CA2086276C - Coated shaped articles and method of making same - Google Patents

Coated shaped articles and method of making same Download PDF

Info

Publication number
CA2086276C
CA2086276C CA 2086276 CA2086276A CA2086276C CA 2086276 C CA2086276 C CA 2086276C CA 2086276 CA2086276 CA 2086276 CA 2086276 A CA2086276 A CA 2086276A CA 2086276 C CA2086276 C CA 2086276C
Authority
CA
Canada
Prior art keywords
carbon atoms
coating composition
equal
meth
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA 2086276
Other languages
French (fr)
Other versions
CA2086276A1 (en
Inventor
Masamoto Uenishi
Tsukasa Mizobuchi
Masatoshi Takesue
Yukio Kobayashi
Shoichi Nagai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Priority to CA 2086276 priority Critical patent/CA2086276C/en
Priority to EP19920122038 priority patent/EP0604677B1/en
Publication of CA2086276A1 publication Critical patent/CA2086276A1/en
Priority to US08/305,553 priority patent/US5470616A/en
Application granted granted Critical
Publication of CA2086276C publication Critical patent/CA2086276C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31507Of polycarbonate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31667Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

Disclosed are shaped articles having a coating layer formed on surface region, wherein the surface region is formed of a polymer derived from a multifunctional acryl-is monomer and having 0.02 to 0.2 µmol/cm2 of acidic groups therein, by curing a coating composition consist-ing essentially of a specific silica polycondensate. The silica polycondensate is obtained by mixing (T) colloidal silica and (II) a specific silicon compound in such a molar ratio that the average number of hydrolyzable groups is within the range of 2.30 to 3.85, and then subjecting them to cohydrolysis and polycondensation. In these shaped articles, the coating layer have excellent properties such as hardness and abrasion resistance, as well as good adhesion.

