JP2005054029A - Composition for active energy ray-curing type coating and plastic molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating composition that is cured by irradiating with active energy ray and forms a coating film composed of a cured material having excellent abrasion resistance and transparency and developing excellent antistatic property, a coating composition that forms a coating film composed of a cured material having excellent lubricating properties and/or fingerprint adhesion resistance besides the above physical properties and a plastic molding having a coating film composed of the cured material of one of the coating compositions. <P>SOLUTION: The coating composition comprises 100 parts by mass of an active energy ray-curable polymerizable monomer (A) containing an active energy ray-curable polymerizable monomer (AI) containing a group in which the hydrogen of an alcoholic hydroxy group is substituted with an alkali metal atom and 0.1-500 parts by mass (calculated as solid) of colloidal silica (B). The coating composition comprises a compound having a silicone-containing part or a fluorine-containing part. The plastic molding has a coating film composed of the cured material of one of the coating compositions. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable coating composition that is cured by irradiation with active energy rays to give a coating having characteristics such as antistatic properties and abrasion resistance, and the coating composition on the surface of a substrate. The present invention relates to a plastic molded article having a coating made of a cured product.

  Today, plastic products such as polycarbonate resins, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, styrene resins such as ABS resin, MS resin and AS resin, vinyl chloride resins, Resin substrates such as cellulose acetate-based resins such as triacetylcellulose are used for containers, instrument panels, packaging materials, various housing materials, optical disk substrates, and plastic lenses because of their excellent lightness, ease of processing, impact resistance, etc. It is used for various applications as a base material for display devices such as liquid crystal displays and plasma displays.

  However, these plastic products are easily damaged because of their low surface hardness. For this reason, transparent resins such as polycarbonate and polyethylene terephthalate have the disadvantage that the inherent transparency and appearance of the resin are significantly impaired by repeated use, and the use of plastic products particularly in fields that require wear resistance is disadvantageous. It is difficult. Therefore, a hard coat material (coating material) is provided for the purpose of imparting abrasion resistance to the surface of the plastic product. However, the hardened layer of the conventional hard coat material has a drawback that static electricity is likely to be generated because of its high surface resistivity. The generated static electricity promotes the adhesion of dust and the like to the product, which has been a cause of damaging the aesthetics and transparency of the product.

  Thus, various hard coat materials having an antistatic function have been proposed. For example, a technique of blending an organic cationic substance such as a quaternary ammonium salt structure is known (see Patent Documents 1 and 2). However, the hardened layer of these hard coat materials is insufficient in water resistance and is not sufficient in abrasion resistance.

  On the other hand, a composition is also known in which conductive fine particles are further blended with a system capable of exhibiting a high degree of wear resistance using both an acrylic monomer and a silicon compound (see Patent Document 3). The cured layer of this composition is excellent in both antistatic properties and wear resistance, but since there are many inorganic filler components such as conductive fine particles, the light transmittance of the cured layer tends to decrease. Also, the substrate adhesion is insufficient. Furthermore, attempts have been made to impart conductivity to the polymer itself obtained from the active energy ray-curable monomer (see Patent Document 4). In this case, good antistatic properties are exhibited, but the wear resistance is not sufficient. In addition, although patent document 4 mentions the combination with an inorganic filler, there is no description about a specific material, addition amount, etc., and it is thought that feasibility is low.

  In addition, when applying a hard coating layer with anti-static performance for display and optical disc applications, there is also a device that improves surface lubricity, reduces the load due to external force applied during cleaning, and facilitates cleaning. Desired. Further, in many cases, anti-fingerprint adhesion properties that prevent adhesion of fingerprints are required.

JP-A-10-279833 (Claims) JP 2000-80169 A (Claims 1-3, 5-8) JP 2002-3751 A (Claims 1 to 6) JP-A-9-241337 (claims 2 to 9, paragraph 0078)

  The problem to be solved by the present invention is to cure by irradiating with active energy rays, and to form a film made of a cured product having good wear resistance, transparency and excellent antistatic properties. It is to provide a coating composition. Another problem to be solved by the present invention is a film made of a cured product having good wear resistance, transparency, antistatic property, and excellent lubricity and / or fingerprint resistance over a long period of time. It is in providing the coating composition which can form.

The present invention provides the following means.
(1) A coating composition containing 0.1 to 500 parts by mass (in terms of solid content) of colloidal silica (B) with respect to 100 parts by mass of the active energy ray-curable polymerizable monomer (A). , Active energy ray-curable polymerizable monomer (A) active mass ray-curable polymerization in which 5 parts by mass or more out of 100 parts by mass has a group in which an alcoholic hydroxyl group is replaced with an alkali metal atom. A coating composition, which is an adhesive monomer (AI).

(2) The active energy ray-curable polymerizable monomer (AI) having a group in which hydrogen of the alcoholic hydroxyl group is substituted with an alkali metal atom is represented by the following formula 1 or formula (1): Coating composition.
CH ₂ = C (R ¹ ) COO-R ² O-M Formula 1
^{_{(CH 2 = C (R 1}} ) COO) m R 3 O- (CONHR 4 NHCOO-R 2 O) n -M
... Formula 2
In Formula 1 or Formula 2, R ¹ is a hydrogen atom or a methyl group, R ² is a diol residue, R ³ is a polyol residue, R ⁴ is a diisocyanate residue, M is an alkali metal atom, and m is The integer of 1-20 and n show the integer of 1-50.

  (3) Modification with an average particle diameter of 1 to 200 nm in which the colloidal silica (B) is surface-modified with a mercaptosilane compound in which an organic group having a mercapto group and a hydrolyzable group and / or a hydroxyl group are bonded to a silicon atom The coating composition according to (1) or (2), which is colloidal silica.

(4) The coating composition according to any one of (1) to (3), further containing 0.01 to 10 parts by mass of the compound (C) with respect to 100 parts by mass of the polymerizable monomer (A). .
However, the compound (C) is represented in the molecule by at least one site (c-1) selected from the group consisting of moieties represented by the following formulas 3 to 7 and the following formulas 8 to 10. It has the site | part (c-2) which consists of at least 1 selected from the group which consists of a part, and an active energy ray hardening functional group (c-3).

_{^{- (SiR 5 R 6 O)}} x - ··· Formula 3
_{- (CF 2 CF 2 O)} p - ··· formula 4
_{- (CF 2 CF (CF 3} ) O) q - ··· Equation 5
_{- (CF 2 CF 2 CF 2} O) r - ··· formula 6
− (CF ₂ O) _s − Formula 7
(In the formula ^3, R 5, ^{R 6} are independently an alkyl group having 1 to 8 carbon atoms, is either a fluorine-containing alkyl group or a phenyl group having 1 to 8 carbon atoms, x is an integer from 1 to 1000 .
In Formulas 4-6, p, q, r, and s are integers of 1-100. )
-R ⁷ - ··· formula 8
_{- (CH 2 CH 2 O)} z - (CH 2 CH (CH 3) O) w - ·· formula 9
_{- (C (= O) C} u H 2u O) t - ··· Equation 10
(In Formula 8, R ⁷ is an alkylene group having 6 to 20 carbon atoms. In Formula 9, z is 0 to 100, w is 0 to 100, and is an integer satisfying 5 ≦ z + w ≦ 100.] 10, u is an integer of 3 to 5, and t is an integer of 1 to 20.)

