JP4761057B2 - SUBSTRATE HAVING COMPOSITE HARD COAT LAYER WITH ANTIFOIDING COATING AGENT FIXED TO HARD COATING LAYER - Google Patents

Description

  The present invention relates to a substrate provided with a composite hard coat layer including an antifouling surface layer provided on the surface of a hard coat layer provided on the surface of a substrate made of a thermoplastic resin or a thermosetting resin. Further, the present invention relates to a substrate and a method for forming the same, wherein an antifouling coating agent comprising an antifouling surface layer comprising a fluorine-based surface treatment agent is fixed to the hard coat layer.

  Various articles that require wear resistance, such as portable electronic devices such as eyeglass lenses, sunglasses, mobile phones, electronic notebooks, music players, and various displays such as liquid crystal displays, CRT displays, plasma displays, EL displays, etc. An optical recording medium such as a CD (Compact Disk) or a DVD (Digital Versatile Disk) is usually provided with a hard coat layer for preventing damage.

  These articles are also often contaminated with fingerprints, sebum, sweat, cosmetics, foods and the like. Such dirt hinders good visibility in the case of eyeglass lenses and also deteriorates the appearance. In an optical recording medium, there may be a failure in signal recording and reproduction. Therefore, it is desirable to impart characteristics that make it difficult for dirt to adhere and that can be easily removed even if dirt is attached. Therefore, in many cases, such an article is provided with an antifouling layer on the hard coat layer.

  On the other hand, silane coupling agents are well known as materials for bonding a substrate surface such as glass or cloth to an organic compound. The silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group undergoes a self-condensation reaction with moisture in the air to form siloxane and form a film. At the same time, a strong and durable coating is obtained by chemically and physically bonding to the surface of glass or metal. Silane coupling agents are widely used as coating agents for various substrate surfaces using this property.

  By the way, the antifouling layer is usually an extremely thin film of 0.1 μm or less, and this film needs to be firmly adhered to the surface of the hard coat layer so as to sufficiently withstand friction and wiping during use. is there. The following example can be given as an attempt to improve the adhesion with the hard coat layer.

  For example, in re-published patent WO2006-81296, a hard coating agent composition containing a curable silicon compound (hydrolyzable polymerizable silicon compound and / or its condensation compound, or silazane compound) is first applied to the surface of an object. A coating agent composition layer is formed, an antifouling coating agent is further applied to form an antifouling coating agent composition layer, and the both layers are simultaneously cured by heating to form a hard coat layer and an antifouling layer. A method of forming is described.

  In JP-A-9-137117, the surface of the hard coat layer is subjected to corona treatment or plasma treatment, and the treated surface is coated with a silane compound having a silanol group by hydrolysis as an antifouling coating agent and cured. Thus, a method for forming an antifouling layer having excellent durability on the resin surface is described.

  However, in the former method, application of a hard coating agent, application of an antifouling coating agent, and heat curing must be performed in a continuous process, and the types of articles that can be applied are limited. In the latter case, a large facility is required for the surface treatment.

Re-published patent WO2006-81296 Japanese Patent Laid-Open No. 9-137117

The present invention is to meet the above requirements, water and oil repellency, releasing property, antifouling property, excellent fingerprint wiping, etc., Pa over fluoropolyether modified in particular excellent adhesion lubricity and good substrate The present invention relates to a base material having a composite hard coat layer to which a fluorine-based antifouling surface layer having a silane and a polyfunctional hydrolyzable group mainly composed thereof is fixed, and a method for forming the same. That is, the present invention relates to a method capable of forming an antifouling layer on a hard coat layer by a simple method without requiring a special apparatus.

  As a result of intensive studies in order to meet the above-mentioned demand, the inventors have found that the coating film of the novel perfluoropolyether-modified silane represented by the general formula (1) is firmly adhered to various hard coat layers, and is repellent. It has been found that it has excellent water and oil repellency, the surface is hardly soiled, and dirt such as fingerprints can be easily wiped off.

