JP2013177503A - Coating composition, transparent coated molded article and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition allowing a transparent coated molded article that is not only excellent in adhesiveness to a base material, wear resistance, transparency and scratch resistance or the like but also excellent in antifouling properties, and to provide the transparent coated molded article and a method for producing the transparent coated molded article.SOLUTION: A coating composition is used for forming a transparent cured material layer on at least a part on a transparent base material. The coating composition contains: a polyfunctional fluorine compound (a) which is a fluorine-containing compound, having three or more polymerizable groups selected from a (meth)acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group and -C(O)OCH=CH, and in which a fluorine content ratio is ≥35.0 mass% of the molecular weight of the fluorine-containing compound and the calculation value of all inter-crosslinking molecular weight is ≤300 when polymerizing the polymerizable groups; and fluorine-containing polysilazane (b).

Description

  The present invention relates to a coating composition, a transparent coated molded article, and a method for producing the same. More specifically, a coating composition for use as a transparent member having a large area such as an outer wall or an arcade, or for a vehicle such as an automobile (inorganic glass, hereinafter the same) and its substitute, transparent The present invention relates to a coated molded product and a manufacturing method thereof.

  In recent years, transparent synthetic resin materials have been used as transparent materials to replace glass. In particular, the aromatic polycarbonate resin is excellent in crush resistance, transparency, lightness, easy processability, and the like, and is used in various fields as a transparent member having a large area such as an outer wall or an arcade by taking advantage of its characteristics. In addition, there is an example in which such a transparent synthetic resin material is used instead of glass (referred to as inorganic glass, hereinafter the same) for vehicles such as automobiles. However, the surface hardness is not sufficient for use as a substitute for glass, and there is a problem that transparency is easily impaired because it is easily damaged and easily worn.

As a coating composition for producing such a transparent coated molded article, in Patent Document 1, a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and a fluorine-containing compound are disclosed. A coating composition containing polysilazane (b) has been proposed. When such a coating composition is used, it is presumed that polysilazane containing fluorine in the cured film is concentrated on the surface, and it is possible to obtain a transparent coated molded article having excellent scratch resistance. It is stated that it can be done.
However, the transparency and abrasion resistance of the transparent coated molded product are not sufficient, and there is room for improvement. Furthermore, no investigation has been made on the antifouling property of the transparent coated molded article.
Further, from the viewpoint of a polymerizable fluorine-containing monomer, the one described in Patent Document 2 is known, but there is no description or suggestion about the use as a coating composition.

JP 11-333987 A JP 2006-028280 A

  The object of the present invention is to solve the above-mentioned problems, and not only is excellent in adhesion to the substrate, wear resistance, transparency and scratch resistance, but also in antifouling properties. An object of the present invention is to provide a coating composition, a transparent coated molded article and a method for producing the same, which give an excellent transparent coated molded article.

  As a result of the inventor's earnest study under the above-mentioned problems, the present inventors have three or more specific polymerizable groups, the fluorine content is in a specific range, and when the polymerizable groups are polymerized, all Forming a coating composition containing a polyfunctional fluorine compound (a) having a calculated molecular weight between crosslinks in a specific range and a fluorine-containing polysilazane (b) on at least a part of the transparent substrate. Thus, it has been found that it is possible to provide a transparent coated molded article having not only excellent adhesion but also excellent transparency before and after an abrasion resistance test and having high antifouling properties, and has completed the invention. Specifically, the above problems have been achieved by the following means.

[1]
A coating composition for forming a transparent cured product layer on at least a part of a transparent substrate, the coating composition comprising a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and- A fluorine-containing compound having three or more polymerizable groups selected from C (O) OCH═CH ₂ , wherein the fluorine content is 35.0% by mass or more of the molecular weight of the fluorine-containing compound, and the polymerizable group A coating composition containing a polyfunctional fluorine compound (a) having a calculated value of molecular weight between crosslinks of 300 or less and a fluorine-containing polysilazane (b) when polymerized.
[2]
The coating composition according to [1], wherein the polyfunctional fluorine compound (a) is represented by the general formula (1).
General formula (1): Rf {-(L) m-Y} n
(In the formula, Rf represents an n-valent group selected from the following f-1 to f-10, n represents an integer of 3 to 6, and L represents an alkylene group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. It is obtained by combining 10 arylene groups, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, -S-, or -N (R)-. Or a group obtained by combining an arylene group having 6 to 10 carbon atoms and —O—, —S—, or —N (R) —, wherein R represents a hydrogen atom or an alkyl having 1 to 5 carbon atoms; M represents 0 or 1. Y represents a polymerizable group selected from a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and —C (O) OCH═CH _2. .)

[3]
The coating composition according to the above [1] or [2], wherein the polyfunctional fluorine compound (a) is any one of the following M-1 to M-13.

[4]
The coating composition according to any one of [1] to [3], wherein the fluorine-containing polysilazane (b) is represented by the following general formula (A).
Formula (A):
^{_{[(Rf'Q) a Si (R}} 1) b (NR 2) 4-a-b / 2] l · [(Rf'Q) c Si (R 1) d O 4-c-d / 2] m [[Rf′Q) _e Si (R ¹ ) _f (NR ² ) _{g / 2} O _{h / 2} ] _n
(In the general formula (A), R ^{1 s} may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group; R ² may be the same or different, and Rf ′ may be the same or different and is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl ether group having 2 to 35 carbon atoms; Q is And a divalent organic group having 2 to 5 carbon atoms; independently in each first structural unit, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is Each is an integer of 1 to 3, and in each second structural unit, c is an integer of 0 to 2, d is an integer of 1 to 3, provided that c + d is an integer of 1 to 3, In the third structural unit, e and f are integers from 0 to 2, and g Fine h is an integer of 1 or 2, provided that be e + f + g + h = 4; l, m and n are numbers equal to or greater than 1).
[5]
The coating composition according to any one of [1] to [4], wherein the coating composition further contains colloidal silica having an average particle size of 200 nm or less.
[6]
It has a transparent base material, and the transparent hardened material layer in which the hardened | cured material of the coating composition as described in any one of said [1]-[5] was formed in at least one part of the said transparent base material surface. Transparent coated molded product characterized by
[7]
The transparent film molded product according to [6], wherein the transparent substrate is a transparent synthetic resin substrate.
[8]
In a method for producing a transparent coated molded article having a transparent synthetic resin base material and a transparent cured product layer formed on at least a part of the surface of the transparent synthetic resin base material, at least a part of the surface of the transparent synthetic resin base material Applying the coating composition according to any one of [1] to [5] above, then curing the polyfunctional fluorine compound (a) by irradiation with active energy rays, and the fluorine-containing composition. The manufacturing method of the transparent covering molded article which performs hardening of polysilazane (b) in arbitrary order or simultaneously.
[9]
In a method for producing a transparent coated molded article having a transparent synthetic resin base material and a transparent cured product layer formed on at least a part of the surface of the transparent synthetic resin base material, at least a part of the surface of the transparent synthetic resin base material Applying the coating composition according to any one of [1] to [5] above, then curing the polyfunctional fluorine compound (a) by irradiation with active energy rays, and the fluorine-containing composition. A method for producing a transparent coated molded article, wherein the polysilazane (b) is cured in any order or simultaneously, and the fluorinated polysilazane (b) is bent in an uncured or partially cured state.

  When the coating composition of the present invention is formed on at least a part of a transparent substrate, it provides not only excellent adhesion but also excellent transparency before and after an abrasion resistance test and a transparent coated molded article having high antifouling properties can do.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less.
Moreover, in the description of groups (atomic groups) in this specification, the description that does not indicate substitution and non-substitution includes those that have a substituent as well as those that do not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[Coating composition of the present invention]
The coating composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is a coating composition that forms a transparent cured product layer on at least a part of a transparent substrate, The coating composition is a fluorine-containing compound having three or more polymerizable groups selected from (meth) acryloyl groups, allyl groups, α-fluoroacryloyl groups, epoxy groups, and —C (O) OCH═CH _2. A polyfunctional fluorine compound having a fluorine content of 35.0% by mass or more of the molecular weight of the fluorine-containing compound and having all the calculated molecular weights between crosslinks of 300 or less when the polymerizable group is polymerized. It contains (a) and fluorine-containing polysilazane (b).