  (5) A plastic molded article having a 0.1 to 50 μm-thick film made of a cured product of the coating composition according to any one of (1) to (4) on the surface of the plastic substrate.

  The coating composition of the present invention contains an active energy ray-curable polymerizable monomer having a group in which hydrogen of an alcoholic hydroxyl group is substituted with an alkali metal atom, and colloidal silica. Is excellent in antistatic properties and wear resistance. In addition, when the coating composition contains the compound (C) of the present invention, lubricity and / or fingerprint resistance can be imparted to the film made of the cured product. Since the compound (C) has appropriate compatibility with other components of the coating composition, the compound (C) can be used without impairing the transparency of the coating film before curing when applied to the substrate surface. Segregates on the coating surface. Since the active energy ray-curable functional group in the compound (C) is bonded and fixed to the resin matrix in the cured product of the coating composition by irradiation with the active energy beam, the cured product of the coating composition The resulting coating has excellent surface lubricity and / or fingerprint resistance over a long period of time.

  In this specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group, and acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid.

  In the coating composition of the present invention, the active energy ray-curable polymerizable monomer (A) (hereinafter sometimes referred to as the polymerizable monomer (A)) is irradiated with active energy rays. In particular, an active energy ray-curable polymerizable monomer (AI) having a group in which hydrogen of an alcoholic hydroxyl group is substituted with an alkali metal atom, and others The polyfunctional polymerizable monomer (AII) and the other polymerizable monomer represented by the monofunctional polymerizable monomer (AIII) which may be contained in the above are comprehensively represented.

  The polymerizable monomer (A) is an active energy ray-curable polymerizable monomer (AI) having a group in which hydrogen of an alcoholic hydroxyl group is substituted with an alkali metal atom (hereinafter referred to as monomer (AI) and May be noted.)

  Since the monomer (AI) has a group in which an alcoholic hydroxyl group hydrogen is substituted with an alkali metal atom and is excellent in conductivity, the monomer (AI) imparts antistatic properties to a film made of a cured product of the coating composition. Examples of the alkali metal atom include lithium, sodium, potassium, rubidium, cesium and the like. Lithium, sodium, and potassium are preferable, and lithium is particularly preferable in view of easy conductivity.

  The monomer (AI) has an active energy ray-curable functional group, and is cured with the polyfunctional polymerizable monomer (AII) or the monofunctional polymerizable monomer (AIII) by the active energy ray. Then, a resin matrix is formed.

  In the coating composition of the present invention, 5 parts by mass or more of 100 parts by mass of the polymerizable monomer (A) is the monomer (AI). It is more preferable that 10 to 100 parts by mass of 100 parts by mass of the polymerizable monomer (A) is the monomer (AI). When the ratio of the monomer (AI) is within this range, the balance between the wear resistance and the antistatic property of the coating formed of the cured product of the coating composition is excellent.

As the monomer (AI), a monomer represented by the following formula 1 or 2 is preferable.
CH ₂ = C (R ¹ ) COO-R ² O-M Formula 1
^{_{(CH 2 = C (R 1}} ) COO) m R 3 O- (CONHR 4 NHCOO-R 2 O) n -M
... Formula 2
In Formula 1 or Formula 2, R ¹ is a hydrogen atom or a methyl group, R ² is a diol residue, R ³ is a polyol residue, R ⁴ is a diisocyanate residue, M is an alkali metal atom, and m is The integer of 1-20 and n show the integer of 1-50.

The diol residue of R ² means a group formed by removing all hydroxyl groups from the diol. Specific examples of the diol include linear or branched alkylene glycols having 2 to 100 carbon atoms (for example, ethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, neo Pentyl glycol, 1,6-hexanediol, 1,9-nonanediol, etc.), bisphenol A or the like or condensates thereof (for example, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymer) Bisphenol A ethylene oxide ring-opening adduct, bisphenol A propylene oxide ring-opening adduct, etc.) and polyester diol (eg, polyadipate diol, polycarbonate) Tojioru, polycaprolactone diol, etc.) and the like. Preferred are polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, and more preferred is polyethylene glycol. Two or more of these may be used in combination.

  The molecular weight of the diol residue is 3000 or less, more preferably 2000 or less. When the molecular weight of the diol residue exceeds 3000, the molecular weight per (meth) acryloyl group increases, and the abrasion resistance of the cured product obtained from the coating composition by adding the monomer (AI) It tends to decrease.

  In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC).

The polyol residue of R ³ means a group formed by removing all hydroxyl groups from a polyol. Examples of the polyol include linear or branched alkylene glycols having 2 to 100 carbon atoms (for example, ethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, etc.) or condensates thereof (for example, diethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, etc.), trimethylolpropane, pentaerythritol, di Examples thereof include pentaerythritol, and trimethylolpropane, pentaerythritol, and dipentaerythritol are preferable.

The diisocyanate residue of R ⁴ means a group formed by removing all isocyanate groups from diisocyanate. Examples of the diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, bis (isocyanatemethyl) cyclohexane, 4,4′-diphenylmethane diisocyanate, and the like. Preferably, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, more preferably isophorone diisocyanate.

  The weight average molecular weight of the monomer (AI) represented by Formula 1 or Formula 2 is usually 100 to 100,000, and if it exceeds 100,000, the viscosity tends to be high and handling tends to be less than 150. The vapor pressure becomes too high, and the possibility of volatilization is increased in the coating process, which is not preferable. Preferably it is 100-30000, More preferably, it is 150-3000.

  In the monomer (AI) represented by Formula 2, m is an integer of 1 to 20, and if it exceeds 20, the molecular weight tends to be high and production tends to be difficult. Preferably it is an integer of 1-15, More preferably, it is an integer of 1-10. Moreover, n is an integer of 1-50, and when it exceeds 50, the viscosity tends to be high and handling tends to be difficult. Preferably it is an integer of 1-20, more preferably an integer of 1-10.

  The monomer (AI) in the present invention has two or more polymerizable functional groups in the molecule from the viewpoint of developing a high level of wear resistance of a coating formed of a cured product of the coating composition. Those having a molecular weight per functional group of 4000 or less are particularly preferred.

  The polyfunctional polymerizable monomer (AII) (hereinafter sometimes referred to as monomer (AII)) is described in paragraphs 0013 to 0052 of JP-A-10-81839. Corresponds to “compound (a)”. That is, it is a polyfunctional polymerizable monomer having two or more (meth) acryloyl groups in one molecule as polymerizable functional groups that can be polymerized by active energy rays.