Description

- 1 - ' SPECTFICATION
Title of the Invention:
Coated Shaped Articles and Method of Making Same Backcrround of the Invention a. Field of the Invention:
This invention relates to shaped articles having high surface hardness and a method of making such shaped articles. The shaped articles of the present invention can be used in various fields of application including, for example, the fields of architecture, automobile industry and optics.
b. Description of the Prior Art:
Synthetic resin shaped articles made of polymethyl methacrylate resin, polycarbonate resins, diethylene glycol bisallyl carbonate resin and the like are lighter in weight and less expensive than glass products. Owing to these advantages, they are used in a wide variety of applications.
However, since such synthetic resin shaped articles have insufficient surface hardness, their surfaces are easily damaged by contact with other objects, impacts, scratches and the like, resulting in a reduced product yield and a spoiled appearance. Especially where these shaped articles are used as optical lenses, fashion glasses, sunglasses, spectacle lenses (such as correcting lenses), windowpanes and the like, any damage caused to ~o~s~~s the surfaces thereof diminishes their commercial value and/or makes them unusable in a short period of time.
Accordingly, it is strongly demanded to improve the surface hardness of such synthetic resin shaped articles.
In order to meet this demand, various attempts have heretofore been made.
In Japanese Patent Publication Nos. 39691/'77, 5554/'87, 157865/'83, 35675/'88, 36349/'88 and 45094/'91, the abrasion resistance of shaped articles are improved by coating them with a coating composition containing a mixture of colloidal silica and a hydrolyzable silicon compound.
In Japanese Patent Publication No. 53701/'85, the abrasion resistance and weather resistance of polycarbon-ate substrates are improved by forming a thermosetting acrylic polymer layer (primer layer) containing an ul-traviolet light absorber on the polycarbonate substrates and then forming thereon a coating layer comprising a mixture of colloidal silica and a hydrolyzable silicon compound.
However, the coating layers disclosed in Japanese Patent Publication Nos. 39691/'77, 5554/'87, 157865/'83, 35675/'88, 36349/°88 and 45094/'91 have the following disadvantages. (1) When they are subjected to a Taber abrasion test according to ASTM D-1044 in which a CS-17 truck wheel is used under a load of 250 g and rotated 5,000 cycles, all of them show a haze of as high as 10 to 50%. Thus, their abrasion resistance is much lower than that of glass plates which show a haze of about 3%. (2) Since the adhesion of the coating 7_ayer to the substrate is obtained by dissolving the substrate with a specific solvent, usable substrates are limited by the type of solvent used. (3) The adhesion of the coating 1_ayer to the substrate is insufficient. More spec.if-~cally, the adhesion of the coating layer to the substrate .i~> reduced when the coating layer is subjected to a durability test for a long period of time.
Moreover, the structure disclosed in Japanese Patent Publication No. 53701/'85 has the disadvantage that, if the primer layer contains a large amount of ultraviolet light.
absorber, the adhesion of the primer layer to the substrate is reduced.
Summary of the Invention:
It is a first object:. of an aspect of the present invention to provide a coating layer--bearing shaped article which has a crosslinked siloxane network structure .represented by (-S~i-O-Si-) in the surface thereof, exhibit excellent surface hardness and abrasion re~;istance, and shows a:n improvement in the adhesion of the coai~i.ng layer to various substrates.
It is a second object of an aspect of the present invention to provide a simplified method of making coating layer-bearing shaped articles having the above-described excel-lent features.
The above-described first object of the present inven-tion is accomplished by an abrasion-resistant shaped article having a coating layer formed on the surface region, wherein the surface region is formed of a polymer having structural units derived from a multifunctional monomer containing two or more (meth)acryloyloxy groups in the molecule and has 0.02 to 0.2 ~cmol/cm2 of acidic groups therein, by curing a coating composition consist-ing essentially of a silica polycondensate obtained by mixing (I) colloidal silica and (II) at least one hydro-lyzable silicon compound having any of the following general formulas (A) to (F) in such a molar ratio that the average number of hydrolyzable groups calculated from the following equation (1) is within the range of 2.30 to 3.85, and then subjecting them to cohydrolysis and poly-condensation.
SiRlaR2b(OR3)c (A) SiR4dR5e(OR6)f (B) SiR7gR8h(OR9)i (C) SiRlOjRllk(OR12)1 (D) SiR13mR14n(OR15)o (E) SiRlspRl7q(OR18)r (F) where R1, R2, R3, R5, R6, R8, R9, R11, R12~ R14~ R15~ R17 and R18 in formulas (A) to (F) are hydrocarbon radicals of 1 to 15 earbon atoms which may have an ether linkage or an ester linkage, R4 in formula (B) is a hydrocarbon radical of 2 to 15 carbon atoms having an epoxy group, R~
in formula (C) is a hydrocarbon radical of 1 to 15 carbon atoms having an amino group, R10 in formula (D) is a hydrocarbon radical of 1 to 15 carbon atoms having a mercapto group, R13 in formula (E) is a hydrocarbon radical of 2 to 15 carbon atoms having a vinyl group, R16 in formula (F) is a hydrocarbon radical of 3 to 15 carbon atoms having a (meth)acryloyloxy group, a, b, d, e, g, h, j, k, m, n, p and q are whole numbers o.f 0 to 3, c is equal to (4-a-b), f is equal to (4-d-e), i is equal to (4-g-h), 1 is equal to (4-j-k), o is equal to (4-m-n), and r is equal to (4-p-q).
Average number of hydrolyzable groups 4[I]-~c(A]+f[B]+i[C]+1[D]+o[E]+r[F]
- (1) [I]+(A]+(B]+[C]+[D]+(E]+[F]
where [A] to [F] are the number of moles of the hydrolyz-able silicon compounds of the general formulas (A) to (F), respectively, present in the reaction mixture, [I]
is the number of moles of the colloidal silica present in the reaction mixture, and c, f, i, 1, o and r are the same whole numbers as defined above for the general formulas (A) to (F).
The above-described second object of the present invention is accomplished by a method of making abrasion-resistant shaped articles which comprises the steps of (a) providing a shaped article having a surface formed of a polymer having structural units derived from a multifunctional monomer containing -two or more (meth)acryloyloxy groups in the molecule, (b) irradiating the surface of the polymer with ultraviolet light having a wavelength of 300 nm or less, (c) subjecting the irra-diated surface to an alkali treatment, (d) coating the irradiated and alkali-treated surface with a coating composition consisting essentially of a silica polycon-densate obtained by mixing (I) colloidal silica and (II) at least one hydrolyzable silicon compound having any of the above general formulas (A) to (F) in such a molar ratio that the average number of hydrolyzable groups calculated from the above equation (1) is within the range of 2.30 to 3.85, and then subjecting them to cohy-drolysis and polycondensation, and (e) curing the coating composition.
Brief Description of the Drawincrs Fig. ~ is a cross-sectional view illustrating a substrate 1 having a polymer layer 2 formed thereon for use in the method of making abrasion-resistant shaped articles in accordance with the present invention;
Fig. 2 is a cross-sectional view illustrating the construction of an abrasion-resistant shaped article in accordance with the present invention which has been made by forming a surface region 3 having a specific quantity ~fl~6~'~~
of acidic groups in the surface of the,polymer layer 2 and then forming a coating layer 4 thereon;
Fig. 3 is a diagram illustrating the state of the polymer structure during ultraviolet light irradiation and alkali treatment steps in the method of 'the present invention;
Fig. 4 is a cross-sectional view illustrating an instance of the ultraviolet light irradiation step in which the polymer layers formed on both sides of a sub-strate are irradiated with ultraviolet light through a glass plate.
Description of the Preferred Embodiments:
In the practice of the present invention, a polymer layer 2 (Fig. 1) is first formed by polymerizing a mono-mer composition containing a multifunctional monomer having two or more (meth)acryloyloxy groups in the mole-rule. Examples of the multifunctional monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, diethylene glycol bis(~-(meth)acryloy-loxypropionate), trimethylolethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ~o~6~~r~
_ g _ tri(2-hydroxyethyl) isocyanate di(meth)acrylate, pentaer-ythritol tetra(meth)acrylate, 2,3-bis(meth)acryloylox-yethyloxymethylbicyclo[2.2.1]heptane, poly--1,2-butadiene di(meth)acrylate, 1,2-bis(meth)acryloyloxymethylhexane, nonaethylene glycol di(meth)acrylate, tetradecaethylene glycol di(meth)acrylate, 10-decanediol di(meth)acrylate, 3,8-bis(meth)acryloyloxymethyltricyclo[5.2.10]decane, hydrogenated bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 1,4-bis((meth)acryloyloxymethyl)cyclohexane, bisphenol A
diglycidyl ether di(meth)acrylate and epoxidized bisphe-nol A di(meth)acrylate. These multifunctional monomers may be used alone or in admixture of two or more.
If necessary, they may be copolymerized with monofunc-tional monomers. It is desirable that the monomer compo-sition contains such a multifunctional monomer in an amount of not less than 30~ by weight. As used herein, the term "(meth)acryloyloxy group" means an acryloyloxy group or a methacryloyloxy group. If a monofunctional monomer alone is used to form a polymer layer, subsequent ultraviolet light irradiation and alkali treatment will fail to produce a sufficient quantity (i.e., within the range of 0.02 to 0.2 f~.mol/cm2) of acidic groups. Thus, it is an essential feature of the present invention to use a multifunctional monomer.
Then, the polymer layer 2 (Fig. 1) is irradiated with 20~02'~6 ultraviolet light having a wavelength of 300 nm or less to break a part of the crosslinked molecular chains.