(Polyfunctional fluorine compound (a))
The polyfunctional fluorine compound (a) of the present invention mainly comprises a plurality of fluorine atoms and carbon atoms (however, it may partially contain oxygen atoms and / or hydrogen atoms) and does not substantially participate in polymerization. (Meth) acryloyl group, allyl group, α-fluoroacryloyl group, epoxy group, and —C through an atomic group (hereinafter also referred to as “fluorine-containing core part”) and a linking group such as an ester bond or an ether bond. (O) A fluorine-containing compound having 3 or more polymerizable groups selected from OCH═CH ₂ , preferably 4 or more, more preferably 4 polymerizable groups.
By having three or more polymerizable groups, the crosslink density of the polymer of the polyfunctional fluorine compound (a) (hereinafter sometimes simply referred to as “polymer”) is increased, and the strength of the cured film obtained is increased. Will improve.

Moreover, the polyfunctional fluorine compound (a) of the present invention is characterized in that the fluorine content is 35.0% by mass or more of the fluorine-containing compound. The fluorine content is preferably 35 to 60% by mass, more preferably 40 to 55% by mass, and still more preferably 40 to 50% by mass.
By setting the fluorine content within the above range, compatibility with materials other than the material (a) for constructing the composition of the present invention is increased and transparency of the transparent coated molded product is improved. It becomes possible to impart dirtiness.

  Furthermore, the polyfunctional fluorine compound (a) of the present invention is characterized in that when all the polymerizable groups of the polyfunctional fluorine compound (a) are polymerized, all the calculated values of the molecular weight between crosslinks are 300 or less. To do. The molecular weight between crosslinks will be described later. The calculated value of the molecular weight between crosslinks is more preferably 250 or less, and still more preferably 200 or less. When the molecular weight between crosslinks when all the polymerizable groups of the fluorine-containing polyfunctional monomer are polymerized exceeds 300, the hardness when the transparent cured product layer is formed decreases, and further, the antifouling property and scratch resistance are reduced. Getting worse.

The polyfunctional fluorine compound (a) of the present invention is preferably represented by the following general formula (1).
General formula (1): Rf {-(L) m-Y} n

(In the formula, Rf represents an n-valent group selected from the following f-1 to f-10, n represents an integer of 3 to 6, and L represents an alkylene group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. It is obtained by combining 10 arylene groups, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, -S-, or -N (R)-. Or a group obtained by combining an arylene group having 6 to 10 carbon atoms and —O—, —S—, or —N (R) —, wherein R represents a hydrogen atom or an alkyl having 1 to 5 carbon atoms; M represents 0 or 1. Y represents a polymerizable group selected from a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and —C (O) OCH═CH _2. .)

In general formula (1), Rf represents a "fluorine-containing core part", represents an n-valent group selected from the above f-1 to f-10, and n represents an integer of 3 to 6.
1/4 or less is preferable and the number of hydrogen atoms / fluorine atoms in Rf is more preferably 1/9 or less. n represents an integer of 3 or more and 6 or less, and n is preferably 4 or more and 6 or less, and most preferably 4.
Rf is preferably a group having a molecular weight between crosslinks of 300 or less when all polymerizable groups are polymerized. The molecular weight between crosslinks will be described later.
Rf is preferably f-1, f-6, or f-7, more preferably f-1 or f-6, from the viewpoint of solubility in a solvent and crosslinking reactivity, and f- 6 is most preferred.

L is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, -S. A group obtained by combining-or -N (R)-, or a group obtained by combining an arylene group having 6 to 10 carbon atoms with -O-, -S-, or -N (R)- Represents.
Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, and a propylene group, and a methylene group is preferable.
Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group.
When L represents an alkylene group or an arylene group, the alkylene group and the arylene group represented by L are preferably substituted with a halogen atom, and preferably substituted with a fluorine atom.
L is a group obtained by combining a single bond (ie, m = 0), —O—, or an alkylene group having 1 to 10 carbon atoms and —O— from the viewpoint of solubility in a solvent and compound synthesis. It is preferable that it is —O— or a group obtained by combining —O— with an alkylene group having 1 to 10 carbon atoms.

Y represents a polymerizable group selected from a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and —C (O) OCH═CH ₂ .
Among these, Y is preferably a (meth) acryloyl group or —C (O) OCH═CH ₂ from the viewpoint of polymerizability.

  R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

  m represents 0 or 1;

  More preferable as the fluorine-containing polyfunctional monomer of the present invention is one represented by the general formula (2) or (3).

Formula (2) Rf- {OC (O ) CH = CH 2} n
Formula (3) Rf- {C (O ) OCH = CH 2} n
In the above formula, Rf and n have the same meanings as those in the general formula (1), and the preferred ranges are also the same.

  Although the preferable specific example of the polyfunctional fluorine compound (a) of this invention is given to the following, this invention is not limited by these.

The fluorine contents of M-1 to M-13 are 37.5, 46.2, 48.6, 49.8, 36.6, 39.8, 47.0, 35.1, 44.9, respectively. 42.5, 36.2, 36.7, 45.8 mass%.
Among M-1 to M-13, M-2 to M-5 or M-9 to M-11 are preferable from the viewpoint of solubility in a solvent and crosslinking reactivity, and M-5 or M- It is more preferably 9 to M-11, and most preferably M-9 or M-10.

  The polyfunctional fluorine compound (a) of the present invention has a fluorine-containing core portion Rf in which all the calculated values of the molecular weight between crosslinks are 300 or less when all the polymerizable groups of the polyfunctional fluorine compound (a) are polymerized. Have. The calculated value of the molecular weight between crosslinks is the polymer in which all the polymerizable groups of the polyfunctional fluorine compound (Ax) are polymerized, and (i) the carbon atoms substituted with 3 or more carbon atoms or silicon atoms are combined. When a silicon atom substituted with 3 or more carbon atoms or oxygen atoms is (ii), it is sandwiched between (i) and (i), (ii) and (ii), or (i) and (ii) Refers to the molecular weight of the atomic group. For example, Ax-2 will be described as an example of the polyfunctional fluorine compound (a). Assuming that all the polymerizable groups of Ax-2 are polymerized, it is expressed as shown in Formula (4).

Formula (4)

In this case, the partial structure which is the target of calculation of the molecular weight between crosslinks defined above is a portion surrounded by a broken line in the formula (4), and the calculated value of the molecular weight between crosslinks is C ₂ F ₄ O = 116, respectively. 0.0 and C ₅ H ₂ F ₆ O ₃ = 224.1, both of which are 300 or less.

  The calculated value of the molecular weight between crosslinks is more preferably 250 or less, and still more preferably 200 or less. When the molecular weight between crosslinks when all the polymerizable groups of the fluorine-containing polyfunctional monomer are polymerized exceeds 300, the hardness when formed into a coating film is lowered.

  As a method for producing these fluorine-containing polyfunctional monomers, a compound having an ester bond, a dialkoxy group, and / or a halogen atom is subjected to liquid phase fluorination, whereby 80 mol% or more, preferably 90 mol% or more of hydrogen. A method of introducing three or more polymerizable groups after substituting atoms with fluorine atoms is preferred. Liquid phase fluorination is described, for example, in US Pat. No. 5,093,432.

The compound to be subjected to liquid phase fluorination is required to be dissolved in a fluorine-based solvent used for liquid phase fluorination or to be liquid, but there is no particular limitation other than that. From the viewpoint of such solubility and reactivity, a compound containing fluorine in advance may be used. In addition, a compound having an ester bond, a dialkoxy group, and / or a halogen atom is preferable because it can serve as a reaction point when a polymerizable group is introduced after liquid phase fluorination.
By introducing fluorine atoms by liquid phase fluorination, it is possible to extremely increase the fluorine content of the portion other than the polymerizable group to be introduced later, and give a resin with extremely high water and ink repellency. A polyfunctional fluorine compound (a) can be obtained.

  Although content in particular of the polyfunctional fluorine compound (a) in the curable composition of this invention does not have a restriction | limiting, 20-100 mass% in all the polymerizable monomers from a viewpoint of sclerosis | hardenability and a composition viscosity. Is preferable, 30 to 100% by mass is more preferable, 40 to 100% by mass is further preferable, and 50 to 100% by mass is particularly preferable.