  Preferred monomers (AII) include compounds having 2 or more, preferably 2 to 50, more preferably 3 to 30, one or more polymerizable functional groups selected from (meth) acryloyl groups. It is done. Among them, a compound having two or more (meth) acryloyl 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. In addition to the polymerizable functional group, compounds having various functional groups and bonds may be used. Examples of such a compound include a (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as “acryl urethane”) and a (meth) acrylic acid ester compound having no urethane bond.

  The acrylic urethane is an acrylic urethane which is a reaction product of pentaerythritol or polypentaerythritol which is a multimer thereof, polyisocyanate, and hydroxyalkyl (meth) acrylate, and is active energy ray-curable polymerization. It is a reaction product of a polyfunctional compound having 2 or more, more preferably 4 to 20, functional groups, or a poly (meth) acrylate containing pentaerythritol or polypentaerythritol, and a polyisocyanate. Examples thereof include polyfunctional compounds which are acrylic urethane and have 2 or more, more preferably 4 to 20, active energy ray-curable polymerizable functional groups.

  Examples of the (meth) acrylic acid ester compound having no urethane bond include pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate. The pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or polyester of polypentaerythritol and (meth) acrylic acid, and preferably has 4 to 20 active energy ray-curable polymerizable functional groups. The isocyanurate-based poly (meth) acrylate is a compound obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or tris (hydroxyalkyl) isocyanurate. , Polyester with (meth) acrylic acid, preferably having 2 to 3 active energy ray-curable polymerizable functional groups.

  The monomer (AII) is particularly preferably one having three or more polymerizable functional groups in the molecule and a molecular weight per functional group of 100 or less from the viewpoint of developing a high level of abrasion resistance. Specific examples of the monomer (AII) satisfying such conditions include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( Preferable examples include (meth) acrylate.

  As the polymerizable monomer (A), an active energy ray-curable polymerizable monomer (AI) having a group in which an alcoholic hydroxyl group is substituted with an alkali metal atom, a polyfunctional polymerizable monomer ( A polymerizable monomer other than AII) may be contained. As such a polymerizable monomer, a monofunctional polymerizable monomer having one (meth) acryloyl group in one molecule or a compound having one or more polymerizable functional groups other than a (meth) acryloyl group There is. However, polymerizable functional groups other than (meth) acryloyl groups are often not sufficiently hardened by active energy rays, and are not easily available, so that a group in which hydrogen of an alcoholic hydroxyl group is substituted with an alkali metal atom. As the polymerizable monomer other than the active energy ray-curable polymerizable monomer (AI) and the multifunctional polymerizable monomer (AII) having one, one (meth) acryloyl group is present in one molecule. The monofunctional polymerizable monomer (AIII) (hereinafter sometimes referred to as monomer (AIII)) is preferable.

As the monomer (AIII), the general formula ^{_{CH 2 = C (R 8)}} COOC k H 2k + 1 (R 8 is a hydrogen atom or a methyl group, _.C k _{H 2k + 1} k is an integer of 1-13 Alkyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol Mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,3-dibromopropyl ( (Meth) acrylate, dicyclopentenyl (meth) ac Rate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium Chloride, 2-hydroxypropyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylic Rate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, morpholine (meth) acrylate, nonylphenoxypolyethylene glycol ( (Meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) Acrylate, phenoxyhexaethylene glycol (meth) acrylate, Enoxy (meth) acrylate, polypropylene glycol (meth) acrylate, 2-sulfonic acid sodium ethoxy (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate , N-vinylcaprolactam, N-vinylpyrrolidone, dicyclopentadienyl (meth) acrylate, isobornyl acrylate and the like.

  The coating composition of the present invention contains 0.1 to 500 parts by mass of colloidal silica (B) as a solid content with respect to 100 parts by mass of the polymerizable monomer (A). Colloidal silica (B) is an ultrafine particle of silicic anhydride dispersed colloidally in a dispersion medium. The content of the colloidal silica (B) as a solid content is preferably 0.1 to 300 parts by mass, particularly preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A). When the thickness is within this range, the coating made of a cured product exhibits sufficient wear resistance, hardly causes haze, and does not easily cause cracks due to external force.

  Although the average particle diameter of the silica particle of colloidal silica (B) is not specifically limited, In order to express the high transparency of the film | membrane consisting of hardened | cured material, 1-1000 nm is preferable, 1-200 nm is more preferable, 1-50 nm Is particularly preferred.

  As the colloidal silica, those dispersed in the following dispersion medium can be used. Specifically, water, methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate , Isoamyl acetate, acetone and the like. Water, lower alcohols, esters, cellosolves, and the like are preferable because they have a certain degree of polarity and are easy to ensure dispersion stability of the sol.

  As the colloidal silica (B), modified colloidal silica in which the particle surface is modified with a hydrolyzate of a hydrolyzable silane compound in order to improve dispersion stability can also be used. Here, “surface-modified with a hydrolyzate” means that the hydrolyzate of the silane compound is physically or chemically bonded to a part or all of the silanol groups on the surface of the colloidal silica particles. It means that the surface properties have been modified. In addition, the silica particle which the thing which the condensation reaction of the hydrolyzate advanced has couple | bonded similarly is also contained. This surface modification can be easily performed by causing hydrolysis or condensation reaction of a part or all of the hydrolyzable group of the silane compound in the presence of colloidal silica particles.

  As the hydrolyzable silane compound, an organic group having a functional group such as a (meth) acryl group, amino group, epoxy group or mercapto group and a hydrolyzable group such as an alkoxy group and / or a hydroxyl group are bonded to a silicon atom. Silane compounds are preferred. For example, 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Etc. are preferable. Among these, a mercaptosilane compound in which an organic group having a mercapto group and a hydrolyzable group and / or a hydroxyl group are bonded to a silicon atom is preferable from the viewpoint of high reactivity with the polymerizable monomer (A). .

  It is preferable that the coating composition of this invention contains a compound (C). Compound (C) includes, in the molecule, at least one site (c-1) selected from the group consisting of moieties represented by the following formulas 3 to 7 and a moiety represented by the following formulas 8 to 10: It has the site | part (c-2) which consists of at least 1 selected from the group which consists of, and an active energy ray-curable functional group (c-3).

_{^{- (SiR 5 R 6 O)}} x - ··· Formula 3
_{- (CF 2 CF 2 O)} p - ··· formula 4
_{- (CF 2 CF (CF 3} ) O) q - ··· Equation 5
_{- (CF 2 CF 2 CF 2} O) r - ··· formula 6
− (CF ₂ O) _s − Formula 7
(In the formula ^3, R 5, ^{R 6} are independently an alkyl group having 1 to 8 carbon atoms, is either a fluorine-containing alkyl group or a phenyl group having 1 to 8 carbon atoms, x is an integer from 1 to 1000 .
In Formulas 4-6, p, q, r, and s are integers of 1-100. ).