Since the bond energy of the crosslinked molecular chains of the polymer layer varies with the compositian of the polymer, it is impossible to generally specify the wave-length of ultraviolet light required to break the cross-linked molecular chains. However., it is desirable to use ultraviolet light having a photon energy of about ~ eV or greater. Thus, it is necessary to use ultraviolet light having a wavelength of 300 nm or less which corresponds to the aforesaid photon energy. Tt is to be understood that a sufficient quantity of acidic groups are not produced by the ultraviolet light irradiation alone.
Subsequently, the ultraviolet light-irradiated polymer layer is subjected to an alkali treatment. It is gener-ally said that the hydrolysis of crosslinked polymers proceeds slowly. However, the present inventors have found that, after the polymer layer is reduced to low-molecular-weight fragments by irradiation with a wave-length of 300 nm or less, it is easy to hydrolyze. The mechanism of the reactions which are believed to take place is schematically illustrated in Fig. 3. The aque-ous alkaline solutions which can be used for this alkali treatment include, for example, aqueous solutions of sodium hydroxide, potassium hydroxide and the like, and such solutions additionally containing suitable solvents 2~862'~6 such as alcohols. The optimum conditions of the alkali treatment cannot be generally specified, because they may vary according to the amount of ultraviolet light expo-sure, and 'the composition and geometry of the ultraviolet light-irradiated portion of the shaped article. ~iowever, sodium hydroxide, for example, is preferably used in the form of an aqueous solution having a concentration of 0.1 to S0~ by weight and more preferably 1 to 30$ by weight.
The temperature tar the alkali treatment is generally within the range of 0 to 100°C and preferably 20 to 80°C.
The time for the alkali treatment is generally within the range of 0.01 to 100 hours and preferably 0.1 to 10 hours.
In the present invention, that part of the polymer layer 2 in which acidic groups have been produced by the above--described ultraviolet light irradiation and alkali treatment is referred to as a surface region 3 (Fig. 2).
This surface region denotes either of (1) the surface part 3 of a polymer layer 2 formed on a substrate 1 from a multifunctional monomer (as illustrated in Fig. 2) and (2) the surface part of a shaped article consisting entirely of a polymer formed from a multifunctional monomer (not shown).
In the former case (1), no particular limitation is placed on the type of the material constituting the substrate 1, but organic polymeric materials are pre-20~02~6 ferred. However, composites consisting of inorganic and organic materials can also be used for the substrate 1.
Useful organic materials include acrylic resins, vinyl chloride resin, polycarbonate resins, polyester resins and the like. Where the polymer layer 2 (Fig. 1) is formed by applying a multifunctional monomer as described above to a surface of the substrate 1, the thickness of the polymer layer 2 is preferably not less than 1 a m and more preferably not less than 3 ~ m.
As used herein, the term "acidic groups" means carbox-yl and hydroxyl groups. In the present invention, the quantity of acidic groups is expressed as the number of micromoles of a basic dye which can be adsorbed onto a unit area of the surface region (i.e., in ~ mol/cm2).
This can be obtained according to the following proce dure.
(1) A O.1M sodium acetate buffer solution (pH 4.5) is prepared.
(2) Using this buffer solution, a 1.0 g/1 Methyl violet solution is prepared.
(3) A shaped article measuring 50 mm x 50 mm2 is im mersed in the above solution (at 25°C) for 72 hours.
(4) The shaped article is taken out of the solution and washed with water.
(5) After washing, the shaped article is wiped dry.
(6) The dye is extracted by soaking the shaped article in 20862'6 N,N-dimethylformamide for 24 hours.
(7) The absorbance of the dye extract is measured at a wavelength of 587 nm.
(8) Separately, a calibration curve is constructed by a series of dye solutions in N,N-dimethylformamide. Using this calibration curve, the concentration of the basic dye per unit area of the surface region of the shaped article is determined.
In the present invention, the acidic groups serve to enhance the bonding strength between the surface region 3 and the coating layer 4 (Fig. 2). In order to achieve sufficient bonding strength, 0.02 to 0.2 ~cmol/cm2 of acidic groups are required. In the present invention, the acidic groups are present in the surface region 3 (Fig. 2) and the inner portion of the polymer layer 2 contains few acidic groups.
If the polymer layer 2 (Fig. 1) is subjected to other conventional procedures for introducing acidic groups (such as plasma treatment, photo-initiated graft polymer-ization and chromium treatment), in place of the proce-dure of the present invention comprising a combination of ultraviolet light irradiation and alkali treatment, good results may not be obtained with respect to the quantity of acidic groups and the ease of operation. After the alkali treatment, the shaped article is usually washed with water. If necessary, the shaped article may be ~0~62'~6 neutralized by washing with an inorganic or organic acid.
The acidic groups so produced neither show any change in quantity even when heated at 80°C for 100 hours, nor bury themselves.
Subsequently, the surface region 3 (Fig. 2) is coated with a coating composition consisting essentially of a silica polycondensate obtained by mixing colloidal silica and at least one hydrolyzable silicon compound having any of the following general formulas (A) to (F) in such a molar ratio that the average number of hydrolyzable groups calculated from the following equation (1) is within the range of 2.30 to 3.85, and then subjecting them to cohydrolysis and polycondensation in the presence of water and an organic solvent (and a hydrolysis cata-lyst and a condensation catalyst, if necessary). Then, the coating composition is heat-treated to further en-hance the degree of polymerization of the silica polycon-densate and thereby form a coating layer 4 (Fig. 2).
SiRlaR2b(OR3)c (A) SiR4dR5e(OR6)f (B) SiR7gR8h(ORg)i (C) SiRlOjRllk(OR12)1 (D) SiR13mR14n(OR15)o (E) SiRl6pRl~q(OR18)r (F) where R1 to R18 and a to r are as previously defined.
Average number of hydrolyzable groups ~U86~p16 4[I]+c[A]+f[B]+i[C]+1[D]+o(F]-t-r[F]
- (1) [I]'~'[A]~'LB]-~'CC]-~'[D]-ALE]'~'[F]
where [I], [A] to [F] and c to r are as previously de-fined. During this process, the hydroxyl, epoxy, amino and/or msrcapto groups possessed by the components of the coating layer 4 (Fig. 2) chemically react with the acidic groups present in the surface region 3 (Fig. 2) to form chemical bonds and further improve such properties as adhesion.
On the other hand, the crosslink density of the polymer layer 2 (Fig. 2) is maintained at the same level as was attained during polymerization. ~'hese properties of the polymer layer 2 and the coating layer 3 cooperate to produce a shaped article which, as a whole, has very good abrasion resistance and durability. It is desirable that the thickness of the surface region 3 extending from the outermost surface toward the inside is within the range of 0.01 to 1 a m. If the thickness of the surface region 3 having acidic groups is greater than 1 a m, the desired hardness may not be obtained, and if it is less than 0.01 ~cm, the coating layer will have poor adhesion due to the shortage of acidic groups.
Where silicon compounds within the scope of the above general formulas (A) to (D) are used, heating means can be used to cure the coating composition applied to the surface region and thereby form a coating layer as will 2~ss~~rc be specifically described later.
The silicon compounds represented by the general formula (A) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltr~.ethoxysilane, ethyltrimethoxysilane, ethyltrie-thoxysilane and phenyltrimethoxysilane.
The silicon compounds represented by the general formula (B) include, for example, glycidoxymethyltrime-thoxysilane, glycidoxymethyltriethoxysilane, ~1-glycidoxyethyltriethoxysilane, y-glycidoxypropyltrime-thoxysilane and y-glycidoxypropyltriethoxysilane.
The silicon compounds represented by the general formula (Cj include, for example, aminomethyltrimethox-ysilane, aminomethyltriethoxysilane, aminomethyltripro-poxysilane, aminomethyltributoxysilane, aminoethyltrime-thoxysilane, aminoethyltriethoxysilane, aminoethyltripro-poxysilane, aminoethyltributoxysilane, aminopropyltrime-thoxysilane, aminopropyltriethoxysilane, aminopropyltri-propoxysilane, aminopropyltributoxysilane, N-aminomethyl-aminomethyltrimethoxysilane, N-aminomethyl-aminomethyltriethoxysilane, N-aminomethyl-aminomethyltripropoxysilane, N-aminomethyl-aminomethyl-tributoxysilane, N-~-aminoethyl-~-aminoethyltrimethoxysilane, N-~1-aminoethyl-R -aminoethyltriethoxysilane, N-~-aminoethyl-p-aminoethyltripropoxysilane and N-,~-aminoethyl-~-aminoe-thyltributoxysilane.
The silicon compounds represented by the general formula (D) include, for example, y-mercaptopropyltrime-thoxysilane, y-mercaptopropyltriethoxysilane, y-mercap-topropyltripropoxysilane, y-mercaptopropyltributoxysi-lane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropox-ysilane, mercaptomethyltributoxysilane, mercaptoethyl-trimethoxysilane and mercaptoethyltriethoxysilane.
Where silicon compounds within the scope of the above general formulas (E) and (F) are used, not only heating means but also actinic radiation exposure means can be used to cure the coating composition and thereby form a coating layer.
The silicon compounds represented by the general formula (E) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane arid vinyltri-butoxysilane.
The silicon compounds represented by the general formula (F) include, for example, methacryloyloxymethyl-trimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltripropoxysilane, methacryloyloxyme-thyltributoxysilane, methacryloyloxyethyltrimethox-ysilane, methacryloyloxyethyltriethoxysilane, methacry-loyloxyethyltripropoxysilane, methacryloyloxyethyltribu-toxysilane, methacryloyloxypropyltrimethoxysilane, metha--1~-cryloyloxypropyltriethoxysilane, methacryloyloxypropyl-tripropoxysilane, methacryloyloxypropyltributoxysilane, acryloyloxymethyltrimethoxysilane, acryloyloxymethyltrie-thoxysilane, acryloyloxymethyltripropoxysilane, acryloy-loxymethyltxibutoxysilane, acryloyloxyethyltrimethoxysi-lane, aczylcyloxyethyltriethoxysilane, acryloyloxyethyl-tripropoxysilane, acryloyloxyethyltributoxysilane, acry-loyloxypropyltrimethoxysilane, acryloyloxypropyltriethox-ysilane, acryloyloxypropyltripropoxysilane and acryloy-loxypropyltributoxysilane.