(Fluorine-containing polysilazane (b))
The coating composition of the present invention contains fluorine-containing polysilazane (b).
Polysilazane is a polymer having two or more [—Si—N—] units (silazane units). In this chemical formula, the remaining two bonds of silicon atoms (tetravalent), nitrogen atoms (trivalent) A hydrogen atom or an organic group is bonded to the remaining one bond. In addition to the polymer having a linear structure composed only of the silazane unit, one or both of the remaining two bonds of the silicon atom of the silazane unit and the bond of the nitrogen atom of the other silazane unit are bonded. An annular structure may be formed. The polymer may consist of repeating cyclic structures only, may be a linear polymer having a cyclic structure in part, and [-Si-O-] units (silica units) as polymerized units. May be included.

  The fluorine-containing polysilazane in the present invention refers to a polysilazane containing a silazane unit in which a monovalent fluorine-containing organic group is bonded to at least one of the remaining two bonds of the silicon atom of the silazane unit. A preferred silazane unit to which a fluorine-containing organic group is bonded is a silazane unit in which a fluorine-containing organic group having one fluorine-containing organic group and one hydrogen atom on a silicon atom and a hydrogen atom bonded to a nitrogen atom is bonded. is there. The fluorine-containing polysilazane may be composed only of the silazane unit having this fluorine-containing organic group, or may contain a silazane unit having this fluorine-containing organic group and another silazane unit. A preferred fluorine-containing polysilazane includes a silazane unit having a fluorine-containing organic group and another silazane unit (particularly a unit of perhydrosilazane). Even a small amount of the fluorine-containing organic group is sufficient to exert the desired effect. For example, those in which 0.1 mol% or more of all silazane units are silazane units having a fluorinated organic group can be used, and those in which 1 to 50 mol% are silazane units having a fluorinated organic group are preferred.

  The fluorine-containing polysilazane (b) in the coating composition of the present invention exhibits good compatibility with the polyfunctional fluorine compound (a). For this reason, compared with the case where the polyfunctional compound which does not contain a fluorine is used, the coating composition which gives the transparent coating molded article excellent in transparency can be obtained.

  The fluorine-containing organic group refers to a monovalent organic group in which one or more hydrogen atoms bonded to carbon atoms of the organic group are substituted with fluorine atoms. For example, there is an organic group in which one or more hydrogen atoms bonded to a carbon atom such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are substituted with a fluorine atom. Preferably, it is an organic group in which 50% or more of hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The fluorine-containing organic group is bonded to the silicon atom by a carbon bond (that is, the fluorine-containing organic group and the silicon atom are bonded by a carbon-silicon bond). The organic group may have an ether bond, an ester bond, an imino bond, or another bond having a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

  A preferred fluorine-containing organic group is a polyfluoroalkyl group. Particularly preferred is a highly fluorinated alkyl group (an alkyl group in which 60% or more, especially 80% or more of the hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms). A small number of hydrogen atoms bonded to carbon atoms may be substituted with chlorine atoms. The polyfluoroalkyl group is preferably linear or linear having a short branch. Moreover, you may have said coupling | bonding between two carbon atoms of a polyfluoroalkyl group. In addition, it is preferable that only the hydrogen atom has couple | bonded with the terminal carbon atom couple | bonded with the silicon atom of this polyfluoroalkyl group.

A particularly preferred fluorine-containing organic group is an organic group having a perfluoroalkyl group which may have an ether bond. A perfluoroalkyl group refers to a fluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The perfluoroalkyl group having an ether bond refers to a group having one or more etheric oxygen atoms existing between two carbon atoms of the perfluoroalkyl group. Hereinafter, these perfluoroalkyl groups which may have an ether bond are referred to as R _perf groups. The R _perf group may be linear or branched. In particular, a straight chain and a straight chain having a short (1 to 2 carbon atoms) side chain such as a trifluoromethyl group are preferred. _{Examples of the} R _perf group include a perfluoroalkyl group having 1 to 20 carbon atoms, particularly 2 to 16 carbon atoms, and a perfluoroalkyl group having an ether bond having 2 to 35 carbon atoms, particularly 4 to 25 carbon atoms and 1 to 7 etheric oxygen atoms. preferable.

Formula _R perf -R- is a organic group having a perfluoroalkyl group _{(wherein, R perf} represents the _{R perf} group, R represents. A divalent organic group having no fluorine atom) represented by Those are preferred.

R is preferably a divalent organic group having 10 or less carbon atoms which may have an ether bond, ester bond, imino bond or other divalent linking group on the R _perf side or between two carbon atoms. In particular, a divalent hydrocarbon group having 2 to 6 carbon atoms (particularly an alkylene group) is preferred.

  The silazane unit to which the fluorine-containing organic group is bonded may have a hydrogen atom or an organic group other than the fluorine-containing organic group on the silicon atom and the nitrogen atom in addition to the fluorine-containing organic group. The silicon atom may have a hydrolyzable group such as an alkoxy group. Examples of such a group include an alkyl group, an alkoxy group, an alkenyl group, an aryl group, a cycloalkyl group, or a group having a substituent such as a halogen atom or a hydroxyl group. A group bonded to a silicon atom other than the preferred fluorine-containing organic group is a hydrogen atom.

  Further, a preferred fluorine-containing polysilazane (b) in the present invention is a fluorine-containing polysilazane represented by the following general formula (A).

Formula (A):
^{_{[(Rf'Q) a Si (R}} 1) b (NR 2) 4-a-b / 2] l · [(Rf'Q) c Si (R 1) d O 4-c-d / 2] m [[Rf′Q) _e Si (R ¹ ) _f (NR ² ) _{g / 2} O _{h / 2} ] _n

(In the general formula (A), R ^{1 s} may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group; R ² may be the same or different, and Rf ′ may be the same or different and is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl ether group having 2 to 35 carbon atoms; Q is And a divalent organic group having 2 to 5 carbon atoms; independently in each first structural unit, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is Each is an integer of 1 to 3, and in each second structural unit, c is an integer of 0 to 2, d is an integer of 1 to 3, provided that c + d is an integer of 1 to 3, In the third structural unit, e and f are integers from 0 to 2, and g Fine h is an integer of 1 or 2, provided that be e + f + g + h = 4; l, m and n are numbers equal to or greater than 1).

In the formula (A), each R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. Examples of the unsubstituted or substituted monovalent hydrocarbon group include methyl, ethyl, propyl, Alkyl groups such as butyl and hexyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and tolyl groups, cycloalkyl groups such as cyclohexyl groups, or a part of hydrogen atoms bonded to carbon atoms of these groups or A halogenated hydrocarbon group, all of which are substituted with halogen atoms, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, such as a 3,3,3-trifluoropropyl group, CF is a _{3 CF 2 CF 2 CH 2 CH} 2 group or the like; ^{R 2} is a hydrogen atom or an alkyl group, e.g., methyl, ethyl, propyl, butyl, be hexyl In certain preferably a hydrogen atom; Rf 'is, for example, the _{formula: C i F 2i + 1 -} ( where, i is an integer of 1 to 20) perfluoroalkyl group represented by, or example, the formula:

(Where j is an integer of 1 to 50) and the like; Q is a divalent organic group having 2 to 5 carbon atoms, for example, the formula: —CH ₂ CH ₂ — Group, an alkylene group such as —CH ₂ CH ₂ CH ₂ — group, a formula: an oxygen-substituted alkylene group such as —CH ₂ OCH ₂ CH ₂ CH ₂ — group, an alkylamide group such as —CONHCH ₂ CH ₂ CH ₂ —, etc. It is.

  a to h are each the above-mentioned integers, provided that a + b, c + d and e + f + g + h are each the above-mentioned integers, and may be the same or different in each structural unit. L, m and n are each an integer of 1 or more, and l + m is preferably 10 to 500. By setting the value of l + m to 10 or more, the strength of the resulting cured film becomes high. On the other hand, by setting the value of l + m to 100 or less, the curability is improved. n is usually an integer of 2 to 100, more preferably 5 to 70.

  Furthermore, the ratio of l and m in the fluorine-containing polysilazane represented by the formula (A) is such that m / (l + m) is 0.05 to 0.5 from the viewpoint of the curing rate and antifouling property of the resulting cured film. A range is preferable.

  Synthesis of fluorinated polysilazane: The fluorinated silazane compound represented by the general formula (A) includes, for example, an organosilane represented by the following general formula (B) and an organopolysiloxane represented by the following average composition formula (C): Can be produced by reacting with at least one selected from ammonia and primary amines.