Therefore, the present invention is a substrate provided with a composite hard coat layer including an antifouling surface layer provided on the surface of a hard coat layer provided on a substrate surface made of a thermoplastic resin or a thermosetting resin, The hard coat layer is composed of a cured product of a surface material containing a silicone-based and / or polyfunctional acrylic compound, and the antifouling surface layer is a perfluoropolyether-modified silane represented by the following general formula (1) and / or its An antifouling coating agent comprising a compound mainly composed of a hydrolyzed condensate is fixed to the hard coat layer, and a substrate provided with a composite hard coat layer and the compound are applied. And a method for forming an antifouling coating layer.
(Z ² Q) _β Rf (QZ ¹ A _α ) _2-β (1)
[Wherein Rf is a divalent perfluoropolyether-containing group selected from the groups represented by the following general formulas (5), (6) and (7) , Q is a divalent linking Rf group and Z group. A group containing an amide, ether, ester or vinyl bond, or a group represented by — (CH ₂ ) _n — (n = 2 to 4) , Z ¹ is a 2-9 valent group having a siloxane bond , Z ² is a monovalent group blocked with a triorganosilyl group represented by the following formula (2), A is a silicon-containing group represented by the following formula (3), α is an integer of 1 to 8, β Is 0, 1 or 2.

（ｂは１〜１０の整数、Ｒは炭素数１〜４のアルキル基またはフェニル基である。）
Ａは、下記式（３）で示される１価の基である。

(B is an integer of 1 to 10, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
A is a monovalent group represented by the following formula (3).

（式中、Ｒは炭素数１〜４のアルキル基またはフェニル基、Ｘは加水分解性基である。ａは２又は３、ｃは１〜６の整数である。）

（式中、Ｙはそれぞれ独立にＦ又はＣＦ ₃ 基、ｒは２〜６の整数、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数でｍ＋ｎは２〜２００、ｓは０〜６の整数である。該一般式中の繰り返し単位の配列はランダムである。）

（式中、ｌは１〜２００の整数、ｄは１〜３の整数である。）

（式中、ＹはＦ又はＣＦ ₃ 基、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数でｍ＋ｎは２〜２００である。該一般式中の繰り返し単位の配列はランダムである。）］

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and c is an integer of 1 to 6.)

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and s is (It is an integer of 0 to 6. The arrangement of repeating units in the general formula is random.)

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, and m + n is 2 to 200. The arrangement of repeating units in the general formula is random. ) ]

  According to the present invention, an antifouling layer firmly adhered to a hard coat layer can be formed simply by applying an antifouling coating agent to a hard coat layer applied to a substrate such as plastic and curing it. It can be applied to any use.

Hereinafter, the present invention will be described in more detail.
In the present invention, an article is first subjected to a hard coat treatment to form a hard coat layer, and a perfluoropolyether-modified silane compound represented by the general formula (1) is applied as an antifouling coating agent by an appropriate method. An antifouling layer is formed by curing.

  The material (base material) of the article to be treated with the surface treatment agent is a base material made of a thermoplastic resin or a thermosetting resin, and specifically, the following is preferable. Celluloid, cellulose acetate, cellulose propionate, cellulose butyrate, aliphatic polyamide such as 6-nylon, 6,6-nylon, 12-nylon, aromatic polyamide, ABS, AS resin, polystyrene, polyethylene (low density or high Density), polyolefins such as polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate and other saturated polyesters, aromatic polyesters, polyether ketones, Polyetheretherketone, Polysulfone, Polyethersulfone, Polyetherimide, Polyarylate, Polymethylpentene, Ionomer, Liquid crystal polymer, Polyi , Polyamideimide, fluororesin, polyphenylene sulfide, (modified) polyphenylene oxide, thermoplastic polyurethane, or epoxy resin, unsaturated polyester, thermosetting polyurethane, polyimide, diethylene glycol bisallyl carbonate (common name) CR-39) polymer, (halogenated) bisphenol A di (meth) acrylate (co) polymer, (halogenated) bisphenol A urethane-modified di (meth) acrylate (co) polymer, diacrylate Examples thereof include thermosetting resins such as compounds and copolymers of vinylbenzyl alcohol and unsaturated thiol compounds.

As the hard coating agent, a silicone type or a polyfunctional acrylic type is suitable.
<Silicone hard coat agent>
Silicone-based hard coat agents contain tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes or their hydrolyzed partial condensates as active ingredients. Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.