-R ⁷ - ··· formula 8
_{- (CH 2 CH 2 O)} z - (CH 2 CH (CH 3) O) w - · Formula 9
_{- (C (= O) C} u H 2u O) t - ·· formula 10
(In Formula 8, R ⁷ is an alkylene group having 6 to 20 carbon atoms. In Formula 9, z is 0 to 100, w is 0 to 100, and is an integer satisfying 5 ≦ z + w ≦ 100.] 10, u is an integer of 3 to 5, and t is an integer of 1 to 20.)

  Compound (C) includes at least one moiety (c-1) selected from the group consisting of the moieties represented by the above formulas 3 to 7 (hereinafter sometimes simply referred to as moiety (c-1)). By containing, the film which consists of hardened | cured material of a coating composition provides lubricity and / or fingerprint adhesion resistance. In this specification, the lubricity means that the dynamic friction coefficient of the surface of the film made of a cured product is 0.1 or less, and the anti-fingerprint adhesion means the oleic acid contact angle of the surface of the film made of a cured product. Means 65 ° or more.

  Depending on the structure of the part (c-1), there are those that simultaneously provide lubricity and anti-fingerprint adhesion, and others that provide only one of them. When site | part (c-1) is a silicone containing unit or a fluorine-containing unit more than fixed molecular weight, lubricity can be provided. When site | part (c-1) is a fluorine-containing unit, fingerprint-proof adhesion property can be provided. In this case, the molecular weight is not particularly limited.

The part represented by Formula 3 has a function of expressing lubricity. In the formula, R ⁵ and R ⁶ may be the same or different for each siloxy unit. The moiety represented by Formula 3 includes a polydimethylsilicone unit, a polymethylphenylsilicone unit, a polydiphenylsilicone unit, R ⁵ and / or R ⁶ is R ^f CH ₂ CH ₂ CH ₂ — (R ^f is polyfluoroalkyl The polyfluoroalkyl silicone unit etc. which are group.) Is preferable. The R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. Specific examples of such R ^f groups are described in paragraph numbers 0009 to 0015 of JP-A No. 2000-282015.
X of Formula 3 shows a polymerization degree, 1-1000 are preferable and 1-500 are more preferable. When x is in this range, the film made of a cured product is excellent in lubricity.

  The moiety represented by the above formula 4 represents a unit of tetrafluoroethylene oxide, the moiety represented by formulas 5 and 6 represents a unit of hexafluoropropylene oxide, and the moiety represented by formula 7 represents a difluoromethylene. Represents a unit. As p, q, r, and s indicating the degree of polymerization, when 1 to 4, there is a tendency that fingerprint resistance is exhibited, and when 5 to 100, both functions of lubricity and fingerprint resistance are exhibited. Is expected.

  In the coating composition of the present invention, a plurality of compounds (C) having a site (c-1) that expresses different functions may be used in combination as the compound (C).

The site | part (c-2) (henceforth "site (c-2)") which has at least 1 selected from the group which consists of a part represented by Formula 8-10 of a compound (C) (henceforth "site (c-2)") is superposition | polymerization. Have a function of developing compatibility with the polymerizable monomer (A).
Since the portion (c-1) of the compound (C) has low affinity with the resin matrix formed from the polymerizable monomer (A), the surface of the resin matrix is bleed when the coating composition is cured. It tends to be out and tends to impair the transparency of the film made of a cured product.

  Since compound (C) has excellent compatibility with polymerizable monomer (A) in part (c-2), the phase with polymerizable monomer (A) that forms a resin matrix in the coating composition Despite having a site (c-1) with a large difference in solubility, it has moderate compatibility with the polymerizable monomer (A).

  In the coating composition of the present invention, since the compound (C) has appropriate compatibility with the polymerizable monomer (A), when the coating composition is applied to a substrate, the coating before curing is applied. Without impairing the transparency of the film, the compound (C) is segregated on the surface of the coating film. For this reason, the transparency of the film which consists of hardened | cured material is not impaired.

  The portion represented by the above formula 8 is an alkylene group having 6 to 20 carbon atoms and has a linear structure or a branched structure. When the number of carbon atoms is in this range, the compatibility of the compound (C) with the polymerizable monomer (A) is appropriate, and the crystallinity of the group is not too strong. And / or excellent fingerprint resistance and transparency. If the alkylene group has less than 6 carbon atoms, the compatibility with other components in the coating composition is low, so the transparency of the coating before curing may be impaired. This means that the transparency of the film made of a cured product is impaired. On the other hand, when the number of carbon atoms exceeds 20, the crystallinity of the group becomes strong, so that the transparency of the film made of a cured product may be impaired.

  The portion represented by the above formula 9 represents a random copolymer of ethylene oxide and propylene oxide, a block copolymer of ethylene oxide and propylene oxide, an ethylene oxide homopolymer, and a propylene oxide homopolymer. As z and w which show a polymerization degree, z is 0-100, w is 0-100, It is an integer which satisfy | fills 5 <= z + w <= 100. Moreover, as z and w, z is 0-80, w is 0-80, and it is more preferable that they are integers satisfying 5 ≦ z + w ≦ 80. However, z and w are expressed by the maximum value of the degree of polymerization of each monomer in the site (c-2). When z and w are within these ranges, the compound (C) has an appropriate compatibility with the polymerizable monomer (A), and the film made of the cured product has lubricity and / or fingerprint resistance. Excellent transparency. When z + w is more than 100, the compatibility of the compound (C) with the polymerizable monomer (A) becomes too high, the compound (C) is less likely to segregate on the surface of the coating film, and the cured film is lubricated. And / or fingerprint adhesion resistance may not be sufficiently exhibited. On the other hand, when z + w is less than 5, the compatibility of the compound (C) with the polymerizable monomer (A) is lowered, and the transparency of the film made of the cured product may be impaired.

  The portion represented by the above formula 10 represents a ring-opening polymer of lactone. U which is the carbon number of the lactone monomer is 3-5. Moreover, as t which shows a polymerization degree, it is an integer of 1-20. However, t is represented by the maximum value of the degree of polymerization of the lactone monomer at the site (c-2). When t is within this range, the crystallinity of the part (c-2) is suppressed, and the transparency of the film made of the cured product is excellent.

In the coating composition of the present invention, a plurality of compounds (C) having different sites (c-2) may be used in combination as the compound (C).
In the compound (C), the active energy ray-curable functional group (c-3) (hereinafter referred to as “functional group (c-3)”) may be any functional group having radical reactivity, Specifically, (meth) acryl group, allyl group, vinyl group, vinyl ether group, halogen substituent, mercapto group and the like are preferable.

  When the compound (C) has a functional group (c-3), when the coating composition is cured by irradiation with active energy rays, the functional group (c-3) also undergoes a curing reaction, and the coating composition It is covalently bonded to the polymerizable monomer (A) forming the resin matrix of the cured product. Thereby, a compound (C) exists in the surface of the film which consists of hardened | cured material of a coating composition, and exists, and since a compound (C) does not volatilize from the surface of a film, it is preferable. Therefore, the surface of the film made of the cured product exhibits lubricity and / or fingerprint resistance over a long period of time.