Formula (B):
(Rf′Q) _a Si (R ¹ ) _b X _4-ab

[Wherein R ¹ , Rf ′, Q, a, b and a + b are as defined in the general formula (A); X is a halogen atom such as chlorine or bromine. ]

Formula (C):
^{_{(Rf'Q) p Si (R 1}} ) q X r O 4-p-q-r / 2

[Wherein R ¹ , Rf ′, Q and X are as defined in the general formula (A), and p, q and r are 0 ≦ p <3, 0 <q <3, 0 <, respectively. r <3, where p + q + r <4. ]

Such fluorine-containing polysilazanes are known, and are described in, for example, JP-A-3-290437 and JP-A-2002-174702. In addition, a coating composition containing fluorine-containing polysilazane is also commercially available, and in the present invention, such a commercially available coating composition (for example, trade name “FPZ” used in the examples described later, manufactured by Tonen Corporation) is used. The fluorine-containing polysilazane in this commercially available coating composition is a silazane unit containing a perfluoroalkyl group-substituted alkyl group in which R _perf is a linear perfluoroalkyl group having 4 to 10 carbon atoms and R is a trimethylene group or a dimethylene group. Is considered to be a fluorine-containing polysilazane containing a relatively small amount (about 5 to 20 mol%) of all silazane units.

  In general, polysilazane including fluorine-containing polysilazane is composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture having a plurality of these structures in the molecule. The molecular weight of polysilazane is preferably a number average molecular weight of 200 to 50,000.

  In order to cure such polysilazane to form silica, heating called firing is usually required. However, in the present invention, when the substrate is a synthetic resin, the firing temperature is limited. That is, it is difficult to cure by heating above the heat resistance temperature of the substrate. Generally, the heat resistance of the cured product of the coating composition is higher than that of the substrate. However, in some cases, the heat resistance of the cured product may be lower than the heat resistance of the substrate, and in that case, it may be necessary to cure the polysilazane at a temperature lower than the heat resistance temperature of the cured product. Therefore, in the present invention, the raw baking temperature of the fluorine-containing polysilazane (b) is preferably 180 ° C. or lower when a normal synthetic resin such as an aromatic polycarbonate resin is used as a base material.

  In order to cure the fluorine-containing polysilazane (b) at a low temperature, the coating composition preferably contains a catalyst. Curing at room temperature is possible depending on the type and amount of the catalyst. Further, the atmosphere for curing is preferably an atmosphere containing oxygen such as in the air.

  As the catalyst, it is preferable to use a catalyst capable of curing polysilazane at a lower temperature. Examples of such a catalyst include fine particles of metals such as gold, silver, palladium, platinum and nickel proposed in JP-A-7-196986, and carboxylic acid complexes thereof proposed in JP-A-5-93275. Can be mentioned.

Further, instead of adding a catalyst to the coating composition, as proposed in JP-A-9-31333, the substrate is directly contacted with a catalyst solution, specifically an amine aqueous solution, or the like. A method of exposing to steam for a certain period of time can also be adopted.

  Since polysilazane is cured by irradiation with active energy rays in the presence of a photoinitiator, the fluorine-containing polysilazane (b) is used in the present invention by optimizing the irradiation conditions of the photoinitiator and active energy rays. Can be cured with active energy rays.

  In the coating composition of the present invention, the ratio of polysilazane (the total of fluorine-containing polysilazane (b) and other polysilazane) to the polyfunctional fluorine compound (a) is not particularly limited, but it is large from the viewpoint of scratch resistance. The functional fluorine compound (a) / polysilazane is preferably in the range of 0.01 to 10 (mass ratio), and further in the range of 0.1 to 5 (mass ratio) from the viewpoint of imparting adhesion to the substrate. It is more preferable that

  In addition, when the fluorine-containing polysilazane (b) is used in combination with another polysilazane, the ratio of the fluorine-containing polysilazane (b) in the total polysilazane is determined by necessary surface characteristics such as water repellency, but sufficient effects Is preferably 10% or more by mass.

(Other ingredients)
The coating composition of the present invention comprises colloidal silica within the range not impairing the effects of the present invention according to various purposes in addition to the above-mentioned polyfunctional fluorine compound (a) and fluorine-containing polysilazane (b). Stabilizers such as other polymerizable monomers, photopolymerization initiators, ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, antisettling agents, pigments , A coloring dye, an infrared absorber, a fluorescent brightener, a dispersant, an antistatic agent, a surfactant such as an antifogging agent, a curing catalyst selected from acids, alkalis and salts, etc. In particular, it is preferable to contain an ultraviolet absorber or a light stabilizer.

-Colloidal silica-
The coating composition of the present invention can contain colloidal silica having an average particle size of 200 nm or less in order to increase the wear resistance and hardness of the transparent cured product layer. The average particle size of the colloidal silica is more preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. By setting the average particle diameter of the colloidal silica within the above range, occurrence of haze can be suppressed.

Moreover, when using colloidal silica, in order to fully exhibit the effect to be used, the amount of colloidal silica is the amount of the active energy ray-curable component (polyfunctional fluorine compound (a) in the coating composition). 5-300 mass parts is preferable with respect to 100 mass parts) (total with the other polymerizable monomer mentioned later), 10-250 mass parts is more preferable, and 10-50 mass parts is still more preferable.
By setting the amount of colloidal silica to 5 parts by mass, sufficient wear resistance can be obtained.
Moreover, the transparency of a transparent hardened | cured material layer can be maintained by setting it as less than 300 mass parts, and when performing secondary processes, such as a hot bending process mentioned later, the crack is cracked. It can be made difficult to occur.

  Further, colloidal silica can be unmodified colloidal silica, but preferably surface-modified colloidal silica is used. The use of surface-modified colloidal silica improves the dispersion stability of the colloidal silica in the composition. It is considered that the average particle size of the colloidal silica fine particles is not substantially changed or slightly increased by modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range. Hereinafter, the surface-modified colloidal silica (hereinafter simply referred to as modified colloidal silica) will be described.

  Various dispersion media are known as a dispersion medium for colloidal silica, and the dispersion medium for raw material colloidal silica is not particularly limited. If necessary, modification can be performed by changing the dispersion medium, and the dispersion medium can be changed after modification. The dispersion medium of the modified colloidal silica is preferably used as the medium (solvent) for the cured composition in the coating composition as it is. The medium of the curable composition in the coating composition is preferably a solvent having a relatively low boiling point, that is, a normal coating solvent from the standpoint of dryness. For reasons such as ease of manufacture, the dispersion medium of the raw material colloidal silica, the dispersion medium of the modified colloidal silica, and the medium of the cured composition in the coating composition are all preferably the same medium (solvent). As such a medium, an organic medium widely used as a solvent for paint is preferable.

  As the dispersion medium, for example, the following dispersion medium can be used. water. Lower alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol. Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethyl cellosolve acetate. Dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone, etc.

  As described above, an organic dispersion medium is particularly preferable as the dispersion medium, and among these organic dispersion media, an organic dispersion medium having no hydroxyl group, such as ethyl cellosolve acetate, xylene, and butyl acetate, is stable in storage of the fluorinated polysilazane (b). From the viewpoint of sex. Note that an integral body of colloidal silica and a dispersion medium in which it is dispersed is called a colloidal silica dispersion.

  The colloidal silica is preferably modified using a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded (hereinafter referred to as a modifier). It is considered that silanol groups are generated by hydrolysis of hydrolyzable silicon groups, and these silanol groups react with and bind to silanol groups which are considered to be present on the colloidal silica surface, and the modifier is bound to the colloidal silica surface. Two or more modifiers may be used in combination. Further, as described later, a reaction product obtained by reacting two kinds of modifiers having reactive functional groups that are reactive with each other in advance can also be used as the modifier.

  The modifier may have two or more hydrolyzable silicon groups or silanol groups, and may be a partial hydrolysis condensate of a compound having hydrolyzable silicon groups or a partial condensate of a compound having silanol groups. May be. Preferably, a compound having one hydrolyzable silicon group is used as a modifying agent (a partially hydrolyzed condensate may be formed during the modification process). The modifier has an organic group bonded to a silicon atom, and at least one of the organic groups is preferably an organic group having a reactive functional group.

  Preferred reactive functional groups are amino groups, mercapto groups, epoxy groups and (meth) acryloyloxy groups. The organic group to which the reactive functional group is bonded is preferably an alkylene group having 8 or less carbon atoms or a phenylene group, excluding the reactive functional group, and particularly preferably an alkylene group having 2 to 4 carbon atoms (particularly a polymethylene group). Specific modifiers include the following compounds, for example, according to the type of reactive functional group.