  Specific examples of trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyldimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyldimethoxyethoxysilane, Ethyltriacetoxysilane, ethyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyldimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltri Methoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethyl Xysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, N-β (aminomethyl) -γ-aminopropyltrimethoxysilane, β -Cyanoethyltriethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ -Glycidoxypropyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-methacryloxypropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-mercap Examples include topropylmethyldiethoxysilane, aminomethylethyldimethoxysilane, N-β (aminomethyl) -γ-aminopropylethyldimethoxysilane, and methylvinyldiethoxysilane.

  These may be used alone or as a mixture of a plurality of components. These compounds may be used singly or in combination of two or more according to the purpose. It is preferably used as a hydrolyzate for the purpose of increasing the reaction rate and lowering the curing temperature. When using 2 or more types together, you may use together after a hydrolysis and may use together before a hydrolysis and perform a cohydrolysis.

The film thickness of the hard coat cured film formed on the various substrates or article surfaces is appropriately selected depending on the type of the substrate, but is usually 0.1 μm to 20 μm, particularly 1 to 10 μm.
In order to improve the properties of the hard coat layer or to increase the refractive index to a predetermined value, these resins may contain 1 to 200 nm of inorganic fine particles. Such inorganic particles are preferably silicon dioxide titanium oxide.

  Moreover, a catalyst can also be added and used. Examples of such a catalyst include amines, metal salts of organic acids, Lewis acids, metal alkoxides, metal chelate compounds, metal halides, and the like. If necessary, stabilizers such as UV absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, antisettling agents, pigments, dyes, dispersants, antistatic agents Further, a surfactant such as an antifogging agent, a curing catalyst selected from acids, alkalis, salts and the like may be appropriately blended and used.

  The hard coat layer is a solution of the above components or a low molecular weight, so that the hard coat layer itself is in a liquid state, so that it is a solvent-free form and used as a treatment liquid, such as dipping method, brush coating, spin coating method, spray coating, flow coating, etc. It is applied by a method and dried at room temperature or under heating (preferably 120 ° C. or lower). After drying, it may be further cured by heat treatment (preferably 120 ° C. or lower).

<Multifunctional acrylic hard coat agent>
It is a radical reactive hard coat agent containing a polyfunctional compound having a plurality of (meth) acryloyl groups in one molecule. [Here, acryloyl group and methacryloyl group are collectively referred to as (meth) acryloyl group. The expression of (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate, and the like is also the same.

  A preferable compound as the polyfunctional compound is a compound having two or more (meth) acryloyl groups. In particular, an esterified product of a compound having two or more hydroxyl groups such as polyhydric alcohol and (meth) acrylic acid is preferable. Examples of such compounds include the following. 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate, trimethylolpropane-EO adduct tri (meth) acrylate, trimethylolpropane-PO adduct tri (meth) acrylate Of hexa (meth) acrylate of dipentaerythritol-caprolactone adduct, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate-caprolactone adduct, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct Tri (meth) acrylate.

In the polyfunctional acrylic hard coat agent, the following compounds can be mixed and used as a reactive diluent together with the polyfunctional compound. Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate.

The film thickness of the hard coat cured film formed on the various substrates or article surfaces is appropriately selected depending on the type of the substrate, but is usually 0.1 μm to 20 μm, particularly 1 to 10 μm.
In order to improve the properties of the hard coat layer or to increase the refractive index to a predetermined value, these resins may contain 1 to 200 nm of inorganic fine particles. Such inorganic particles are preferably silicon dioxide titanium oxide.

  The polyfunctional acrylic hard coat agent usually contains a photopolymerization initiator for curing. As the photopolymerization initiator, known to well-known ones can be used. A commercially available product that is readily available is particularly preferred. A plurality of photopolymerization initiators may be used in the transparent cured product layer. Examples of the photopolymerization initiator include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, α-acylose). Oxime esters), sulfur-containing photopolymerization initiators (for example, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide photopolymerization initiator is preferred. Moreover, a photoinitiator can also be used in combination with photosensitizers, such as amines.

  Specific examples of the photopolymerization initiator include the following compounds. 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-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, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoy Isobutyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4 '-Tetrakis (t-butylperoxycarbonyl) benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4', 4 "-diethylisophthalophenone, α-acyloxime ester, methylphenyl Glyoxylate, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropyl Pyrthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

  If necessary, stabilizers such as UV absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, anti-settling agents, pigments, dyes, dispersants, electrification A surfactant selected from an inhibitor, an antifogging agent, etc., a catalyst selected from acids, alkalis, salts, and the like may be appropriately blended and used.