Also useful are silicon compounds obtained by replac-ing the trialkoxysilane groups in the foregoing compounds with dimethoxymethylsil.ane, dimethoxyethylsilane, dimet-hoxypropylsilane, diethoxymethylsilane, diethoxyethylsi-lane, diethoxypropylsilane, dimethoxybutylsilane, diet-hoxybutylsilane, dibutoxymethylsilane, dipropoxyethylsi-lane, dipropoxypropylsilane, dipropoxybutylsilane, dibu-toxymethylsilane, dibutoxyethylsilane, dibutoxypropylsi-lane, dibutnxybutylsilane and like groups.
Colloidal silica (i.e., silica particles) is commer-cially available as a "colloidal silica solution" com-prising silica particles dispersed in water or an alco-hol/water mixture. In order to improve the dispersion stability of the silica particles, this solution is adjusted to an acidic or alkaline pH. In the present invention, the optimum particle diameter of colloidal silica (or silica particles), the content of silica particles in the colloidal silica solution (i.e., its solid content), and the pH of the colloidal silica solu-tion may be chosen as desired. In particular, the opti-mum colloidal silica solution may vary according to the type of hydrolyzable silicon compound used. Usable x commercial products include Cataloid S (solid content 20-30 wt.$; pH 8-10;: manufactured by Catalysts and Chemi-cals Industries Co.,. Ltd.), OSCAL-1432 (solid content 30 wt.~; pH 2-3; manufactured by Shokubai Kasei Kogyo K.K.), Snowtex C (solid content 30 wt.~; pH 8-10; manufactured by Nissan Chemical 7Cndustries, Ltd.), IPA-ST (solid content 30 wt.~; pH 2-3; manufactured by Nissan Chemical Industries, Ltd.) and the like. All of these commercial-ly available colloidal silicas have an average particle diameter of 10-20 gym.
Colloidal silica (i.e., silica particles) may be used in such an amount that the average number of hydrolyzable groups (as will be described later) is within the range of 2.30 to 3.85. Moreover, in the silica polycondensate-forming composition comprising colloidal silica (I) and at lE~ast one hydrolyzable silicon compound (II), colloidal silica (I) is desirably present in an amount of 10 to 40~ by weight. If the amount of colloi-dal silica (I) is less than 10$ by weight, the surface hardness of the coai~ing layer tends to be insufficient.
%~ trademark ~o~~~~s If the amount of colloidal silica (I) is greater than 40~
by weight, the coating layer tends to produce cracks in a severe environment.
The hydrolyzable silicon compounds which can be used as component (II) are divided into four classes according to the number of hydrolyzable groups in the molecule.
They range from monofunctional silicon compounds having one hydrolyzable group to tetrafunctional silicon com-pounds having four hydrolyzable groups. In the present invention, the weight proportion of colloidal silica (I) and the hydrolyzable silicon compound (II) is limited on the basis of experimental results, assuming that (1) hydrolyzable silicon compounds are completely hydrolyzed in a solution and their hydrolyzable groups are all converted to -OH groups and (2) colloidal silica is considered to be a tetrafunctional silicon compound. The average number of hydrolyzable groups is a value calcu-laced from the above equation (I) and corresponds to the average crosslink density of the silica polycondensate (the coating layer) cured by heat treatment. In the present invention, as described previously, colloidal silica (I) and the hydrolyzable silicon compound (II) are mixed in such a molar ratio that the average number of hydrolyzable groups is within the range of 2.30 to 3.85.
If the average number of hydrolyzable groups is greater than 3.85, the heat-treated coating layer is subject to 2oss~~s cracking, and if the average number of hydrolyzable groups is less than 2.30, the heat-treated coating layer does not have sufficient abrasion resistance. Prefera-bly, an average number of hydrolyzable groups within the range of 3.30 to 3.60 is used to obtain a coating layer having excellent abrasion resistance and durability.
Then, a silica polycondensate is obtained by subject-ing the above-described mixture to cohydrolysis and polycondensation. This cohydrolysis and polycondensation can be effected by stirring the mixture in the presence of water and an organic solvent (and a hydrolysis cata-lyst and a condensation catalyst, if necessary) at a temperature ranging from room temperature to the reflux temperature for a period of about 1 to 10 hours. Where a compound having the general formula (A), (B), (D), (E) or (F) is used as the hydrolyzable silicon compound (II), it is desirable to adjust the mixture to a pH of 4 to 5 in that the mixture is hydrolyzed rapidly and can be stored for a long period of time. This pH adjustment can be made by adding an acid as a hydrolysis catalyst. Specif-ic examples of useful acids include citric acid, benzoic acid, acetic acid, hydrochloric acid and nitric acid.
Where a compound having the general formula (C) is used, such an acid need not be used.
The condensation catalyst which is used as required is a latent catalyst which is inactive, for example, in the form of a solution but manifests its effect upon heating, and can be selected from amine salts of carboxylic acids and quaternary ammonium salts of carboxylic acids.
Specific examples thereof include d.imethylamine acetate, ethanolamine acetate, dimethylaniline formate, tetraethy-lammonium benzoate, sodium acetate and sodium propionate.
The condensation catalyst is preferably used in an amount of about 0.05 to 1~ by weight based on the total weight of the mixture.
The amount of water added for hydrolysis may be any suitable amount that is sufficient for hydrolysis.
The organic solvents which can be used for purposes of cohydrolysis and polycondensation include aleohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol;
ketones such as acetone and methyl ethyl ketone; and ethers such as tetrahydrofuran .
The coating composition used in the present invention consists essentially of the silica polycondensate ob-tamed by the above-described cohydrolysis and polycon-densation. If desired, a catalyst which promotes the reaction between the acidic groups present in the surface region and the functional groups (i.e., epoxy, amino and/or mercapto groups) possessed by the hydrolyzable silicon compounds may be added to the coating composi-tion. Far example, in order to promote reaction with epoxy groups, there may be used a perchloric acid com-2086~'~6 pound which is known as a catalyst for 'the ring-opening of epoxy groups. Specific examples of such perchloric acid compounds include ammonium perchlorate, perchloric acid, magnesium perchlorate, potassium perchlorate, sodium perchlorate, zinc perchlorate and aluminum per-chlorate.
Furthermore, as described in Japanese Patent Publica-tion No. 28094/'88, an alkyl (meth)acrylate polymer may also be added to the coating composition in order to further improve the adhesion of the coating layer without impairing its appearance (e. g., transparency and smooth-ness). The alkyl (meth)acrylate polymer preferably has a molecular weight characterized,by an intrinsic viscosity jr~] within the range of 0.01 to 0.30 g/1 and can be a homopolymer of a monomer selected from alkyl (meth)acry-fates having an alkyl group of 1 to 8 carbon atoms or a copolymer of such monomers. Specific examples of the alkyl (meth)acrylate polymer include homopolymers and copolymers of methyl (meth)acrylate, ethyl (meth)acry-late, propyl (meth)acrylate, butyl (meth)acrylate, isobu-tyl (meth)acrylate, amyl methacrylate, hexyl,methacry-late, octyl methacrylate, 2-ethyl-1-hexyl (meth)acrylate, 3-pentyl acrylate, 3-methyl-1-hexyl (meth)acrylate and 3-methyl-1-butyl (meth)acrylate. These polymers may be used alone or in admixture of two or more.
In order to apply the above-described coating composi-tion to the surface region, there may be employed any of various techniques such as spray coating, spin coating and dip coating. However, dip coating is preferred for shaped articles having a simple configuration and spray coating is preferred for shaped articles having a complex configuration.
Then, the coating composition applied to the surface region is cured according to any conventional method to form a coating layer. During this process, the reactive functional groups present in the silica polycondensate (for example, the epoxy, amino and/or mercapto groups possessed by the compounds of the general formulas (A) to (F)) chemically react with the acidic groups (carboxyl and hydroxyl groups) present in the surface region, resulting in enhanced adhesion. Useful conventional methods include the application of heat and exposure to actinic radiation such as ultraviolet light arid y rays.
Where any of tile hydrolyzable silicon compounds repre-rented by the general formulas (Aj to (F) is used, the coating layer can be formed through curing by the appli-cation of heat. This can be done, for example, by heat-ing the coated shaped article in an oven at 100-130°C for a period of time ranging from about 10 minutes to about hours.
Where a vinyl- or (meth)acryloyloxy-containing silicon compounds of the general formulas (E) or (F) is used, the coating layer can advantageously be formed through curing by exposure to actinic radiation. This exposure to actinic radiation can be carried out under any suitable conditions that are well known in -the art.
After being cured by the application of heat or by exposure to actinic radiation, the coating layer may have a thickness of 1 to 30 ~cm and preferably 1 to 10 a m. If the thickness of the coating layer is less than 1 ,um, the resulting shaped article does not have sufficient surface hardness and abrasion resistance. If the thick-ness of the coating layer is greater than 30 a m, the coating layer shows a reduction in adhesion and tends to produce cracks.
The present invention is more specifically explained with reference to the following examples. In these examples, the coated shaped articles were evaluated according to the following procedure.
1. Abrasion resistance Using a Taber abrader (manufactured by Toyo Seiki Seisakusho K.K.), a CS-17 truck wheel was pressed against a sample under a load of 250 g and rotated 1,000, 3,000 and 5,000 cycles. Thereafter, the sample was washed with a neutral detergent and its total light transmittance (Tt) and haze (H) were measured with a Model HR-100 transmissometer (manufactured by Murakami Color Technolo-gy Laboratory).