(I). (Meth) acryloyloxy group-containing silanes 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, and the like.

(B). Amino group-containing silanes 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N- (N-vinylbenzyl-2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

(C). Mercapto group-containing silanes 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and the like.

(D). Epoxy group-containing silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltriethoxysilane.

(E). Isocyanate group-containing silanes 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and the like.

  Examples of the reaction product obtained by reacting the two modifiers having reactive functional groups in advance include, for example, a reaction product of an amino group-containing silane and an epoxy group-containing silane, an amino group-containing silane, There are reaction products of (meth) acryloyloxy group-containing silanes, reaction products of epoxy group-containing silanes and mercapto group-containing silanes, reaction products of two molecules of mercapto group-containing silanes, and the like.

  The modification of the colloidal silica is usually performed by bringing a modifier having a hydrolyzable group into contact with the colloidal silica in the presence of a catalyst for hydrolysis. For example, the modification can be performed by adding a modifier and a catalyst to the colloidal silica dispersion and hydrolyzing the modifier in the colloidal silica dispersion.

  Examples of the catalyst include acids and alkalis. Preferably, an acid selected from inorganic acids and organic acids is used. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. As the organic acid, formic acid, acetic acid, oxalic acid, (meth) acrylic acid and the like can be used. The reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is preferably in the range of 0.5 to 24 hours depending on the temperature.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but 1 to 100 parts by mass of the modifier is appropriate for 100 parts by mass of the colloidal silica (solid content in the dispersion).

-Other polymerizable monomers-
The coating composition of the present invention can contain another polymerizable monomer different from the polyfunctional fluorine compound (a).
Examples of other polymerizable monomers include polyfunctional compounds and monofunctional compounds.
The “polyfunctional compound” in the present invention is different from the “polyfunctional fluorine compound” in that it does not contain fluorine.
Examples of the polymerizable functional group include unsaturated groups such as (meth) acryloyl group, vinyl group and allyl group, and groups having the same, and (meth) acryloyl group is preferable.

  As a polyfunctional compound that can be used in the coating composition of the present invention, one type of polyfunctional compound may be used, or a plurality of types of compounds may be used. In the case of a plurality of compounds, different compounds in the same category or different compounds in the category may be used. For example, in the case of acrylic urethane described below, a combination of different compounds each of which is acrylic urethane may be used, or a combination in which one is acrylic urethane and the other is an acrylate compound having no urethane bond.

  The polyfunctional compound is preferably a compound having two or more polymerizable functional groups selected from (meth) acryloyl groups. In particular, a compound having an acryloyl group that is more easily polymerized by ultraviolet rays is preferable. More preferably, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of (meth) acrylic acid and a compound having two or more hydroxyl groups such as a polyhydric alcohol is preferable.

  The polyfunctional compound may be a compound having two or more polymerizable functional groups in one molecule, or may be a compound having the same polymerizable functional group. Moreover, 2-50 pieces are preferable and, as for the sum total of the polymerizable functional group in 1 molecule of a polyfunctional compound, 3-30 pieces are more preferable.

  In the coating composition, two or more polyfunctional compounds may be contained as the polyfunctional compound. Moreover, the monofunctional compound which has one polymerizable functional group may be contained with the polyfunctional compound. As this monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable.

  In addition, when using this monofunctional compound together in the coating composition, the ratio of the monofunctional compound to the total of the polyfunctional compound and the monofunctional compound is not particularly limited, but is 0 to 60% by mass. Preferably, 0 to 30% by mass is more preferable. By setting the ratio of the monofunctional compound to 60% by mass or less, the hardness and abrasion resistance of the cured coating film can be made sufficient.

  Furthermore, the polyfunctional compound may be a compound having various functional groups and bonds in addition to the polymerizable functional group. For example, it may have a hydroxyl group, a carboxyl group, a halogen atom, a urethane bond, an ether bond, an ester bond, a thioether bond, an amide bond, a diorganosiloxane bond, or the like. In particular, a (meth) acryloyl group-containing compound having a urethane bond (so-called acrylic urethane) and a (meth) acrylic acid ester compound having no urethane bond are preferable. Hereinafter, the two kinds of polyfunctional compounds described above will be described.

(1) (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane)
Examples of the compounds include the following compounds (a) to (c).
(I). A reaction product of a compound (X1) having a (meth) acryloyl group and a hydroxyl group and a compound having two or more isocyanate groups (hereinafter referred to as polyisocyanate).
(B). A reaction product of the compound (X2) having the above compound (X1) and two or more hydroxyl groups and a polyisocyanate.
(C). A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate group and the compound (X2).

  In these reaction products, it is preferable that an isocyanate group does not exist, but a hydroxyl group may exist. Therefore, in the production of these reaction products, it is more preferable that the total number of moles of hydroxyl groups in all reaction raw materials is equal to or greater than the total number of moles of isocyanate groups.

  The compound (X1) in the above (i) and (b) may be a compound having one (meth) acryloyl group and one hydroxyl group, each having two or more (meth) acryloyl groups and one hydroxyl group. The compound may be a compound having one (meth) acryloyl group and two or more hydroxyl groups, or a compound having two or more (meth) acryloyl groups and hydroxyl groups.

  Specific examples include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, and the like in this order. These are monoesters of a compound having two or more hydroxyl groups and (meth) acrylic acid, or a polyester leaving one or more hydroxyl groups.

  Further, the compound (X1) may be a ring-opening reaction product of a compound having one or more epoxy groups and (meth) acrylic acid. The reaction between the epoxy group and (meth) acrylic acid causes the epoxy group to ring open to form an ester bond and a hydroxyl group, resulting in a compound having a (meth) acryloyl group and a hydroxyl group. Moreover, the epoxy group of a compound having one or more epoxy groups can be opened to form a hydroxyl group-containing compound, which can be converted to a (meth) acrylic acid ester.

  As the compound having one or more epoxy groups, a polyepoxide called a so-called epoxy resin is preferable. The polyepoxide is preferably a compound having two or more glycidyl groups such as polyhydric phenols-polyglycidyl ether (for example, bisphenol A-diglycidyl ether) or an alicyclic epoxy compound. Furthermore, a reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group can also be used as the compound (X1). Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate.

  The polyisocyanate in the above (a) and (b) may be an ordinary monomeric polyisocyanate, or a prepolymer compound such as a polyisocyanate multimer or modified product or an isocyanate group-containing urethane prepolymer. .

  Specific monomeric polyisocyanates include, for example, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate) [MDI], hexamethylene diisocyanate, isophorone diisocyanate, trans Examples include cyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI], hydrogenated XDI, and hydrogenated MDI (the abbreviations in []).

  The multimer includes a trimer (isocyanurate-modified product), a dimer, a carbodiimide-modified product, etc., and the modified product is a urethane-modified product obtained by modification with a polyhydric alcohol such as trimethylolpropane, Examples include burette modified products, allophanate modified products, and urea modified products. Examples of the prepolymer-like material include an isocyanate group-containing urethane prepolymer obtained by reacting a polyol such as a polyether polyol or a polyester polyol described later with a polyisocyanate. Two or more of these polyisocyanates can be used in combination.

  As the polyisocyanate, non-yellowing polyisocyanate (polyisocyanate having no isocyanate group directly bonded to an aromatic nucleus) is particularly preferable. Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate. As described above, multimers and modified products of these polyisocyanates are also preferable.

  Next, examples of the compound (X2) in the above (b) and (c) include polyhydric alcohol and polyol having a higher molecular weight than polyhydric alcohol. The polyhydric alcohol is preferably a polyhydric alcohol having 2 to 20 hydroxyl groups, and particularly preferably a polyhydric alcohol having 2 to 15 hydroxyl groups. The polyhydric alcohol may be an aliphatic polyhydric alcohol, or an alicyclic polyhydric alcohol or a polyhydric alcohol having an aromatic nucleus. Examples of the polyhydric alcohol having an aromatic nucleus include polyepoxide ring-opened products having an aromatic nucleus such as an alkylene oxide adduct of polyhydric phenols and polyhydric phenols-polyglycidyl ether.

  Specific examples of the polyhydric alcohol include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, Methylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, ring-opened product of bisphenol A-diglycidyl ether, vinylcyclohexenedi Examples thereof include ring-opened products of oxides.

  Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polyether ester polyol, and polycarbonate polyol. A hydroxyl group-containing vinyl polymer can also be used as the polyol. Two or more of these polyhydric alcohols and polyols can be used in combination.

  Specific examples of the polyol include, for example, ring-opening polymerization of cyclic esters such as polyethylene glycol, polypropylene glycol, bisphenol A-alkylene oxide adduct, polyether polyol such as polytetramethylene glycol, and poly-ε-caprolactone polyol. Polyester polyol obtained by reaction of a polybasic acid such as adipic acid, sebacic acid, phthalic acid, maleic acid, fumaric acid, azelaic acid, glutaric acid and the polyhydric alcohol with 1,6-hexanediol The polycarbonate diol obtained by reaction of phosgene is mentioned.

  Further, examples of the hydroxyl group-containing vinyl polymer include a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether, and hydroxyalkyl (meth) acrylate and a hydroxyl group-free monomer such as olefin. . Examples of the compound (X3) in the above (iii) include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

  (2) As a (meth) acrylic acid ester compound having no urethane bond, which is a preferable compound in the polyfunctional compound, a compound having two or more hydroxyl groups similar to the compound (X2) described in (1) Polyester with (meth) acrylic acid is preferred. The compound having two or more hydroxyl groups is preferably the polyhydric alcohol or polyol described in (1). Furthermore, a (meth) acrylic acid ester compound which is a reaction product of polyepoxide and (meth) acrylic acid is also preferable, and is commercially available as an epoxy resin such as a glycidyl ether polyepoxide or an alicyclic polyepoxide as a polyepoxide. Can be used. Specific examples of the polyfunctional compound not containing a urethane bond include the following compounds (a) to (c).

(I). (Meth) acrylate of aliphatic polyhydric alcohol For example, 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, Examples include dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate.

(B). (Meth) acrylates of polyhydric alcohols or polyphenols having an aromatic nucleus or triazine ring, for example, tris (2- (meth) acryloyloxyethyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) -2-hydroxy Ethyl isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) bisphenol A, bis (2- (meth) acryloyloxyethyl) bisphenol S, bis (2- (Meth) acryloyloxyethyl) bisphenol F, bisphenol A dimethacrylate.

(C). (Meth) acrylate of hydroxyl group-containing compound-alkylene oxide adduct, (meth) acrylate of hydroxyl group-containing compound-caprolactone adduct, (meth) acrylate of polyoxyalkylene polyol For example, tri (meth) of trimethylolpropane-EO adduct Acrylate, tri (meth) acrylate of trimethylolpropane-PO adduct, hexa (meth) acrylate of dipentaerythritol-caprolactone adduct, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate-caprolactone adduct, Tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate-caprolactone adduct (EO represents ethylene oxide, PO represents propylene oxide).

  Specific preferred polyfunctional compounds are the following acrylic urethane and polyfunctional compounds having no urethane bond. In the case of acrylic urethane, acrylic urethane which is a reaction product of pentaerythritol or its multimer polypentaerythritol, polyisocyanate and hydroxyalkyl (meth) acrylate), or hydroxyl-containing poly (meth) of pentaerythritol or polypentaerythritol A polyfunctional compound which is an acrylic urethane which is a reaction product of acrylate and polyisocyanate and has 3 or more (preferably 4 to 20) polymerizable functional groups is preferable.

  As the polyfunctional compound having no urethane bond, pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate are preferable. Pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or polyester of polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 polymerizable functional groups). Isocyanurate-based poly (meth) acrylate is tris (hydroxyalkyl) isocyanurate or an addition product obtained by adding 1 to 6 moles of caprolactone or alkylene oxide to 1 mole thereof and a polyester (meth) acrylic acid ( Having 2 to 3 polymerizable functional groups). It is also preferable to use these preferred polyfunctional compounds and polyfunctional compounds having two or more other polymerizable functional groups (particularly poly (meth) acrylates of polyhydric alcohols) in combination.

  As the monofunctional compound that can be used in the coating composition of the present invention, for example, a compound having one (meth) acryloyl group in the molecule is preferable. Such a monofunctional compound may have a functional group such as a hydroxyl group or an epoxy group. Preferred monofunctional compounds are (meth) acrylic acid esters, ie (meth) acrylates.

  Specific monofunctional compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth). Examples include acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate.

-Photopolymerization initiator-
The coating composition of the present invention preferably contains a photopolymerization initiator. Known photopolymerization initiators can be used. A commercially available product that is readily available is particularly preferred. A plurality of photopolymerization initiators may be used in the coating composition.
Examples of the photopolymerization initiator include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, benzoylbenzoates, α-acylose). Oxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. . In particular, it is preferable to use an acylphosphine oxide photopolymerization initiator and a diacylphosphine oxide photopolymerization initiator. Moreover, a photoinitiator can also be used in combination with photosensitizers, such as amines.

  Specific photopolymerization initiators include, for example, 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-methyl-propan-1-one, 1- (4-dodecylphenyl) -2-methyl-propan-1-one, 1 -{4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- {4- (methylthio) phenyl} -2 -Morpholinopropan-1-one, benzyl, benzoin, benzoin methyl ether, benzoy Ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl 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, methylphenylglyoxylate, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methyl Ruthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 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, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

  The amount of the photopolymerization initiator in the coating composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable component (the total of the polyfunctional fluorine compound and other polymerizable monomers). In particular, 0.1 to 10 parts by mass is preferable.

-UV absorber-
The coating composition of the present invention preferably contains a known or well-known ultraviolet absorber that is commercially available. Examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a salicylic acid ultraviolet absorber, and a phenyltriazine ultraviolet absorber.

  Specific examples of the compound include octyl 3- {3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl} propionate, 2- (3,5-di-t -Pentyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,4 -Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, p t-butylphenyl salicylate, 2- {2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole, 3- (3-benzotriazole-4-hydroxy-5-t-butylphenyl) propionic acid 2- Hydroxy-3-methacryloyloxypropyl is mentioned.

-Light stabilizer-
The coating composition of the present invention preferably contains a hindered amine light stabilizer that is usually used as a light stabilizer for synthetic resins.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinimide, 1 -[2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionyloxy] -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) sebacate, 2-butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N -Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetra Carboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, bis (2,2,6,6-tetramethyl-4- Piperidyl) .di (tridecyl) butane-1,2,3,4-tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butane-1,2, 3,4-tetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl- 4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis {N- ( 2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxy Ethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-t-octylamino-4,6-dichloro-1,3,5-triazine / N, N'- Bis (2,2,6,6-tetra Methyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

[Transparent coated molded products]
The present invention relates to a transparent coated molded article having a transparent substrate and a transparent cured product layer in which a cured product of the coating composition is formed on at least a part of the surface of the transparent substrate.

(Base material)
The transparent substrate used in the present invention is not particularly limited as long as it is a transparent substrate, but it is preferable to use a transparent synthetic resin substrate or a glass substrate. From the viewpoint of ease of bending, the transparent substrate is transparent. It is more preferable to use a synthetic resin base material.

As the transparent synthetic resin base material, for example, a transparent synthetic resin such as an aromatic polycarbonate resin, a polymethyl methacrylate resin (acrylic resin), or a polystyrene resin can be used, and an aromatic polycarbonate resin is particularly preferable.
This substrate is molded, for example, a sheet-like substrate such as a flat plate or corrugated plate, a film-like substrate, a substrate molded into various shapes, a laminate in which at least the surface layer is made of various transparent synthetic resins, etc. There is. In particular, a sheet-like substrate or a film-like substrate is preferable.

As the glass substrate, for example, an alkali-free glass plate is preferable.
As the glass substrate, one that has been subjected to surface treatment in advance can be used. Examples of the surface treatment include cleaning with a UV cleaning device, brush cleaning using a cleaning agent, and ultrasonic cleaning.

  Moreover, although the thickness of a base material is not specifically limited, 1-100 mm is preferable from a viewpoint of rigidity and intensity | strength. Setting the thickness of the substrate within the above range is also preferable from the viewpoint of the ease of bending when a transparent synthetic resin substrate is used as the transparent substrate.

[Method for producing transparent coated molded article]
The transparent coated molded article of the present invention is coated with a coating composition containing a polyfunctional fluorine compound (a) and a fluorine-containing polysilazane (b) on at least a part of the substrate surface, and then cured. Can be obtained.