  The hard coating agent can be applied by a method such as dipping, brush coating, spin coating, spray coating, or flow coating, and can be cured by irradiation with ultraviolet rays, electron beams, or other energy beams.

Next, an antifouling coating agent is applied to the formed hard coat layer to form an antifouling layer. The antifouling coating agent is represented by the following average composition formula (1).
(Z ² Q) _β Rf (QZ ¹ A _α ) _2-β (1)
[Wherein Rf is a divalent perfluoropolyether-containing group, Q is a divalent group linking the Rf group and the Z group, Z ¹ is a 2-9 valent group having a siloxane bond, and Z ² is A monovalent group blocked with a triorganosilyl group represented by the formula (2), A is a silicon-containing group represented by the following formula (3), α is an integer of 1 to 8, and β is 0, 1 or 2.

（ｂは１〜１０の整数、Ｒは炭素数１〜４のアルキル基またはフェニル基である。）
Ａは、下記式（３）で示される１価の基である。

(B is an integer of 1 to 10, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
A is a monovalent group represented by the following formula (3).

（式中、Ｒは炭素数１〜４のアルキル基またはフェニル基、Ｘは加水分解性基である。ａは２又は３、ｃは１〜６の整数である。）］

(Wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and c is an integer of 1 to 6)]

Here, Rf is a divalent perfluoropolyether-containing group, regardless of whether it is linear or branched. The perfluoropolyether structure includes a number of repeating units of —C _g F _2g O— (wherein g of each unit is an integer of 1 to 6). C _g F _2g O) _h and the like. Here, h is an integer of 1 to 500, preferably 2 to 400, more preferably 10 to 200.

Examples of the repeating unit —C _g F _2g O— represented by the above formula include the following units. In addition, the said perfluoroalkyl ether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
—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-
_{-CF 2 CF 2 CF 2 CF 2} CF 2 CF 2 O-
-C _{(CF 3)} 2 O-

In the case of perfluoropolyether groups, perfluoroether groups of various chain lengths are included. Among these, perfluoroethers having a repeating unit of a perfluoroether group having about 1 to 4 carbon atoms represented by the following units are shown. Polyether.
—CF ₂ O—
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-

  In the above formula (1), the divalent perfluoroether-containing group is preferably selected from the groups represented by the following general formulas (5), (6) and (7).

（式中、Ｙはそれぞれ独立にＦ又はＣＦ_３基、ｒは２〜６の整数、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数でｍ＋ｎは２〜２００、ｓは０〜６の整数である。該一般式中の繰り返し単位の配列はランダムである。）

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and s is (It is an integer of 0 to 6. The arrangement of repeating units in the general formula is random.)

（式中、ｌは１〜２００の整数、ｄは１〜３の整数である。）

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3.)

（式中、ＹはＦ又はＣＦ_３基、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数でｍ＋ｎは２〜２００である。該一般式中の繰り返し単位の配列はランダムである。）

(Wherein Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, and m + n is 2 to 200. The arrangement of repeating units in the general formula is random. .)

  In the case of the above-mentioned perfluoropolyether-containing group, perfluoroether groups having various chain lengths are included, preferably a perfluoropolyether-containing group having a perfluoroether group having about 1 to 4 carbon atoms as a repeating unit. . M, p, and q in the above chemical structural formula each represents an integer of 1 or more. Specifically, a range of 1 to 50, more preferably 10 to 40 is preferable. In addition, the molecular structure of perfluoropolyether is not limited to those exemplified.

  Furthermore, in the formula (1), it is preferable in terms of slipperiness that Rf is a perfluoropolyether-containing group selected from the group represented by the following general formula (4).

（式中、ｅ＝０〜５０、ｆ＝１〜５０及びｅ＋ｆ＝２〜６０の整数である。）

(In the formula, e = 0 to 50, f = 1 to 50 and e + f = 2 to 60 are integers.)

    In the formula, Q is a linking group between the Rf group and the Z group, and examples thereof include amide, ether, ester, and a group containing a vinyl bond.