2~~~~7~

2. Adhesion The adhesion of the coating layer of a sample was evaluated by an adhesive tape peeling test. Specifical-ly, by cutting the surface of the sample with a cutter knife at intervals of 1.5 mm, 11 parallel cuts were made in each of two orthogonal directions to form a total of 100 squares in the coating layer. A strip of cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was applied to the squares under pressure and peeled off upward and quickly. Of the 100 squares, the number of the unremoved squares was counted and used as an index to the adhesion of the coating layer.
3. Durability (a) Thermal shock test Using a thermal shock tester, a sample was subjected to thermal cycles each comprising exposure to an atmos-phere at -30°C for 2 hours and then at 80°C for 3 hours.
After the sample was subjected to 5 thermal cycles, its appearance was examined and its total light transmittance (Tt) and haze (H) were measured.
(b) Accelerated weathering test Using a sunshine weatherometer (manufactured by Suga Testing Machines Co., Ltd.) having a black panel tempera-ture of 63°C, a sample was subjected to a 500 hour weath-Bring test in which the sample was cyclically exposed to water spray for 12 minutes and dried for 48 minutes.

2080~'~6 Thereafter, its adhesion was evaluated and its appearance was visually examined for changes.
(c) Water immersion test A sample was immersed in warm water at 60°C for 100 hours. Thereafter, the adhesion and abrasion resistance of the sample were evaluated.
Formation of substrates having acidic groups in the surface region thereof:
(1) Monomer solutions were prepared by adding 35 parts by weight of isopropyl alcohol and 20 parts by weight of toluene to 45 parts by weight of each of monomer composi-Lions No. 1 to 5 shown in Table 1. Substrates were dipped into each of the monomer solutions and then taken out at a speed of 1 m/min to form a monomer solution film on the surfaces thereof. The substrates comprised poly-methyl methacrylate (PMMA) plates (commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Acrylite L) and polycarbonate (PC) plates (commercially available from Mitsubishi Rayon Co., Ltd, under the trade name of Dialite).
Then, as illustrated in Fig. 4, each substrate with the monomer solution film thereon was sandwiched between two glass plates (commercially available under the trade name of BK-7) having a thickness of 1.5 mm, and irradiat-ed from outside the glass plates with ultraviolet light from a high-pressure mercury vapor lamp to effect photo-2~~~~°~6 polymerization of the monomers. The reason why the substrate was covered with 'the glass plates is that the monomer solution film can be cured only in the absence of air. Under these conditions, ultraviolet light having wavelengths shorter than 300 nm was absorbed by the glass plates. The integrated energy of ultraviolet light at 365 nm was 2,508 mJ/cm2 and the thickness of the photo-cured polymer layer 2 (Fig. 1) was 20 E.~m. For purposes of irradiation, there was used a Model UV5003 Ultraviolet Light Irradiator (manufactured by Mitsubishi Rayon Engi-neering Co., Ltd.). This light source emits ultraviolet light having a principal wavelength of 365 nm and also wavelengths of 300 nm or less. The integrated energy of ultraviolet light was measured by means of a Model Uv-350 Ultraviolet Actinometer (manufactured by Oak Seisakusho K.K.). This actinometer (Model UV-350) has.a peak sensi-tivity wavelength of 360 nm and a measurable wavelength range of 320-390 nm.
(2) Using a high-pressure mercury vapor lamp, the polymer layer formed as described in paragraph {1) was irradiated with ultraviolet light containing short-wave-length light of 300 nm or less to partially break the crosslinked molecular chains. For this purpose, the surface of the polymer layer was directly exposed to ultraviolet light .from the high-pressure mercury vapor lamp. The integrated energies of ultraviolet light ~~ '~'~'~

applied to the polymer layer are shown in Table 1. For purposes of irradiation, the same ultraviolet light irradiator (Model UV5003) as described above was used.
The integrated energies of ultraviolet light were meas-ured by means of Model UV-350 and Model UV-350-25 U1-traviole;: Actinometers (manufactured by Oak Seisakusho K.K.). The latter actinometer (Model UV-350-25) has a peak sensitivity wavelength of 254 nm and a measurable wavelength range of 241-271 nm.
Then, the ultraviolet light-irradiated polymer layer was hydrolyzed by soaking it in a 10-20 wt.o aqueous solution of sodium hydroxide (having a temperature of 25-50°C). The conditions of hydrolysis and the measured quantity of acidic groups so produced are shown in Table 1.
As can seen from the data marked with (A), (E), (I), (M) and (R), the quantity of acidic groups was insuffi-cient when no alkali treatment of the polymer layer was performed.
Preparation of coatinG composition solutions, <Coating composition solution Nos. I-III>
A colloidal silica solution containing 30 wt.~ of colloidal silica dispersed in isopropyl alcahol (commer-dally available from Nissan Chemical Industries, Ltd.
under the trade name of IPA-ST), y-glycidoxypropyltrimethoxysilane (commercially available 2(~~62"l ~
_ 29 _ from Toshiba Silicone Co., Ltd. under the trade name of TSL-8350), first-class grade tetraethoxysilane (commer-cially available from Katayama Chemical Industry Co., Ltd.), y-glycidoxypropylmethyldiethoxysi.lane (commer-cially available from Shin-Etsu Chemical Co., Ltd. under the trade name of KBE-402), isopropyl alcahol and 1/1000N
hydrochloric acid were mixed according to each of the formulations shown in Table 2. This mixture was heated to 70'C and stirred at that temperature for 7 hours.
After the resulting solution was cooled to room tempera-ture, magnesium perchlorate was added thereto as a cata-lyst for the ring-opening of epoxy groups, and dissolved therein to prepare a coating composition solution. The average numbers of hydrolyzable groups of coating compo-sitian solution Nos. I-III, as calculated from the above equation (1), are. shown in Table 2. These coating compo-sition solution Nos. I-III were all adjusted to pH 4.5.
<Coating composition solution No. IV>
15.7 g of N-(~-aminoethyl)aminopropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.
under the trade name of KBM-S03), 50.0 g of y-glycidoxypropyltrimethoxysilane (TSL-8350), 56.0 g of an isopropyl alcohol-dispersed colloidal silica solution (IPA-ST), 547.4 g of isopropyl alcohol and 4.3 g of puri fied water were mixed, and this mixture was stirred at room temperature (25°C) for 7 hours. In order to promote hydrolysis and polycondensation, 'the resulting solution was allowed to stand at room temperature for 5 days and used as a coating composition solution. The average number of hydrolyzable groups of this solution was 3.5.
The silane compound TSL-8350 was used in an amount equal to its epoxy equivalent. The solids content of the solution at the time of mixing was 13.0 by weight based on its total weight. The reason why the above-described formulation was used is that, if the solids content at the time of mixing is greater than 20~ by weight and the amount of water added is greater than 30~ by weight of the stoichiometric amount required for hydrolysis, the shelf-life of the solution will become extremely short.
When stored at room temperature, this solution remained colorless and clear for 10 days after preparation, but became increasingly turbid from then on.
<Coating composition solution No. V>
270.0 g of y -mercaptopropyltrimethoxysilane (KBM-803), 162.0 g of y-glycidoxypropyltrimethoxysilane (TSL-8350), 412.0 g of an isopropyl alcohol-dispersed colloi-dal silica solution (IPA-ST) and 222.5 g of 1/1000N
hydrochloric acid were mixed, and this mixture was stirred at room temperature (25'C) for an hour. Then, the resulting solution was stirred at 70'C for 3 hours to promote hydrolysis. After the solution was cooled again to room temperature, 3.0 g of magnesium perchlorate was dissolved therein to prepare a coating composition solu-tion. The average number of hydrolyzable groups of this solution was 3.50 and its solids content at the time of mixing was 30~ by weight based on its total weight.
<Coating composition solution No. Vx>
70.0 g of ~y-methacryloyloxypropyltrimethoxysilane (commercially available from Nippon Unicar Co., Ltd.
under the trade name of A-174), 100.0 g of an isopropyl alcohol-dispersed colloidal silica solution (IPA-ST) and 30.2 g of 1/1000N hydrochloric acid were mixed. This mixture was stirred at 70°C for 3 hours to promote hy-drolysis. After the resulting solution was cooled again to roam temperature, 0.5 g of benzoin isopropyl ether and 0.5 g of methyl phenyl glyoxylate were added thereto as photo-initiators to prepare a coating composition solu-tion. The average number of hydrolyzable groups of this solution was 3.641.
Examples 1-18 In Examples 1-5, 7-15, l7.and 18, a resin plate having acidic groups (one of (A) to (U) in Table 1) was dipped into one of coating composition solution Nos. I-V and taken out at a speed of 50 cm/min. Then, the coated resin plate was cured in an oven at 105'C for 3 hours to obtain a coated shaped article. Tn Examples 6 and 16, a resin plats having acidic groups ((D) or (Q) in Table 1) was dipped into coating composition solution No. VI and ~o~s~~s taken out at a speed of 1 m/min. In order to evaporate the solvent from the coating film, the coated resin plate was allowed to stand in an oven at 80°C for 5 minutes.
Then, using an ultraviolet light irradiator (W-5003), the coated resin plate was irradiated with 365 nm ul-traviolet light having an energy of 3,000 mJ/cm2 to obtain a coated shaped article. The results of evalua-tion of the coated shaped articles thus obtained are shown in Table 3.
Comparative Example 1 According to the formulation for coating composition solution VII shown in Table 4, various ingredients (i.e., IPA-ST, GPTMSi, TEOSi, IPA and 1/1000N HC1) were mixed.
This mixture was heated to 70°C and stirred at that tem perature for 7 hours. After the resulting solution was cooled to room temperature, magnesium perchlorate (in the amount shown in Table 4) was added thereto as a catalyst for the ring-opening of epoxy groups and dissolved there-in to prepare a coating composition solution. A resin plate ((C) in Table 1) was dipped into this coating composition solution and taken out at a speed of 1 m/min.
The coated resin plate was thermally cured in an oven at 105°C for 3 hours. After heat treatment, however, the resulting coating layer was found to be cracked.
Comparative Exam lp a 2 According to the formulation for coating composition solution VIII shown in Table 4, various ingredients (i.e., IPA-ST, GPDM;Si, IPA and 1/1000N HC1) were mixed.
This mixture was heated to 70'C and stirred at that temperature for 7 hours. After the resulting solution was cooled to room temperature, magnesium perchlorate (in the amount shown in Table 4) was added thereto as a catalyst for the ring-opening of epoxy groups and dis-solved therein to prepare a coating composition solution.
A resin plate ((C) in Table 1) was dipped into this coating composition solution and taken out at a speed of 1 m/min. The coated resin plate was thermally cured in an oven at 105'C fo.r 3 hours. The resulting coating layer was not smooth because of poor leveling properties and was found to lack abrasion resistance in that the coating layer was easily damaged by #0000 steel wool pressed against it;..
Comparative ExamQles 3-7 The results of evaluation of several shaped articles outside the scope of the present invention are shown in Table 5. In Comparative Example 3, a resin plate ((A) in Table 1) having an insufficient quantity of acidic groups was coated with coating composition solution No. III. In Comparative Example 4, a polymethyl methacrylate (PMMA) plate (commercially available from Mitsubishi Rayon Co., %<
Ltd. under the trade name of Acrylate L) was coated di rectly with coating composition solution No. III. In <trademark.