  Here, the means for applying the coating composition is not particularly limited, and a known method can be adopted, for example, a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, Examples thereof include a blade coating method, an air knife coating method, a spin coating method, a slit coating method, and a micro gravure coating method.

Moreover, the following three methods are mentioned as a method of hardening the coated composition for coating.
(I). After coating the coating composition, after irradiation of a sufficient amount of active energy rays to sufficiently cure the polyfunctional fluorine compound (a), the fluorine-containing polysilazane (b) (with other polysilazane) The partially cured product or the uncured product (including the case of combined use, the same shall apply hereinafter) is heated, left at room temperature, or exposed to the vapor of a curing catalyst solution of fluorine-containing polysilazane (b).

(B). After coating the coating composition, the uncured product of the fluorinated polysilazane (b) was heated, allowed to stand at room temperature, or cured by exposure to the vapor of a curing catalyst solution of the fluorinated polysilazane (b). Thereafter, the polyfunctional fluorine compound (a) is cured by irradiating a sufficient amount of active energy rays.

(C). A method in which the polyfunctional fluorine compound (a) and the fluorine-containing polysilazane (b) are cured almost simultaneously by irradiation with the energy beam. In this method, since the curing of the fluorine-containing polysilazane (b) is usually slower than the curing of the polyfunctional fluorine compound (b), it is considered that the curing is actually performed by the same process as the method (a).

As the active energy ray for curing the polyfunctional fluorine compound, ultraviolet rays are particularly preferable.
However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. As the ultraviolet light source, a xenon lamp, a pulse 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, a tungsten lamp, or the like can be used.

The coating composition can be used after being diluted with a solvent in order to be applied to a substrate. Dilution with a solvent is usually essential, and a solvent is used unless the polyfunctional fluorine compound (a) is a particularly low-viscosity liquid. As the solvent, a solvent that is soluble in both the polyfunctional fluorine compound (a) and polysilazane is used. When colloidal silica is added, the dispersion medium of the raw material colloidal silica may be used as a solvent as it is.

  Furthermore, it is preferable to select and use an appropriate solvent depending on the type of substrate. Among these, when the storage stability of the fluorine-containing polysilazane (b) is taken into consideration, a solvent containing no hydroxyl group in the molecule is particularly preferable.

  Specific examples include hydrocarbons, halogenated hydrocarbons, ketones, ethers and esters. For example, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene and other hydrocarbons, methylene chloride, Halogenated hydrocarbons such as chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran, Examples include ethers such as tetrahydropyran, and esters such as n-butyl acetate and diethylene glycol monoacetate.

  The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the drying temperature conditions, and the like. Usually, it is preferably 100 times or less, more preferably 0.1 to 50 times by mass with respect to the curable component (total of active energy ray-curable component and polysilazane) in the composition.

  In addition, when the coating composition after coating contains a solvent, after drying and removing the solvent, the polyfunctional fluorine compound (a) is cured by irradiation with ultraviolet rays or the like, and further, fluorine-containing polysilazane ( b) can be cured by methods such as heating, standing at room temperature, irradiation with active energy rays, or exposure to the vapor of the curing catalyst solution.

  The thickness of the layer of the cured product formed using the coating composition of the present invention is preferably 0.1 to 50 μm from the viewpoint of the efficiency of curing with active energy rays and the wear resistance after curing. . A more preferable layer thickness is 1 to 30 μm.

  Since the transparent coated molded article of the present invention has surface characteristics such as wear resistance and scratch resistance almost equal to those of glass, it can be used in various applications where glass has conventionally been used. Of various applications, in the case of an application as a window material for a vehicle, a bent molded product is often required. However, when using a base material that has been bent in advance, it becomes difficult to form a transparent cured product layer by coating and curing the coating composition.

  Therefore, the transparent coated molded article that has been bent is formed on the base material with an uncured product, a partially cured product or a completely cured product of the polyfunctional fluorine compound (a), and an uncured product of the fluorine-containing polysilazane (b) or After forming a layer of an uncured or partially cured product of a coating composition containing a partially cured product, the substrate having this layer is bent, and then the uncured or partially cured fluorine-containing polysilazane (b) In the case where an uncured product or a partially cured product of the polyfunctional fluorine compound (a) is present, it is preferable that the coating composition is completely cured to produce the product.

  According to this, the uncured product or partially cured product of the fluorinated polysilazane (b) is cured by heating for bending, but the fluorinated polysilazane (b) is usually not cured compared to the time required for bending. Since the time required for curing the cured product or the partially cured product is long, there is little possibility that bending processing becomes difficult due to the curing of the fluorine-containing polysilazane (b).

  Specifically, for example, after coating the coating composition on a substrate, the polyfunctional fluorine compound (a) is uncured, partially cured or completely cured, and fluorine-containing polysilazane (b). The polysilazane-containing uncured product or partially-cured product is heated to the heat softening temperature of the substrate for about 5 minutes, followed by bending. Thereafter, the uncured product or partially cured product of the fluorinated polysilazane (b) is kept at a temperature at which it can be cured or left at room temperature, irradiated with active energy rays, or vaporized into the curing catalyst solution of the fluorinated polysilazane (b). It is cured by exposure, and when there is an uncured product or a partially cured product of the polyfunctional fluorine compound (a), it is cured by irradiation with active energy rays, whereby the bending-molded coating molding of the present invention Goods are obtained. By such a method, the base material is deformed before the fluorine-containing polysilazane (b) is completely cured, and then a hard silica layer is formed, so that problems such as cracks in the cured product layer do not occur. .

  The above-described method enables bending of transparent coated molded products having excellent wear resistance, so vehicle windows, motorcycle windshields, goggles, showcases with curved surfaces, etc. that could not be used conventionally. Application to is possible.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
<Preparation of coating composition (A)>
In a 500 mL four-necked flask equipped with a stirrer and a condenser tube, 15 g of butyl acetate, 15 g of xylene, 2.5 g of 2- {2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole, 2-methyl 0.5 g of -1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one and bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate 5 g was added and dissolved, followed by 25 g of the polyfunctional fluorine compound (M-1) of the present invention and a low-temperature-curable perfluoroalkyl group-containing polysilazane xylene solution (solid content 20 mass%, manufactured by Tonen Co., Ltd., trade name “FPZ ] 62.5 g was added and stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating composition (A).

<Creation of transparent cured product layer>
Coating the coating composition (A) on a base material (transparent aromatic polycarbonate resin plate with a thickness of 3 mm, expressed as PC) using a bar coater (wet thickness 16 μm), in a hot air circulating oven at 80 ° C. For 5 minutes. This is irradiated with ultraviolet rays of 2000 mJ / cm ² (ultraviolet integrated energy amount in the wavelength range of 300 to 390 nm, the same shall apply hereinafter) using a high-pressure mercury lamp in an air atmosphere and then held in a hot air circulation oven at 100 ° C. for 120 minutes. The sample which formed the transparent hardened | cured material layer with a film thickness of 5 micrometers was prepared. Each measurement shown below was performed using this sample.

[Initial haze value, abrasion resistance]
According to the abrasion resistance test method in JIS-R3212, the haze was measured with a haze meter when a 500 g weight was combined with each of two CS-10F wear wheels for 500 rotations. The haze value was measured at four locations on the wear cycle orbit, and the average value was calculated.
The initial haze value indicates the haze value (%) before the wear resistance test, and the wear resistance indicates the value (%) of (haze value after wear test) − (haze value before wear test).

[Adhesion]
The sample is made with 11 razor cuts at intervals of 1 mm with a razor blade to make 100 grids. The number (m) of the grids remaining without peeling off the coating when the commercially available cellophane tape is well adhered and then suddenly peeled 90 degrees forward is expressed as m / 100. The initial adhesion after sample preparation and the moisture resistance adhesion after storage for 7 days under an atmosphere of 60 ° C. and 95% were also measured.

[Anti-fouling test]
As an index of surface contamination resistance, the sample was conditioned at 25 ° C and 60% RH for 2 hours, and then “Magic ink” (trade name) was attached to the sample surface, and then wiped off with a cleaning cloth. As a result, the “magic ink” adhesion was evaluated as follows.

A: The mark of “magic ink” can be completely wiped off.
○: A trace of “magic ink” is visible.
Δ: A trace of “magic ink” is visible.
X: Traces of “magic ink” are hardly wiped off.