  As a specific example, the following formula

などが挙げられる。

Etc.

In the above formula, Z ¹ may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, but is preferably a silicon functional group and more preferably has a siloxane bond. .

  Specific examples include the following.

  In the formula, X represents a hydrolyzable group and has 3 or more at the terminal, but may be the same or different. Specific examples thereof include alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, oxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy group and methoxyethoxy group, and acetoxy groups. And an alkenyloxy group having 2 to 10 carbon atoms such as an acyloxy group having 1 to 10 carbon atoms and an isopropenoxy group, a halogen group such as chloro group, bromo group and iodo group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.

  R is a lower alkyl group having 1 to 4 carbon atoms or a phenyl group, specifically a methyl group, an ethyl group, a phenyl group, or the like. Among them, a methyl group is preferable. a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. Although b is 2 or more and 2-5 are preferable from the coexistence of the adhesiveness to a base material, and antifouling performance, it is not limited to this.

  Further, the antifouling coating agent may be diluted with an appropriate solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), fluorine Modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, minerals) Examples thereof include spirits, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, a fluorine-modified solvent is desirable in terms of solubility and wettability, and particularly m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine and the like.

The solvent may be used alone or in combination of two or more. In any case, it is preferable to uniformly dissolve the components. The concentration of the silane and / or partial hydrolytic condensate thereof of formula dissolved in the solvent (1) is optimal concentration varies depending on the processing method, 0.01 to 50 wt%, in particular 0.05 to 20 It is preferable that it is weight%.

  Thus, as a processing method of the antifouling coating agent diluted in the solvent, it can be processed by a known method such as brushing, dipping, spraying, vapor deposition processing or the like. The optimum processing temperature varies depending on the processing method. For example, in the case of brush coating or dipping, a temperature range of room temperature to 120 ° C. is desirable. As the treatment humidity, it is desirable to perform the treatment under humidification in order to promote the reaction.

  In addition, since process conditions differ with the silane compound and other additives to be used, it is desirable to optimize each time.

  The antifouling coating agent may be hydrolyzed in advance. This makes the hydrolyzable silicon functional group the corresponding silanol (SiOH). Silanol is dehydrated and condensed between a plurality of molecules to form a siloxane bond (—Si—O—). Dehydration condensation proceeds quickly and oligomers are produced. It may be left (cured) for 1 to 24 hours after hydrolysis so that the dehydration condensation proceeds sufficiently. By using such hydrolyzed and partially condensed oligomer, the adhesion of the antifouling coating agent can be improved and the curing time can be shortened.

If necessary, the antifouling coating agent is a condensation catalyst, for example, an organic titanate such as tetrabutyl titanate or tetraisopropyl titanate; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (ethylacetoacetate) Organic titanium chelate compounds such as titanium; organoaluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); organozirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctate , Dibutyltin dilaurate, dibutyltin di (2-ethylhexanoate), dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctoate Organotin compounds of the following: metal salts of organic carboxylic acids such as tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate and zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; benzyltriethyl Quaternary ammonium salts such as ammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; guanidyl groups such as tetramethylguanidylpropyltrimethoxysilane Organic silicon compounds; organic acids (such as acetic acid and methanesulfonic acid) and inorganic acids (such as hydrochloric acid and sulfuric acid) may be added. These can be used singly or in combination of two or more.
Of these, acetic acid, tetra-n-butyl titanate, dibutyltin diacetate and the like are particularly desirable. The addition amount is a catalytic amount, and is usually 0.01 to 20 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of silane and / or its partial hydrolysis condensate.

  The present invention can be applied to the following articles. That is, the surface of various display elements such as spectacle lenses, sunglasses, antireflection filters, liquid crystal displays, CRT displays, plasma displays, EL displays, optical recording media such as CDs (Compact Disks) and DVDs (Digital Versatile Disks), mobile phones , Portable electronic devices such as electronic notebooks, music players, window glass for automobiles, trains, airplanes, etc., sanitary products such as headlamp covers, bathtubs, washstands, building materials for exterior walls, building materials for kitchens, arts, etc.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this. In the following examples, the physical properties in the table are measured by the following test methods.