  Compound (C) has both a site (c-1), a site (c-2) and a functional group (c-3) in the molecule. The form of binding at each site in compound (C) is not particularly limited. Specific examples of the binding form of each site in the compound (C) include the following examples.

  1. Linear type The part (c-1), the part (c-2), and the functional group (c-3) are connected linearly. Hereinafter, it is described as “linear type”.

  In the production of the linear type, as the raw material for forming the site (c-1), a material in which the end of the site (c-1) is hydroxyl-modified is preferably used. For example, polydimethyl silicone whose terminal is hydroxyl-modified, polyhexafluoropropylene oxide whose terminal is hydroxyl-modified, polytetrafluoroethylene oxide whose terminal is hydroxyl-modified, and the like are preferable.

  Then, by polymerizing monomers such as ethylene oxide, propylene oxide, and lactone monomer to the terminal hydroxyl group of the site (c-1), the site (c-2) is adjacent to the site (c-1). Can be built. Alternatively, a polymer such as polyethylene glycol or polypropylene glycol can be linked to the site (c-1) by a urethane bond using a bifunctional isocyanate or the like as the site (c-2).

  In the operations so far, the terminal of the site (c-2) is a hydroxyl group. Therefore, as a method of introducing the functional group (c-3), a method of esterification using (meth) acrylic acid, (meth) acrylic acid chloride or the like, or a urethane using 2- (meth) acrylic acid ethyl isocyanate. Preferred examples include a method of bonding by bonding, a method of introducing 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like through a bifunctional isocyanate via a urethane bond. It is done.

  In addition, a polymer having one end of a polymer such as polyethylene glycol or polypropylene glycol already modified with (meth) acrylic group is used, and bifunctional isocyanate is used between the terminal hydroxyl group of site (c-1). The method of connecting a site | part (c-2) and a functional group (c-3) at a time adjacent to a site | part (c-1) by making a urethane bond is also mentioned preferably.

  2. Copolymerization type A radical polymerizable macromer having a moiety (c-1) and a radical polymerizable macromer having a moiety (c-2) are prepared, and after the macromer is copolymerized, a functional group (c-3) is prepared. ) Type to introduce. Hereinafter, it is referred to as “copolymerization type”.

  Preferred examples of the macromer having the moiety (c-1) include those in which one end of polydimethylsilicone is modified with a (meth) acryl group, fluorine-containing polyalkylene oxide ester of (meth) acrylic acid, and the like.

  Examples of the macromer having the moiety (c-2) include those in which one end of a polymer such as polyethylene glycol and polypropylene glycol is modified with (meth) acrylic group, alkyl ester of (meth) acrylic acid, and lactone ring opening. Preferred are those in which one end of the polymer is modified with a (meth) acrylic group.

  Examples of the functional group (c-3) include a method in which the above two kinds of macromers are copolymerized and then introduced into the terminal thereof. For example, a method of esterifying the terminal hydroxyl group of the above two kinds of macromers to which (meth) acrylic group is not added with (meth) acrylic acid, (meth) acrylic acid chloride, etc., 2-methacrylic A method of bonding by urethane bonding using acid ethyl isocyanate is preferred.

  Alternatively, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like are copolymerized together with the two types of macromers, and then (meth) acrylic acid, ( The method of esterifying using a (meth) acrylic acid chloride etc., and the method of making it couple | bond by a urethane bond using 2-methacrylic acid ethyl isocyanate are also mentioned.

  The coating composition of this invention contains 0.01-10 mass parts of compounds (C) with respect to 100 mass parts of polymerizable monomers (A). The preferred content of compound (C) is 0.1 to 5 parts by mass. When the amount of the compound (C) is within this range, when the coating composition is applied to the substrate surface, the compound (C) is segregated on the coating film surface without damaging the transparency of the coating film before curing. . For this reason, the transparency of the film which consists of hardened | cured material is not impaired, and this film surface is excellent in lubricity and / or fingerprint adhesion resistance. Further, if the amount of the compound (C) is within this range, the curability of the coating composition is not lowered, and the compound (C) is fixed on the surface of the coating when cured, so that the coating The surface develops excellent lubricity and / or fingerprint resistance over a long period of time.

  The coating composition of the present invention may contain a known function-imparting agent in addition to the compound (C) described above. Examples of such known function-imparting agents include silicone-based function-imparting agents typified by silicone oil, fluorine-based function-imparting agents, and fatty acid ester-based function-imparting agents typified by fatty acid ester waxes. When a known function-imparting agent is included, it is contained in an amount of 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the total mass of the compound (C) and the known function-imparting agent.

In addition to the above-mentioned composition, the coating composition of the present invention contains 0.1 to 20 parts by mass of the active energy ray polymerization initiator (D) with respect to 100 parts by mass of the polymerizable monomer (A). Is preferable, and it is more preferable to contain 0.2-10 mass parts. When the amount of the active energy ray polymerization initiator (D) is in this range, the curability is sufficient, and all the active energy ray polymerization initiators (D) are decomposed during the curing, which is preferable.
The active energy ray polymerization initiator (D) here includes a wide range of known photopolymerization initiators.
In addition, when the active energy ray is an electron beam, X-ray, radiation, or high-frequency ray, which will be described later, and the polymerization reaction is started by simply irradiating them, the polymerization initiator (D) is included in the coating composition. It does not have to be.

  Specific examples of known photopolymerization initiators include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates). , Α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxides (eg, acyldiarylphosphine oxides), and other photopolymerization initiators is there. Two or more photopolymerization initiators may be used in combination. The photopolymerization initiator may be used in combination with a photosensitizer such as amines. Specific examples of the photopolymerization initiator include the following compounds, but are not limited thereto.

  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, 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, benzoin 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, (1-phenyl-1,2-propanedione-2 (o-ethoxycarbonyl) oxime), α-acyloximes Le, methylphenyl glyoxylate.

  4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 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.

  In the coating composition of the present invention, an ultraviolet absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, a pigment (organic coloring) Pigments, inorganic pigments), colored dyes, infrared absorbers, optical brighteners, dispersants, antifogging agents, and coupling agents, one or more functional compounding agents may be included.

  In the present invention, an organic solvent may be added to the coating composition for the purpose of improving the coating property of the coating composition and the adhesion to the plastic substrate. The organic solvent is not particularly limited as long as there is no problem in the solubility of the polymerizable monomer (A), colloidal silica (B), compound (C), active energy ray polymerization initiator (D), and other additives. However, what is necessary is just to satisfy the said performance. Two or more organic solvents can be used in combination. The amount of the organic solvent used is preferably 100 times or less, particularly preferably 50 times or less, by mass with respect to the polymerizable monomer (A). If the magnification is more than 100 times, it is difficult to ensure the film thickness of the film made of the cured product.