(Examples 2 to 10)
In Example 1, instead of the fluorine-containing polyfunctional compound (M-1), the fluorine-containing polyfunctional compound of the present invention shown in Table 1 was used, and the substrate shown in Table 1 was used as the substrate. The sample which formed the transparent hardened | cured material layer similarly to 1 was created, and the same evaluation was performed.
Here, in the examples in which the substrate is described as “GL”, after cleaning with a UV cleaning device, brush cleaning is performed using a cleaning agent, ultrasonic cleaning with ultrapure water is further performed, and then heat treatment is performed at 120 ° C. for 3 minutes. Then, a non-alkali glass plate (thickness 1 mm) whose surface state was stabilized was used.

(Comparative Examples 1-3)
In Example 1, instead of the fluorine-containing polyfunctional compound (M-1), dipentaerythritol hexaacrylate shown in Table 1 (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA), tetrafunctional urethane acrylate (Japan) A sample in which a transparent cured product layer was formed in the same manner as in Example 1 except that Kayaku Co., Ltd., trade name: U-4HA) was used and the base material shown in Table 1 was used as the base material. The same evaluation was performed.

(Comparative Examples 4 and 5)
In Example 1, the fluorine-containing polyfunctional compound (M-1) or (M-9) was used, and a xylene solution of a low-temperature curable perhydropolysilazane (instead of a low-temperature curable perfluoroalkyl group-containing polysilazane xylene solution ( A sample in which a transparent cured product layer was formed in the same manner as in Example 1 except that a solid content of 20% by mass, manufactured by Tonen Co., Ltd., trade name “L110”) was used, and the same evaluation was performed.

(Example 11)
<Preparation of coating composition (B)>
In a 500 mL four-necked flask equipped with a stirrer and a condenser tube, 15 g of butyl acetate, 15 g of xylene, 2.5 g of 2- {2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole, 2-methyl 0.5 g of -1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one and bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate 5 g was added and dissolved, followed by 25 g of the polyfunctional fluorine compound (M-1) of the present invention, mercaptosilane-modified colloidal silica dispersion (xylene-dispersed colloidal silica (silica content 30 mass%, average particle size 11 nm)) To 100 parts by mass, 5 parts by mass of 3-mercaptopropyltrimethoxysilane and 3.0 parts by mass of 0.1N hydrochloric acid are added, and at 100 ° C. 30g, prepared by aging at room temperature for 12 hours after heating and stirring), xylene solution of low temperature curable perfluoroalkyl group-containing polysilazane (solid content 20% by mass, manufactured by Tonen Corporation, trade name "FPZ") 62.5g Was added at room temperature for 1 hour in a nitrogen atmosphere to obtain a coating composition (B).

<Creation of transparent cured product layer>
The coating composition (B) was applied to the substrate PC using a bar coater (wet thickness 16 μm) and held in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with 3000 mJ / cm ² of ultraviolet light in an air atmosphere using a high pressure mercury lamp to form a transparent cured product layer having a thickness of 5 μm. Each measurement was performed using this sample.

(Examples 12 to 14)
In Example 11, a transparent cured product layer was formed in the same manner as in Example 11 except that the fluorine-containing polyfunctional compound of the present invention shown in Table 1 was used instead of the fluorine-containing polyfunctional compound (M-1). Samples were prepared and evaluated in the same manner.

(Example 15)
In Example 11, the coating composition (B) was coated on a base material using a bar coater (wet thickness 16 μm) and held in a hot air circulation oven at 80 ° C. for 5 minutes, and then this was placed in an air atmosphere. Irradiate UV light of 200 mJ / cm ² using a high-pressure mercury lamp, then hold it in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after taking out, 300 mmR so that the coated surface of the transparent cured product layer becomes convex. It was pressed against a mold with curvature and bent. Furthermore, as a result of observing the appearance of what was irradiated with ultraviolet rays of 3000 mJ / cm ² using a high-pressure mercury lamp, it had a good cured product layer with high transparency and no cracks or wrinkles.

<Fluorine-containing polyfunctional compound of the present invention>

  The transparent coated molded article in which the coating composition of the present invention is formed on at least a part of a transparent substrate is excellent in adhesiveness regardless of whether an aromatic polycarbonate resin plate or an alkali-free glass plate is used as the transparent substrate. In addition, it has excellent transparency before and after the abrasion resistance test, and has high antifouling properties. On the other hand, in the comparative example, the performance of either transparency or antifouling property before and after the abrasion resistance test is inferior, and the adhesion and these performances cannot be made compatible.

Claims (9)

A coating composition for forming a transparent cured product layer on at least a part of a transparent substrate, the coating composition comprising a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and- A fluorine-containing compound having three or more polymerizable groups selected from C (O) OCH═CH ₂ , wherein the fluorine content is 35.0% by mass or more of the molecular weight of the fluorine-containing compound, and the polymerizable group A coating composition containing a polyfunctional fluorine compound (a) having a calculated value of molecular weight between crosslinks of 300 or less and a fluorine-containing polysilazane (b) when polymerized. The coating composition according to claim 1, wherein the polyfunctional fluorine compound (a) is represented by the general formula (1).
General formula (1): Rf {-(L) m-Y} n
(In the formula, Rf represents an n-valent group selected from the following f-1 to f-10, n represents an integer of 3 to 6, and L represents an alkylene group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. It is obtained by combining 10 arylene groups, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, -S-, or -N (R)-. Or a group obtained by combining an arylene group having 6 to 10 carbon atoms and —O—, —S—, or —N (R) —, wherein R represents a hydrogen atom or an alkyl having 1 to 5 carbon atoms; M represents 0 or 1. Y represents a polymerizable group selected from a (meth) acryloyl group, an allyl group, an α-fluoroacryloyl group, an epoxy group, and —C (O) OCH═CH _2. .)

The coating composition according to claim 1 or 2, wherein the polyfunctional fluorine compound (a) is any one of the following M-1 to M-13.

The coating composition according to any one of claims 1 to 3, wherein the fluorine-containing polysilazane (b) is represented by the following general formula (A).
Formula (A):
^{_{[(Rf'Q) a Si (R}} 1) b (NR 2) 4-a-b / 2] l · [(Rf'Q) c Si (R 1) d O 4-c-d / 2] m [[Rf′Q) _e Si (R ¹ ) _f (NR ² ) _{g / 2} O _{h / 2} ] _n
(In the general formula (A), R ^{1 s} may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group; R ² may be the same or different, and Rf ′ may be the same or different and is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl ether group having 2 to 35 carbon atoms; Q is And a divalent organic group having 2 to 5 carbon atoms; independently in each first structural unit, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is Each is an integer of 1 to 3, and in each second structural unit, c is an integer of 0 to 2, d is an integer of 1 to 3, provided that c + d is an integer of 1 to 3, In the third structural unit, e and f are integers from 0 to 2, and g Fine h is an integer of 1 or 2, provided that be e + f + g + h = 4; l, m and n are numbers equal to or greater than 1).   The coating composition according to any one of claims 1 to 4, wherein the coating composition further contains colloidal silica having an average particle size of 200 nm or less.   It has a transparent base material, and the transparent hardened material layer in which the hardened material of the constituent for covering according to any one of claims 1 to 5 was formed in at least a part of the surface of the transparent base material, Transparent coated molded product.   The transparent film molded product according to claim 6, wherein the transparent substrate is a transparent synthetic resin substrate.   In a method for producing a transparent coated molded article having a transparent synthetic resin base material and a transparent cured product layer formed on at least a part of the surface of the transparent synthetic resin base material, at least a part of the surface of the transparent synthetic resin base material Application of the coating composition according to any one of claims 1 to 5, followed by curing of the polyfunctional fluorine compound (a) by irradiation with active energy rays, and the fluorine-containing polysilazane (b ) Is cured in any order or simultaneously.   In a method for producing a transparent coated molded article having a transparent synthetic resin base material and a transparent cured product layer formed on at least a part of the surface of the transparent synthetic resin base material, at least a part of the surface of the transparent synthetic resin base material Application of the coating composition according to any one of claims 1 to 5, followed by curing of the polyfunctional fluorine compound (a) by irradiation with active energy rays, and the fluorine-containing polysilazane (b ) Is cured in any order or simultaneously, and the fluorine-containing polysilazane (b) is bent in an uncured or partially cured state.