[Synthesis Example 1]
50 g of perfluoropolyether having α · ω-unsaturated bonds at both ends represented by the following formula (I):

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）
１，３トリフルオロメチルベンゼン７５ｇ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０４４２ｇ（Ｐｔ単体として１．１×１０^−７モルを含有）を入れて９０℃に加熱撹拌した。ペンタメチルジシロキサン１．８５ｇを滴下して９０℃で２時間熟成し、その後、下記式（ＩＩ）に示すテトラメチルジシロキサン（ＨＭ）とビニルトリメトキシシラン（ＶＭＳ）との１：１付加反応物（ＨＭ−ＶＭＳ）７．５ｇを滴下して９０℃で２時間熟成し、１Ｈ−ＮＭＲで原料のアリル基が消失したのを確認した後、溶剤や未反応のペンタメチルジシロキサン及びＨＭ−ＶＭＳを減圧溜去した後、白濁の液体パーフルオロポリエーテル（化合物１）５０．５ｇ（比重：１．６３ 屈折率１．３１９）を得た。

(P / q = 0.9 p + q≈45)
75 g of 1,3 trifluoromethylbenzene and 0.0442 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as Pt alone) were added and heated to 90 ° C. with stirring. 1.85 g of pentamethyldisiloxane was added dropwise and aged at 90 ° C. for 2 hours, and then a 1: 1 addition reaction of tetramethyldisiloxane (HM) and vinyltrimethoxysilane (VMS) represented by the following formula (II) The product (HM-VMS) (7.5 g) was added dropwise and aged at 90 ° C. for 2 hours. After confirming the disappearance of the allyl group of the raw material by 1H-NMR, the solvent, unreacted pentamethyldisiloxane and HM- After the VMS was distilled off under reduced pressure, 50.5 g (specific gravity: 1.63, refractive index: 1.319) of a cloudy liquid perfluoropolyether (Compound 1) was obtained.

（但し、Ｙは−ＣＨ_２ＣＨ_２−及び−ＣＨ（ＣＨ_３）ＣＨ_２−が６１：３９の比率で混在する。）

(However, Y is a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ — in a ratio of 61:39.)

The NMR and IR charts of the obtained compound 1 are shown in FIGS. ^{The data of 1} H-NMR (TMS standard, ppm) is shown below.

From the above results, it was found that the structural formula of the obtained compound was as follows.

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

(P / q = 0.9 p + q≈45)

  Here, in X, the following (a) and (b) are mixed at a ratio of 38:62.

（但し、Ｙは−ＣＨ_２ＣＨ_２−及び−ＣＨ（ＣＨ_３）ＣＨ_２−が６１：３９の比率で混在する。）

(However, Y is a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ — in a ratio of 61:39.)

[Synthesis Example 2]
50 g of perfluoropolyether having α · ω-unsaturated bonds at both ends represented by the following formula (I):

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）
１，３トリフルオロメチルベンゼン７５ｇ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０４４２ｇ（Ｐｔ単体として１．１×１０^−７モルを含有）を入れて９０℃に加熱撹拌した。ペンタメチルジシロキサン１．８５ｇを滴下して９０℃で２時間熟成し、その後、下記式（ＩＩＩ）に示す化合物（Ｈ４Ｑ）２０．５ｇを滴下して９０℃で３時間熟成し、１Ｈ−ＮＭＲで原料のアリル基が消失したのを確認した後、溶剤や過剰のＨ４Ｑを減圧溜去した後、活性炭処理を行った後無色透明の液体パーフルオロポリエーテル４６．８ｇを得た。

(P / q = 0.9 p + q≈45)
75 g of 1,3 trifluoromethylbenzene and 0.0442 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as Pt alone) were added and heated to 90 ° C. with stirring. 1.85 g of pentamethyldisiloxane was added dropwise and aged at 90 ° C. for 2 hours, and then 20.5 g of the compound (H4Q) represented by the following formula (III) was added dropwise and aged for 3 hours at 90 ° C. After confirming disappearance of the allyl group of the raw material, the solvent and excess H4Q were distilled off under reduced pressure, and after activated carbon treatment, 46.8 g of colorless and transparent liquid perfluoropolyether was obtained.