  Examples of the organic solvent include lower alcohols such as ethyl alcohol, butyl alcohol and isopropyl alcohol, ketones such as methyl isobutyl ketone, methyl ethyl ketone and acetone, ethers such as dioxane, diethylene glycol dimethyl ether, tetrahydrofuran and methyl t-butyl ether, and methyl cellosolve. Organic solvents such as cellosolves such as ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether acetate are preferred. In addition, esters such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, diethyl succinate, diethyl adipate, dibutyl phthalate, dioctyl phthalate and the like, chlorinated fluorinated hydrocarbons Also, chlorinated hydrocarbons such as trichloroethane, halogenated hydrocarbons such as fluorinated hydrocarbons, hydrocarbons such as toluene, xylene and hexane can be used. It is preferable to select an appropriate organic solvent according to the type of substrate on which the film is formed.

The coating composition of the present invention is a method of dipping, spin coating, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating, etc. on a plastic substrate. In the case of a composition containing an organic solvent, it is dried and then cured by irradiation with active energy rays.
In addition, as an active energy ray, an ultraviolet-ray, an electron beam, X-ray | X_line, a radiation, a high frequency ray etc. are mentioned preferably, Especially the ultraviolet-ray which has a wavelength of 180-500 nm is economically preferable.

  Active energy ray sources include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and other ultraviolet irradiation devices, electron beam irradiation devices, X-ray irradiation devices, high-frequency generators, etc. Can be used.

  The irradiation time of the active energy ray can be appropriately changed depending on conditions such as the type of the polymerizable monomer (A), the type of the active energy ray polymerization initiator (D), the thickness of the coating, and the active energy ray source. Usually, the object is achieved by irradiation for 0.1 to 60 seconds. Further, for the purpose of completing the curing reaction, heat treatment can be performed after irradiation with active energy rays.

  As the thickness of the coating, various thicknesses can be adopted as desired. Usually, a film having a thickness of 0.1 to 50 μm is preferable, a thickness of 0.2 to 20 μm is more preferable, and a thickness of 0.3 to 10 μm is particularly preferable. When the thickness of the coating is in this range, it is preferable because the wear resistance is sufficient and the coating is deeply cured.

  Since the film made of the cured product of the composition of the present invention has the above-mentioned properties, the plastic base material forming the film may be a transparent plastic material, a plastic material with poor wear resistance, or a dynamic friction. A plastic material having a large coefficient is preferable. Specifically, for example, aromatic polycarbonate resin, polymethyl methacrylate resin, polymethacrylimide resin, polystyrene resin, polyvinyl chloride resin, unsaturated polyester resin, polyolefin resin, ABS resin, MS ( And methyl methacrylate / styrene) resin.

Hereinafter, although this invention is demonstrated based on an Example (Examples 1-4) and a comparative example (Example 5), this invention is not limited to these.
The raw material compounds used in the examples are described below.

[Raw compound]
(1) Polymerizable monomer (A)
AI-1: LiO-group-containing bifunctional urethane acrylate, which is a compound represented by Formula 2. “U-201PAT-80” (80% by mass of monomer, 20% by mass of toluene) manufactured by Shin-Nakamura Chemical Co., Ltd. was used.
AII-1: Acrylic urethane having an average acryloyl group number of 15 and a molecular weight of 2300 per molecule, obtained by reacting a hydroxyl group-containing dipentaerythritol polyacrylate with hexamethylene diisocyanate.
AII-2: Dipentaerythritol hexaacrylate.

(2) Colloidal silica (B)
B-1: Propylene glycol monomethyl ether acetate dispersed colloidal silica (silica content 30% by mass, average particle size 11 nm) (100 parts by mass) was added 3-mercaptopropyltrimethoxysilane (2.5 parts by mass). Colloidal silica surface-modified with a hydrolysis condensate of mercaptosilane obtained by stirring at 50 ° C. for 3 hours and then aging for 12 hours at room temperature.

  B-2: 3-Mercaptopropyltrimethoxysilane (2.5 parts by mass) was added to butyl acetate-dispersed colloidal silica (silica content 30% by mass, average particle size 11 nm) (100 parts by mass) at 50 ° C. Colloidal silica surface-modified with a hydrolysis condensate of mercaptosilane obtained by stirring at room temperature for 3 hours and then aging at room temperature for 12 hours.

(3) Compound (C)
C-1: (Compound imparting lubricity)
In a 300 mL four-necked flask equipped with a stirrer and a condenser tube, titanium tetraisobutyl oxide (80 mg), dimethyl silicone oil having a hydroxyl group at one end (trade name “X-22-170BX”, manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxyl value 18.5.) (100 g) and ε-caprolactone (25 g) were added and held at 150 ° C. for 5 hours to obtain a compound in which ε-caprolactone was ring-opened and added to one end of a white wax-like dimethylsilicone oil. It was.

  The obtained compound was cooled to room temperature, butyl acetate (50 g) and 2,6-di-t-butyl-p-cresol (250 mg) were added, and the mixture was stirred for 30 minutes, and then 2-methacryloyloxyethyl isocyanate (5. 05 g) was added, and the mixture was further stirred at room temperature for 24 hours to obtain a butyl acetate solution (solid content concentration: 72% by mass) of the compound (C-1) whose one end was modified with a methacryl group.

C-2: (Compound imparting lubricity and anti-fingerprint adhesion)
Hereinafter, tetramethylsilane is referred to as TMS, CClF ₂ CF ₂ CHClF as AK-225, and CCl ₂ FCClF ₂ as R-113.

Step 1. Commercially available polyoxyethylene glycol monomethyl ether (CH ₃ O (CH ₂ CH ₂ O) _n H, n = 8.3 (average value)) (25 g) and AK-225 (20 g), NaF (1.2 g), Pyridine (1.6 g) was placed in the flask and stirred vigorously while keeping the internal temperature at 10 ° C. or lower to bubble nitrogen. There FCOCF the _{(CF 3) OCF 2 CF (} CF 3) OCF 2 CF 2 CF 3 (46.6g), was added dropwise the internal temperature 5 ° C. over 3.0 hours while keeping below. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 12 hours and then at room temperature for 24 hours to recover the crude liquid. The crude liquid was filtered under reduced pressure, and then the recovered liquid was dried with a vacuum dryer (50 ° C., 5.0 torr) for 12 hours. The crude liquid obtained here was dissolved in 100 ml of AK-225 and washed three times with 1000 ml of saturated sodium bicarbonate water to recover the organic phase. Further, magnesium sulfate (1.0 g) was added to the collected organic phase, and the mixture was stirred for 12 hours. Thereafter, pressure filtration was performed to remove magnesium sulfate, and AK-225 was distilled off with an evaporator to obtain 56.1 g of a polymer that was liquid at room temperature. ^{As a result of 1} H-NMR and ¹⁹ F-NMR analysis, the obtained polymer was CH ₃ O (CH ₂ CH ₂ O) _n C (O) CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (n represents the same meaning as described above).