Comparative Examples 5-7, the results of abrasion tests with commercially available surface--hardened plates and a glass plate. Acrylite MR is a surface-hardened acrylic resin plate manufactured by Mitsubishi Rayon Co., Ltd.
and Dialite SH is a surface-hardened polycarbonate plate manufactured by Mitsubishi Rayon Co., Ltd. The glass plate is a commercial product (sold under the trade name of BK-7) having a thickness of 2 mm.

Table 1 (Substrates (A) 1~0 (U) having acidic groups thereon) Polymer layer Integrated ener of ultraviolet lig~~ for Monomer composition breakin of molecular No. Substrate chains ~mJ/cm2) Monomers wt.~ 365 nm 254 nm 1 PMMA 1~6-Hexanediol 60 3762 1500 diacrylate Equimolar condensate 39 of trimeth~,rlolethane/

acrylic ac=~d/succinic ac di Photo-in~t:Lator 1 ( Darocur 1:L 7 3 ) 2 PMMA Dipentaeryi:.hritol 50 3762 1500 hexaacrylai~e 1, 6-Hexanediol 49 diacrylate Photo-init.-Lator 1 ( Darocur 1:L 7 3 ) 3 PMMA Neopentylg:Lycol 50 3762 1500 diacrylate Trimethy to:Lpropane 10 t i r acrylatca 1, 6-Hexane<iiol 20 diacrylate Pentaerythritol 19 triacry~atE~

Photo-initiator 1 ( Darocur l :l7 3 ) 4 PC 1~6-Hexanediol 60 3762 1500 diacrylat.e Equimolar condensate 39 of trimeth~~lolethane/

acry lic ac'~d/succinic acid Photo-initiator 1 ( Darocur 1:173 ) PC Dipentaerythritol 50 3762 150() hexaacrylate lc6-Hexaned.iol 49 diacrylate Photo-initiator 1 (Darocur :1173) *trademark 20~62'~6 Surface region Aque ous NaOH solution Quantity of for alkali treatment acidic groups Tempera-~Concentra- Soakinq (x10-2 ~Cmol/cm2) Lure (C) tion (wt.g) ti me (~r) 50 10 0 7.0 (A) 0.5 40.0 (B) 1.0 80.0 (C) 1.5 100.2 (D) 25 20 0 8.0 (E) 1.0 50.1 (F) 2.0 61.8 (G) 24.0 37.2 (H) 25 10 0 5.0 (I) 0.5 50.2 (J) 1.0 70.5 (IG) 2.0 42.5 (L) 25 10 0 7.5 (M) 0.5 77.2 (N) 1.0 75.9 (O) 2.0 77.7 (~) 24.0 51.0 (Q) 25 20 0 8.0 (R) 1.0 50.5 (S) 2.0 51.5 (T) 24.0 37.2 (U) 2oss~~r6 Table 2 (Coating composition solution Nos. I-III) Formulation of coating composition solution Coatin - -g compo- ColloidalHydrolyzable1/1000N Mg(C104)2 HCl sition silica silicon (hydrolysis(ring- IPA

solutionsolution com ounds catal st) o eninq No (I ~ ~ ca ST) ) a s~

. g (g ~ (g) ~y ) (g) g I 250.0 GPTMSi 33.8 107.8 3.6 282.0 TEOSi 100.0 GPDMSi 70.3 II 250.0 GPTMSi 22.5 105.5 3.6 282.0 TEOSi 100.0 GPDMSi 80.5 III 250.0 GPTMSi 11.3 103.5 3.6 282.0 TEOSi 100.0 GPDMSi 90.5 GPTMSi: y -Glycidoxypropyltrimethoxysilane.
TEOSi: Tetraethoxysilane.
GPDMSi: y -Glycidoxypropylmethyldimethoxysilane.
IPA: Isopropyl alcohol.
Average Aq ing number conditions of hydrolyzable groups 70C, 7 hr 3.643 70C, 7 hr 3.610 70'C, 7hr 3.602 Table 3 (Evaluation of performance of coated shaped articles) Coating Thick- Initial Haze (~) after Ex. Subst-compose-ness performance abrasion test No rate Lion of ---coati . solutionng Adhesion Tt H 1000 3000 layer 5000 No. (,um) (~) (~) (cycles) 1 (B) I 2.5 100/100 94.4 0.1 1.0 1.5 2.9 2 (B) II 2.3 100/100 94.0 0.1 1.0 1.5 2.9 3 (C) III 2.3 100/100 94.1 0.1 1.0 1.5 2.9 4 (C) IV 2.0 100/100 94.1 0.1 1.0 1.5 2.9 (D) V 2.5 100/100 94.1 0.1 1.0 1.5 2.9 6 (D) VI 3.5 100/100 94.1 0.1 1.0 1.5 2.9 7 (F) I 2.5 100/100 94.1 0.1 1.0 1.7 3.0 8 (G) II 2.5 100/100 94.1 0.1 1.0 1.5 3.5 9 (J) I 2.7 100/100 94.1 0.1 1.0 1.5 3.5 (K) II 2.6 100/100 94.1 0.1 1.0 1.5 3.5 11 (N) I 3.5 100/100 93.0 0.1 2.4 2.9 6.7 12 (N) II 2.5 100/100 93.0 0.1 2.6 2.9 5.7 13 (N) TII 2.5 100/100 93.2 0.1 2.4 3.9 6.7 14 (O) IV 2.7 100/100 93.1 0.1 2.3 2.9 5.7 (P) V 2.6 100/100 93.1 0.1 2.1 2.9 5.5 16 (Q) VI 2.6 100/100 93.1 0.1 2.0 2.7 5.7 17 (S) I 2.8 100!100 92.8 0.1 2.1 2.9 6.5 18 (T) II 2.8 100/100 92.8 0.1 2.2 3.5 6.8 Tt: Total light transmittance.
H: Haze.
*: These designations correspond to those even in the "Quantity of acidicgroups column of Tale 1.

