H1 , R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms; X ¹ , X ² , X ³ : a hydrolyzable group; p: an integer of 0 to 3; q: 1 or 2; r: 0 or 1 And q+r is a number of 1 or 2; however, there are a plurality of X ¹ and a plurality of X ² , X ³ , R in the formula (a-1) or the formula (a-2) or the formula (a-3). ^{When H1} and YQ ² , they may be different from each other or the same. The method for producing an anti-fingerprint adhesive agent according to the first aspect of the invention, wherein the partial hydrolysis-condensation product has a fluorine atom content of 20 to 40% by mass, and the R ^f- based F (CF ₂ in the above formula (a-1) ₄ -, F(CF ₂ ) ₆ - or a valent group represented by R ^f1 OR ^f2 - and having 2 to 40 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is acceptable a perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms). The method for producing an anti-fingerprint adhesive agent according to the first aspect of the invention, wherein the partially hydrolyzed condensate is a partially hydrolyzed condensate obtained by hydrolyzing and partially condensing a mixture of hydrolyzable decane compounds, the hydrolyzable decane compound mixture being The above-mentioned hydrolyzable decane compound (a-2) and 20 to 300 moles of the aforementioned hydrolyzable decane compound are contained in an amount of from 1 to 800 moles per 100 moles of the hydrolyzable decane compound (a-1). A-3). The method for producing an anti-fingerprint adhesive agent according to the first aspect of the invention, wherein the water is added in an amount of 5 to 100 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture. The method for producing an anti-fingerprint adhesive agent according to the second aspect of the invention, wherein the water is added in an amount of 5 to 100 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture. The method for producing an anti-fingerprint adhesive agent according to the third aspect of the invention, wherein the water is added in an amount of 5 to 100 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture. The method for producing an anti-fingerprint adhesive agent according to the third aspect of the invention, wherein the water is added in an amount of 5 to 40 parts by mass based on 100 parts by mass of the hydrolyzable decane compound mixture. The method for producing an anti-fingerprint adhesive agent according to the first aspect of the invention, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to the second aspect of the invention, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to claim 3, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to the fourth aspect of the invention, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to claim 5, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to claim 6, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive agent according to claim 7, wherein the organic solvent contains a compound having a hydroxyl group and having a dielectric constant of 5 to 20 at 25 °C. The method for producing an anti-fingerprint adhesive according to any one of claims 1 to 14, wherein the acid is nitric acid. A composition for a hard coating film comprising a partial hydrolyzed condensate and a photopolymerizable component, wherein the content of the following partial hydrolyzed condensate in the total solid content of the composition is 0.01 to 20% by mass; Hydrolyzed condensate: a hydrolyzable decane compound (a-1) represented by the following formula (a-1), a hydrolyzable decane compound (a-2) represented by the following formula (a-2), and the following formula (a-3) a partially hydrolyzed condensate of a mixture of hydrolyzable decane compounds (a-3), and having a fluorine atom content of 2.5 to 40% by mass; in the presence of water, an organic solvent and an acid, a hydrolyzable decane compound a partially hydrolyzed condensate of a hydrolyzed and partially condensed fluorine atom content of 2.5 to 40% by mass; the hydrolyzable decane compound represented by the following formula (a-1) in a molar ratio of the mixture of the hydrolyzable decane compound (a-1) 100 mol, containing 1 to 23,000 mol of the hydrolyzable decane compound (a-2) represented by the following formula (a-2) and 20 to 11,500 mol of the following formula (a-3) Hydrolyzable decane compound (a-3); [Chemical 2] The symbols in the formulas (a-1), (a-2), and (a-3) are as follows: R ^f : F(CF ₂ ) ₄ -, F(CF ₂ ) ₆ - or R ^f1 OR ^f2 - a valent group having 2 to 100 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is a perfluoroalkyl group having an etheric oxygen atom between carbon atoms and carbon atoms) ); Q ¹ : a divalent organic group having 1 to 10 carbon atoms and no fluorine atom; Y: a group having an ethylenic double bond; Q ² : a divalent organic group having 1 to 6 carbon atoms and no fluorine atom R ^H1 , R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms; X ¹ , X ² , X ³ : a hydrolyzable group; p: an integer of 0 to 3; q: 1 or 2; r: 0 or 1 and q+r is a number of 1 or 2; however, there are a plurality of X ¹ and a plurality of X ² , X ³ , and R ^{H1 in the} formula (a-1) and the formula (a-2) or the formula (a-3). When YQ ² , the same may be different from each other. The composition for a hard coating film according to claim 16, wherein the partial hydrolysis condensate has a fluorine atom content of 20 to 40% by mass, and the R ^f system F(CF ₂ ) in the above formula (a-1) _4- , F(CF ₂ ) ₆ - or a valent group represented by R ^f1 OR ^f2 - and having 2 to 40 carbon atoms (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is acceptable a perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms). The composition for a hard coat film according to claim 16 or 17, wherein the photopolymerizable component contains a photopolymerizable compound and a photopolymerization initiator. The composition for a hard coat film according to claim 16 or 17, wherein the film obtained by hardening the composition for the hard coat film is at least transparent to visible light. A substrate having a hard coat layer, comprising: a substrate; and a hard coat layer formed on the base by a composition for a hard coat film according to any one of claims 16 to 18. A cured film of at least a portion of the surface of the material. A touch panel characterized by having a substrate having a hard coat layer as in claim 20 of the patent application.