  Step 2. To a 2.500 mL Hastelloy autoclave, R-113 (1560 g) was added and stirred, and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at 20 ° C. were installed in series. In addition, the liquid return line for returning the aggregated liquid to the autoclave was installed from the cooler kept at -20 ° C. After blowing nitrogen gas for 1.0 hour, fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas) was blown for 1 hour at a flow rate of 24.8 L / h.

  Next, a solution obtained by dissolving the product (27.5 g) obtained in Step 1 in R-113 (1350 g) was injected over 30 hours while blowing 10% fluorine gas at the same flow rate.

  Next, 12 mL of R-113 solution was injected while blowing 10% fluorine gas at the same flow rate. At this time, the internal temperature was changed to 40 ° C. Subsequently, an R-113 solution (6 mL) in which 1 wt% of benzene was dissolved was injected. Further, after blowing fluorine gas for 1.0 hour, nitrogen gas was blown for 1.0 hour.

After completion of the reaction, the solvent was removed by vacuum drying (60 ° C., 6.0 hours) to obtain 45.4 g of a product which was liquid at room temperature. As a result of NMR analysis, CF ₃ O (CF ₂ CF ₂ O) _n C (O) CF (CF ₃ ) in which 99.9% of the total number of hydrogen atoms in the product obtained in Step 1 was replaced with fluorine atoms. it was confirmed that OCF ₂ CF _{(CF 3)} a compound represented by OCF 2 _CF 2 _{CF 3.}

  Step 3. A 300 mL round bottom flask charged with a stirrer chip was thoroughly purged with nitrogen. Methanol (36 g), NaF (5.6 g) and AK-225 (50 g) were added, and the product obtained in Step 2 (43.5 g) was added dropwise, followed by vigorous stirring while bubbling at room temperature. did. The eggplant flask outlet was sealed with nitrogen.

  After 8 hours, a vacuum pump was installed in the cooling pipe to keep the system under reduced pressure, and excess methanol and reaction by-products were distilled off. After 24 hours, 26.8 g of product which was liquid at room temperature was obtained.

As a result of analysis, a compound represented by CF ₃ O (CF ₂ CF ₂ O) _n-1 CF ₂ C (O) OCH _{3 in} which the total amount of ester groups of the product obtained in Step 2 was converted to methyl ester Was confirmed to be the main product.

Step 4. A 300 mL round bottom flask charged with a stirrer chip was thoroughly purged with nitrogen. 2-Propanol (30 g), AK-225 (50.0 g) and NaBH ₄ (4.1 g) are added to dilute the product obtained in step 3 (26.2 g) to AK-225 (30 g). And dripped. Thereafter, the mixture was vigorously stirred at room temperature, and the round bottom flask outlet was sealed with nitrogen.

  After 8 hours, a vacuum pump was installed in the cooling pipe to keep the system under reduced pressure, and the solvent was distilled off. After 24 hours, AK-225 (100 g) was added, and a 0.2 N hydrochloric acid aqueous solution (500 g) was added dropwise with stirring. After dropping, stirring was maintained for 6 hours. Thereafter, the organic phase was washed with distilled water (500 g) three times, and the organic phase was recovered by two-layer separation. Further, magnesium sulfate (1.0 g) was added to the collected organic phase, and the mixture was stirred for 12 hours. Thereafter, pressure filtration was performed to remove magnesium sulfate, and AK-225 was distilled off with an evaporator to obtain 24.8 g of a polymer that was liquid at room temperature.

As a result of the analysis, the main product is a compound represented by CF ₃ O (CF ₂ CF ₂ O) _n-1 CF ₂ CH ₂ OH in which the total amount of ester groups of the product obtained in Step 3 is reduced. It was confirmed.

Step 5. In a 300 mL four-necked flask equipped with a stirrer and a condenser tube, titanium tetraisobutoxide (80 mg), CF ₃ O (CF ₂ CF ₂ O) _n-1 CF ₂ CH ₂ OH (100 g) and 25 g ε-Caprolactone was added and heated at 150 ° C. for 5 hours to obtain a white wax-like compound in which ε-caprolactone was ring-opened and added to the end of perfluoropolyethylene oxide.

  Subsequently, 1,3-bis (trifluoromethyl) benzene (60 g) and 2,6-di-t-butyl-p-cresol (60 mg) were added and stirred for 30 minutes, and then 2-methacryloyloxyethyl isocyanate (15 0.5 g) was added and stirred at room temperature for a further 24 hours to complete the reaction. Then, 1,3-bis (trifluoromethyl) benzene as a solvent was distilled off at 40 ° C. under reduced pressure to obtain a compound (C-2) whose terminal was modified with a methacryl group.

C-3: (Compound that imparts fingerprint resistance)
In the same manner as in Steps 1 to 4 of the synthesis of C-2, using (CH ₃ O (CH ₂ CH ₂ O) _n H (n = 3.3 (average value)), CF ₃ O (CF ₂ to obtain a _{CF 2 O) n-1 CF} 2 CH 2 OH.

In a 300 mL four-necked flask equipped with a stirrer and a condenser tube, titanium tetraisobutoxide (80 mg), CF ₃ O (CF ₂ CF ₂ O) _n-1 CF ₂ CH ₂ OH (100 g) and 25 g ε-Caprolactone was added and heated at 150 ° C. for 5 hours to obtain a white wax-like compound in which ε-caprolactone was ring-opened and added to the end of perfluoropolyethylene oxide.

  The obtained compound was cooled to room temperature, butyl acetate (56 g) and 2,6-di-t-butyl-p-cresol (60 mg) were added, and the mixture was stirred for 30 minutes, and further 2-methacryloyloxyethyl isocyanate (6. 0 g) was added, and the mixture was further stirred at room temperature for 24 hours to obtain a butyl acetate solution (solid content concentration: 70% by mass) of the compound (C-3) whose terminal was modified with a methacryl group.

[Example 1]
Into a 300 mL four-necked flask equipped with a stirrer and a condenser tube, monomer (AI-1) (12.8 g, 16 g as “U-201PAT-80”), monomer (AII-1) (64 g ), Compound (C-1) (0.40 g), 1-hydroxycyclohexyl phenyl ketone (4.0 g) as an active energy ray polymerization initiator, hydroquinone monomethyl ether (1.0 g) as a thermal polymerization inhibitor, and organic solvent Butyl acetate (35.0 g) was added and homogenized by stirring for 1 hour at room temperature and in the light-shielded state.

  Subsequently, while stirring, colloidal silica (B-1) (23.8 g in terms of solid content, 75.0 g as a dispersion) was slowly added, and the mixture was further homogenized by stirring for 1 hour at room temperature and in the light-shielded state. . And dibutyl ether (35.0g) was added as an organic solvent, and it stirred at normal temperature and the state of light-shielding for 1 hour, and obtained the coating composition.