~~86~~6 After After thermal water shock test After accelerated immersion h test i Adhesion Tt H Tt H weat er ng test (~) (~) ($) (~) (after S00 hours) 100/100 94.4 0.3 94.4 0.1 Initial erformance was main~a~.ned.
100/100 94.0 0.3 94.0 0.1 ditto 100/100 94.1 0.3 94.1 0.1 ditto 100/100 94.1 0.3 94.1 0.1 ditto 100/100 94.1 0.3 94.1 0.1 ditto 100/100 94.1 0.3 94.1 0.1 ditto 100/100 94.0 0.2 94.1 0.1 ditto 100/100 94.1 0.2 94.1 0.1 ditto 100/100 94.1 0.2 94.1 0.1 ditto 100/100 94.1 0.2 94.1 0.1 ditto 100/100 93.0 0.1 93.0 0.1 ditto 100/100 93.0 0.1 93.0 0.1 ditto 100/100 93.3 0.1 93.2 0.1 ditto 100/100 93.2 0.1 93.1 0.1 ditto 100/100 93.2 0.1 93.1 0.1 ditto 100/100 93.1 0.1 93.1 0.1 ditto 100/100 92.5 0.1 92.5 0.1 ditto 100/100 92.6 0.1 92.6 0.1 ditto 2o~s2~rs Table 4 (Coating composition solution Nos. VII and VIII) Coating Average compositionFormulation number of l ti so hydrolyzable u on No, groups VII IPA-ST 250.0g 3.900 GPTMSi 40.0 g TEOSi 45.0 g IPA 282.0g 1/1000N HC1 49.4 g Mg(C104)Z 2.5 g VIII IPA-ST 33.3 g 2.290 GPTMSi 160.0g IPA 373.4g 1/1000N HC1 108.0g Mg(C104)2 2.5 g Table 5 (Evaluation of performance in Comparative Examples 3-7) Coating Thick- Initial Comp, compose-ness performance E t it of t ti S
b x. s s coa e ion ng u ra No. solutionlayer Adhe- Tt H

No. (,um) sion (~) (~) 3 (A) in Table 1 III 2.5 0/100 94.1 0.1 4 PMMA III 2.5 0/100 94.1 0.2 Surface-hardened - - 93.0 0.1 plate (Acrylite MR) 6 Surf ace-.hardened- - 9 0 . 0 0 .

plate ((Dialite SH) 7 Glass plate - - 93.0 0.1 Haze (~) after abrasion test Adhesion ft t er wa 1000 3000 5000 er (cycles) a immersion test 2.2 4.2 18.5 0/100 23.1 29.1 45.9 0/100 13.1 17.7 34.7 -10.4 25.5 47.0 -1.4 2.4 3.5 -

Claims (10)

1. An abrasion-resistant shaped article having a coating layer formed on the surface region, wherein the surface region is formed of a polymer having structural units derived from a multifunctional monomer containing two or more (meth)acryloyloxy groups in the molecule and has 0.02 to 0.2 µmol/cm2 of acidic groups therein, by curing a coating composition consisting essentially of a silica polycondensate obtained by mixing (I) colloidal silica and (II) at least one hydrolyzable silicon compound having any of the following general formulas (A) to (F) in such a molar ratio that the average number of hydrolyzable groups calculated from the following equation (1) is within the range of 2.30 to 3.85, and then subjecting them to cohydrolysis and polycondensation, the formulas (A) to (F) being SiR1a R2b (OR3)c (A) SiR4d R5e (OR6)f (B) SiR7g R8h (OR9)i (C) SiR10j R11k (OR12)l (D) SiR13m R14n(OR15)o (E) SiR16p R17q(OR18)r (F) where R1, R2, R3 R5, R6, R8, R9, R11, R12, R14, R15, R17 and R18 in formulas (A) to (F) are hydrocarbon radicals of 1 to 15 carbon atoms which may have an ether linkage or an ester linkage, R4 in formula (B) is a hydrocarbon radical of 2 to 15 carbon atoms having an epoxy group, R7 in formula (C) is a hydrocarbon radical of 1 to 15 carbon atoms having an amino group, R10 in formula (D) is a hydrocarbon radical of 1 to 15 carbon atoms having a mercapto group, R13 in formula (E) is a hydrocarbon radical of 2 to 15 carbon atoms having a vinyl group, R16 in formula (F) is a hydrocarbon radical of 3 to 15 carbon atoms having a (meth)acryloyloxy group, a, b, d, e, g, h, j, k, m, n, p and q are whole numbers of 0 to 3, c is equal to (4-a-b), f is equal to (4-d-e), i is equal to (4~g~h), 1 is equal to (4-j-k), o is equal to (4~m~n), and r is equal to (4-p-q), and equation (1) being Average number of hydrolyzable groups 4[I]+c[A]+f[B]+i[C]+l[D]+o[E]+r[F]
=~__________________________________~(1) [I]+[A]+[B]+[C]+[D]+[E]+[F]
where [A] to [F] are the number of moles of the hydrolyzable silicon compounds of the general formulas (A) to (F), respectively, present in the reaction mixture, [I] is the number of moles of the colloidal silica present in the reaction mixture, and c, f, i, l, o and r are the same whole numbers as defined above for the general formulas (A) to (F).
2. An abrasion-resistant shaped article as claimed in claim 1 wherein the polymer having structural units derived from a multifunctional monomer is obtained by polymerizing a monomer composition containing 30% by weight or more of the multifunctional monomer.
3. An abrasion-resistant shaped article as claimed in claim 1 wherein the coating composition additionally contains an alkyl (meth)acrylate polymer.
4. An abrasion-resistant shaped article as claimed in claim 1 wherein the coating layer is formed by curing the coating composition by the application of heat.
5. An abrasion-resistant shaped article as claimed in claim 1 wherein the hydrolyzable silicon compound (II) comprises at least one compound having the general formula (E) or (F) and the coating layer is formed by curing the coating composition by exposure to actinic radiation.
6. A method of making abrasion-resistant shaped articles which comprises the steps of (a) providing a shaped article having a surface formed of a polymer having structural units derived from a multifunctional monomer containing two or more (meth)acryloyloxy groups in the molecule, (b) irradiating the surface of the polymer with ultraviolet light having a wavelength of 300 nm or less, (c) subjecting the irradiated surface to an alkali treatment, (d) coating the irradiated and alkali-treated surface with a coating composition consisting essentially of a silica polycondensate obtained by mixing (I) colloidal silica and (II) at least one hydrolyzable silicon compound having any of the following formulas (A) to (F) in such a molar ratio that the average number of hydrolyzable groups calculated from the following equation (1) is within the range of 2.30 to 3.85, and then subjecting them to cohydrolysis and polycondensation, and (e) curing the coating composition, the formulas (A) to (F) being SiR1a R2b (OR3)c ~ (A) SiR4d R5e (OR6)f~ (B) SiR7g R8h (OR9)i~ (C) SiR10j R11k (OR12)l ~ (D) SiR13n R14n(OR15)o ~(E) SiR16p R17q(OR18)r ~(F) where R1, R2, R3 R5, R6, R8, R9, R11, R12, R14, R15, R17 and R18 in formulas (A) to (F) are hydrocarbon radicals of 1 to 15 carbon atoms which may have an ether linkage or an ester linkage, R4 in formula (B) is a hydrocarbon radical of 2 to 15 carbon atoms having an epoxy group, R7 in formula (C) is a hydrocarbon radical of 1 to 15 carbon atoms having an amino group, R10 in formula (D) is a hydrocarbon radical of 1 to 15 carbon atoms having a mercapto group, R13 in formula (E) is a hydrocarbon radical of 2 to 15 carbon atoms having a vinyl group, R16 in formula (F) is a hydrocarbon radical of 3 to 15 carbon atoms having a (meth)acryloyloxy group, a, b, d, e, g, h, j, k, m, n, p and q are whole numbers of 0 to 3, c is equal to (4-a-b), f is equal to (4-d-e), i is equal to (4-g-h), 1 is equal to (4-j-k), o is equal to (4-m-n), and r is equal to (4-p-q) , and equation (1) being Average number of hydrolyzable groups 4[I]+c[A]+f[B]+i[C]+l[D]+o[E]+r[F]
=~__________________________________ ~(1) [I]+[A]+[B]+(C]+[D]+[E]+[F]
where [A] to [F] are the number of moles of the hydrolyzable silicon compounds of the general formulas (A) to (F), respectively, present in the reaction mixture, [I] is the number of moles of the colloidal silica present in the reaction mixture, and c, f, i, l, o and r are the same whole numbers as defined above for the general formulas (A) to (F).
7. A method of making abrasion-resistant shaped articles as claimed in claim 6 wherein the polymer having structural units derived from a multifunctional monomer is obtained by polymerizing a monomer composition containing 30% by weight or more of the multifunctional monomer.
8. A method of making abrasion-resistant shaped articles as claimed in claim 6 wherein the coating composition additionally contains an alkyl (meth)acrylate polymer.
9. A method of making abrasion-resistant shaped articles as claimed in claim 6 wherein the coating composition is cured by the application of heat.
10. A method of making abrasion-resistant shaped articles as claimed in claim 6 wherein the hydrolyzable silicon compound (II) comprises at least one compound having the general formula (E) or (F) and the coating composition is cured by exposure to actinic radiation.
CA 2086276 1992-12-23 1992-12-24 Coated shaped articles and method of making same Expired - Fee Related CA2086276C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA 2086276 CA2086276C (en) 1992-12-24 1992-12-24 Coated shaped articles and method of making same
EP19920122038 EP0604677B1 (en) 1992-12-24 1992-12-28 Method of making coated shaped articles
US08/305,553 US5470616A (en) 1992-12-23 1994-09-14 Coated shaped articles and method of making same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA 2086276 CA2086276C (en) 1992-12-24 1992-12-24 Coated shaped articles and method of making same
EP19920122038 EP0604677B1 (en) 1992-12-24 1992-12-28 Method of making coated shaped articles
US08/305,553 US5470616A (en) 1992-12-23 1994-09-14 Coated shaped articles and method of making same