Furthermore, 25 g of the above-mentioned perfluoropolyether, 30 g of 1,3 trifluoromethylbenzene, 0.0225 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.2.times.10.sup.- ⁶ mol as a simple substance of Pt). The mixture was heated and stirred at 90 ° C. After dropwise addition of 4.63 g of trimethoxysilane and aging at 80 ° C. for 3 hours, the solvent was distilled off under reduced pressure, and 26.8 g of a colorless transparent liquid (Compound 2) (specific gravity: 1.65, refractive index: 1.313) was obtained. Obtained.

The NMR and IR charts of the obtained compound 2 are shown in FIGS. ^{The data of 1} H-NMR (TMS standard, ppm) is shown below. (Including benzene)

From the above results, it was found that the structural formula of the obtained compound was as follows.

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

(P / q = 0.9 p + q≈45)

  Here, in X, the following (c) and (d) are mixed at a ratio of 57:43.

（但し、Ｙは−ＣＨ_２ＣＨ_２−及び−ＣＨ（ＣＨ_３）ＣＨ_２−が７９：２１の比率で混在する。）

(However, Y is a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ — in a ratio of 79:21.)

[Synthesis Example 3]
50 g of perfluoropolyether (I) having α · ω-unsaturated bonds at both ends shown in Synthesis Example 1, 75 g of 1,3 trifluoromethylbenzene, 0.0442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (1.1 × 10 ⁻⁷ mol as Pt alone) was added and stirred at 90 ° C. with heating. After adding 8.4 g of the addition reaction product (HM-VMS) represented by the above formula (II) dropwise and aging at 90 ° C. for 2 hours, and confirming the disappearance of the allyl group of the raw material by 1H-NMR, After the HM-VMS of the reaction was distilled off under reduced pressure, 56.3 g (specific gravity: 1.63, refractive index: 1.319) of white cloudy liquid perfluoropolyether (Compound 3) was obtained.

The NMR and IR charts of the obtained compound 3 are shown in FIGS. ^{The data of 1} H-NMR (TMS standard, ppm) is shown below.

From the above results, it was found that the structural formula of the obtained compound was as follows.

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

(P / q = 0.9 p + q≈45)

  Here, X is represented by the following formula.

（但し、Ｙは−ＣＨ_２ＣＨ_２−及び−ＣＨ（ＣＨ_３）ＣＨ_２−が６１：３９の比率で混在する。）

(However, Y is a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ — in a ratio of 61:39.)

[Create specimen]
A 2 mm thick, 25 mm wide, 100 mm long test piece (manufactured by Riken Optech Corporation) made of a polymer of diethylene glycol bisallyl carbonate (commonly known as CR-39) is a silicone hard coating agent (KP-64: Shin-Etsu Chemical Co., Ltd.). The test piece was pulled up at a speed of 150 mm per minute, air-dried at room temperature for 10 minutes, and then heat-cured at 120 ° C. for 1 hour. In this way, a silicone hard coat layer was provided on the surface of the test piece.

[Examples 1 to 3]
Compounds 1 to 3 synthesized in Synthesis Examples 1 to 3 are dissolved in Novec HFE-7200 (manufactured by Sumitomo 3M) to form a 0.2% solution, and dibutyltin diacetate is added thereto to a concentration of 100 ppm. To obtain a treatment liquid. Next, the test piece (2 mm × 25 mm × 100 mm) provided with the silicone hard coat layer prepared by the above method is immersed in the treatment liquid, pulled up at a speed of 150 mm / min, and in an atmosphere of 25 ° C. and humidity 45%. It was left to stand for 48 hours to form a cured film. The following evaluation was performed using this test piece.

[Example 4]
A mixture of 2.3 g of isobutyl alcohol and 6.7 g of Novec HFE-7200 was prepared from 1.0 g of compound 3 synthesized in Synthesis Example 3, and 50 mg of a 0.1 N aqueous hydrochloric acid solution was added thereto. This mixture was aged at room temperature for 3 days to carry out partial hydrolysis of the alkoxysilyl group of compound 3. Next, 10.0 g of this mixture was diluted 50 times with Novec HFE-7200 to obtain a treatment solution. Using this treatment solution, the test piece was treated in the same manner as in Examples 1 to 3 to form a cured film. The following evaluation was performed using this test piece.