The resulting coating composition was applied to the surface of a substrate (a transparent aromatic polycarbonate resin sheet having a thickness of 3 mm, 100 mm × 100 mm) using a spin coater (4000 rpm × 10 seconds), and hot air at 90 ° C. The film was formed by holding in a circulating oven for 1 minute to dry. Next, the film was cured by irradiating with 1000 mJ / cm ² (ultraviolet integrated energy amount in the wavelength region of 300 to 390 nm; the same shall apply hereinafter) using a high-pressure mercury lamp to cure the cured product having a film thickness of 1.2 μm. A layer 1 was formed to obtain Sample 1 having a cured product layer on the surface of the substrate. Using the sample 1, the following measurements and evaluations were performed. The results are shown in Table 2.

[Examples 2 to 5]
Except for changing the types and amounts used of the polymerizable monomer (A), colloidal silica (B), and compound (C) in Example 1 to the types and amounts described in Table 1 below, the same manner as in Example 1 was performed. Samples 2 to 5 were manufactured, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 2.

  In each example, measurement and evaluation of various physical properties were performed by the following methods.

[Antistatic property]
After a high voltage (10 KV) was applied to the sample for a certain period of time by using a method defined in JIS K1049, the time until the charged voltage decreased to ½ was measured. Note that a static Honestometer manufactured by Sicid Static Electric Co., Ltd. was used for the measurement.

[transparency]
About the sample, haze (%) of four places was measured with the haze meter, and the average value was computed.

[Abrasion resistance]
According to the abrasion resistance test method in ISO9352, the haze when a 500 g weight was combined with each of two CS-10F wear wheels and rotated 500 times was measured with a haze meter. The haze was measured at four locations on the cycle raceway of the wear wheel, and the average value was measured. Abrasion resistance indicates a value (%) of (haze after wear test) − (initial haze).

[Adhesion]
The surface of the sample was cut with 11 razor blades at 1 mm intervals in the vertical and horizontal directions, 100 squares were made, and commercially available cellophane tape (manufactured by Nichiban Co., Ltd.) was adhered closely, and then suddenly moved forward 90 degrees. It is represented by the number of grids remaining without peeling off the coating when peeled.

[Lubricity]
For the initial sample and the sample after the moisture resistance test (after storage for 7 days in an atmosphere of 60 ° C. and 95% humidity), the dynamic friction coefficient of the sample surface was measured by the following procedure. The dynamic friction coefficient is the weight of the sliding piece (g) required to move the load horizontally under the following conditions.
It was determined as (necessary weight / load).
Test pad: Non-woven fabric made of cellulose (trade name “Bencot”, manufactured by Asahi Kasei Corporation)
Load: 500g (Contact area 50mm x 100mm)
Travel distance: 20mm
Movement speed: 10 mm / min Test environment: 25 ° C., relative humidity 45%.

[Fingerprint resistance]
Samples before the test (initial stage) and after the moisture resistance test (after storage for 7 days in an atmosphere of 60 ° C. and 95% humidity) against oleic acid, one of human sebum components, as a measure of fingerprint resistance The contact angle was measured. The surface with higher fingerprint resistance tends to have a higher contact angle with respect to oleic acid.
Using an automatic contact angle meter (DSA10D02: manufactured by Cruz, Germany), 3 μL of oleic acid droplets were made on the needle tip in a dry state (20 ° C., relative humidity 65%), and this was brought into contact with the sample surface. Made drops. The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid are in contact, and is defined as an angle including the liquid.

The plastic molded product having a coating comprising a cured product of the coating composition of the present invention on the surface thereof has greatly improved wear resistance and is excellent in antistatic property, so that it is difficult for dust and dust to adhere to it. And as a surface coating agent for optical disks.

Claims (5)

  A coating composition containing 0.1 to 500 parts by weight (in terms of solid content) of colloidal silica (B) with respect to 100 parts by weight of an active energy ray-curable polymerizable monomer (A), the active energy The active energy ray-curable polymerizable monomer having 5 parts by mass or more of 100 parts by mass of the linear curable polymerizable monomer (A) having a group in which hydrogen of an alcoholic hydroxyl group is substituted with an alkali metal atom. A coating composition characterized by being a body (AI). The active energy ray-curable polymerizable monomer (AI) having a group in which hydrogen of the alcoholic hydroxyl group is substituted with an alkali metal atom is represented by the following formula 1 or formula 2. Composition.
CH ₂ = C (R ¹ ) COO-R ² O-M Formula 1
^{_{(CH 2 = C (R 1}} ) COO) m R 3 O- (CONHR 4 NHCOO-R 2 O) n -M
... Formula 2
In Formula 1 or Formula 2, R ¹ is a hydrogen atom or a methyl group, R ² is a diol residue, R ³ is a polyol residue, R ⁴ is a diisocyanate residue, M is an alkali metal atom, and m is The integer of 1-20 and n show the integer of 1-50.   The colloidal silica (B) is a modified colloidal silica having an average particle diameter of 1 to 200 nm, which is surface-modified with a mercaptosilane compound in which an organic group having a mercapto group and a hydrolyzable group and / or a hydroxyl group are bonded to a silicon atom. The coating composition according to claim 1 or 2. The coating composition according to any one of claims 1 to 3, further comprising 0.01 to 10 parts by mass of the compound (C) with respect to 100 parts by mass of the polymerizable monomer (A).
However, the compound (C) is represented in the molecule by at least one site (c-1) selected from the group consisting of moieties represented by the following formulas 3 to 7 and the following formulas 8 to 10. It has the site | part (c-2) which consists of at least 1 selected from the group which consists of a part, and an active energy ray hardening functional group (c-3).
_{^{- (SiR 5 R 6 O)}} x - ··· Formula 3
_{- (CF 2 CF 2 O)} p - ··· formula 4
_{- (CF 2 CF (CF 3} ) O) q - ··· Equation 5
_{- (CF 2 CF 2 CF 2} O) r - ··· formula 6
− (CF ₂ O) _s − Formula 7
(In the formula ^3, R 5, ^{R 6} are independently an alkyl group having 1 to 8 carbon atoms, is either a fluorine-containing alkyl group or a phenyl group having 1 to 8 carbon atoms, x is an integer from 1 to 1000 .
In Formulas 4-6, p, q, r, and s are integers of 1-100. )
-R ⁷ - ··· formula 8
_{- (CH 2 CH 2 O)} z - (CH 2 CH (CH 3) O) w - ··· Equation 9
_{- (C (= O) C} u H 2u O) t - ··· Equation 10
(In Formula 8, R ⁷ is an alkylene group having 6 to 20 carbon atoms. In Formula 9, z is 0 to 100, w is 0 to 100, and is an integer satisfying 5 ≦ z + w ≦ 100.] 10, u is an integer of 3 to 5, and t is an integer of 1 to 20.) A plastic molded article having a coating having a thickness of 0.1 to 50 µm made of a cured product of the coating composition according to any one of claims 1 to 4 on the surface of the plastic substrate.