[Comparative Examples 1 and 2]
Test pieces were prepared and evaluated in the same manner as in Examples 1 to 3 except that the following compounds 4 and 5 were used instead of the perfluoro-modified silanes of Compounds 1 to 3 used in the Examples.

Compound 4

Compound 5

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

(P / q = 0.9 p + q≈45)

[Evaluation Method for Water and Oil Repellency of Film]
Using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.), the receding contact angle of the cured film with respect to water and oleic acid was measured to evaluate water and oil repellency.

[Evaluation of abrasion resistance of film]
A rubbing test was conducted using a rubbing tester under the following conditions to evaluate the abrasion resistance of the cloth.
Evaluation environmental conditions: 25 ° C, humidity 40%
Rubbing material: Eight nonwoven fabrics were wrapped and wrapped around the tip (1.5 cm × 1.5 cm) of a tester in contact with the sample, and fixed with a rubber band. A load of 1 kg was applied and it was worn out 2000 times. After the wear test, the water contact angle of the cured coating was measured and used as an index of wear resistance.

The evaluation results are shown in Table 1.

化合物３＊：化合物３の部分加水分解物

Compound 3 *: Partial hydrolyzate of Compound 3

As described above, in Examples 1 to 4, it can be seen that the water contact angle after the abrasion test is larger than that of Comparative Examples 1 and 2, and the adhesion is high.

2 is an NMR chart of Compound 1. 2 is an IR chart of Compound 1. 2 is an NMR chart of Compound 2. 4 is an IR chart of Compound 2. 3 is an NMR chart of Compound 3. 4 is an IR chart of Compound 3.

Claims (4)

A base material provided with a composite hard coat layer including an antifouling surface layer provided on the surface of a hard coat layer provided on the surface of a base material made of a thermoplastic resin or a thermosetting resin, A perfluoropolyether-modified silane represented by the following general formula (1) and / or a hydrolysis-condensation product thereof is composed of a cured product of a surface material containing a silicone-based and / or polyfunctional acrylic compound. A base material provided with a composite hard coat layer, wherein an antifouling coating agent comprising a compound as a main component is fixed to the hard coat layer.
(Z ² Q) _β Rf (QZ ¹ A _α ) _2-β (1)
[Wherein Rf is a divalent perfluoropolyether-containing group selected from the groups represented by the following general formulas (5), (6) and (7) , Q is a divalent linking Rf group and Z group. A group containing an amide, ether, ester or vinyl bond, or a group represented by — (CH ₂ ) _n — (n = 2 to 4) , Z ¹ is a 2-9 valent group having a siloxane bond , Z ² is a monovalent group blocked with a triorganosilyl group represented by the following formula (2), A is a silicon-containing group represented by the following formula (3), α is an integer of 1 to 8, β Is 0, 1 or 2.

(B is an integer of 1 to 10, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
A is a monovalent group represented by the following formula (3).

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and c is an integer of 1 to 6.)

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and s is (It is an integer of 0 to 6. The arrangement of repeating units in the general formula is random.)

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, and m + n is 2 to 200. The arrangement of repeating units in the general formula is random. ) ] In formula (1), Q is
_{-CH 2 OCH 2 CH 2 CH 2} -, - CF 2 OCH 2 CH 2 CH 2 -, - (CH 2) n - (n = 2~4),

(In the formula, Me represents a methyl group.)
A group selected from: Z ¹ is represented by the following formula:

(In the formula, Me represents a methyl group.)
From a group selected, one of the bonds of Q bonded one of the bonds of Rf, one of the other bonds of Q bonded one of the bonds of Z ¹ or Z ^2, the Z ¹ the remaining bonds substrates composite hard coat layer according to claim 1, wherein the one that binds to a. The base material provided with the composite hard coat layer according to claim 1 or 2 , wherein the hydrolyzable group X in the formula (3) is an alkoxy group. A method of forming a composite hard coat layer comprising a hard coat layer in contact with a substrate surface made of a thermoplastic resin or a thermosetting resin and an antifouling surface layer in contact with the hard coat layer, wherein the base on which the hard coat layer is formed A compound comprising, as a main component, a perfluoropolyether-modified silane represented by the general formula (1) and / or a hydrolysis-condensation product thereof is applied to the surface of the hard coat layer. The method for forming a composite hard coat layer according to any one of 1 to 3 .

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