Publications (2)

Publication Number Publication Date
CA2086276A1 CA2086276A1 (en) 1994-06-25
CA2086276C true CA2086276C (en) 2001-12-11

Family

ID=27169301

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2086276 Expired - Fee Related CA2086276C (en) 1992-12-23 1992-12-24 Coated shaped articles and method of making same

Country Status (3)

Country Link
US (1) US5470616A (en)
EP (1) EP0604677B1 (en)
CA (1) CA2086276C (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2086276C (en) * 1992-12-24 2001-12-11 Masamoto Uenishi Coated shaped articles and method of making same
WO1995021220A1 (en) * 1994-02-02 1995-08-10 Mitsubishi Rayon Co., Ltd. Coating composition and surface-coated molding produced therewith
EP0730015B1 (en) * 1995-02-28 1999-01-13 Dow Corning Corporation Method for making organically-modified, radiation-curable siloxane resins
JP3189773B2 (en) * 1998-01-09 2001-07-16 三菱電機株式会社 Method of forming resist pattern, method of manufacturing semiconductor device using the same, and semiconductor device
US6517939B1 (en) 1999-09-03 2003-02-11 Engelhard Corporation Noble metal coated substrate pigments
KR20010085131A (en) * 2000-02-28 2001-09-07 김은엽 Method of scratch-resistant multi-layer coating with silicon agent on the surface of polymer
ES2359228T3 (en) * 2000-10-21 2011-05-19 Evonik Degussa Gmbh SYSTEMS OF CURABLE VARNISHES BY RADIATION.
US20040099132A1 (en) * 2002-11-27 2004-05-27 Parsons Christopher V. Tactile metronome
CA3084272A1 (en) 2017-12-07 2019-06-13 Basf Coatings Gmbh Scratch and mar resistant automotive coatings

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3986997A (en) * 1974-06-25 1976-10-19 Dow Corning Corporation Pigment-free coating compositions
GB2018621B (en) * 1978-04-12 1982-03-24 Gen Electric Polycarbonate article coated with an adherent durable silica filled organopolysiloxane coating and process for produing same
US4299746A (en) * 1978-11-30 1981-11-10 General Electric Company Silicone resin coating composition
US4277287A (en) * 1978-11-30 1981-07-07 General Electric Company Silicone resin coating composition
US4413088A (en) * 1978-11-30 1983-11-01 General Electric Co. Silicone resin coating composition especially suited for primerless adhesion to cast acrylics
US4368236A (en) * 1978-11-30 1983-01-11 General Electric Co. Silicone resin coating compositions
US4477528A (en) * 1979-04-27 1984-10-16 General Electric Company Silicone resin coating composition especially suited for primerless adhesion to cast acrylics
US4353959A (en) * 1979-12-21 1982-10-12 General Electric Company Abrasion resistant silicone coated polycarbonate article having an acrylic primer layer containing a U.V. absorbing compound
US4373060A (en) * 1980-05-30 1983-02-08 General Electric Company Silicone coating for unprimed plastic substrate and coated articles
US4382983A (en) * 1980-07-24 1983-05-10 Sumitomo Chemical Company, Limited Method for the formation of abrasion-resistant coating film
JPS58157865A (en) * 1982-03-11 1983-09-20 Toshiba Silicone Co Ltd Coating composition
JPH0642002B2 (en) * 1983-07-29 1994-06-01 セイコーエプソン株式会社 Plastic lens
JPS60103347A (en) * 1983-11-11 1985-06-07 Seiko Epson Corp Plastic photochromic lens
JPS60174622A (en) * 1984-02-20 1985-09-07 Matsushita Electric Works Ltd Sandwich molding device
DE3613082A1 (en) * 1985-05-07 1986-11-13 Hüls AG, 45772 Marl ADHESIVE ADHESIVES ON THE BASIS OF RADIANT, POLYESTERS CONTAINING (METH) ACRYLIC GROUPS
US5139815A (en) * 1990-08-13 1992-08-18 H. P. Smith, Inc. Acid catalyzed silicone release layers
JPH04234442A (en) * 1990-12-28 1992-08-24 Mitsubishi Rayon Co Ltd Production of permanently antistatic molding
JPH04327519A (en) * 1991-04-26 1992-11-17 Sanyo Chem Ind Ltd Aqueous gelatinous hairdressing
CA2086276C (en) * 1992-12-24 2001-12-11 Masamoto Uenishi Coated shaped articles and method of making same

Also Published As

Publication number Publication date
EP0604677A1 (en) 1994-07-06
US5470616A (en) 1995-11-28
CA2086276A1 (en) 1994-06-25
EP0604677B1 (en) 1999-08-11

Similar Documents

Publication Publication Date Title
CA1158794A (en) Abrasion resisting ultraviolet light curable hard coating compositions
US5385955A (en) Organosilane coating composition for ophthalmic lens
KR100377042B1 (en) Coating compositions, methods for their preparation, and surface coatings using them
EP1914259B1 (en) Primer composition and coated article
US20090269504A1 (en) Flexible hardcoats and substrates coated therewith
EP1471120A2 (en) Protective coat-forming coating composition, coated article, and multilayer laminate
MX2012005061A (en) Coating composition comprising an alkoxysilane, and polysiloxane, and a plurality of particles.
RU2514939C2 (en) Polysiloxane coatings with hybrid copolymers
JP5788014B2 (en) Composition and film comprising the same
CA2086276C (en) Coated shaped articles and method of making same
EP0463747B1 (en) Coated plastic molded articles and processes for their preparation
JP2012056167A (en) Plastic substrate for glazing
MXPA02003532A (en) Coating materials.
EP2268751A2 (en) Oleophilic compositions, coatings employing the same, and devices formed therefrom
KR101885404B1 (en) Active energy ray-curable composition, laminate, and method for producing laminate
JP4861648B2 (en) Laminated body
JP2000177070A (en) Ultraviolet absorbing laminated resin material
JP4487770B2 (en) Curable resin composition and antireflection material
JPH0372302A (en) Composition for coating
JP2009046526A (en) Resin film for improving resistance
JPH10102002A (en) Composition for photocurable coating agent and formation of coated film
JP4287015B2 (en) Transparent plastic composite with protected surface
JP2004035614A (en) Coated polycarbonate plate-like molded article
JP3204698B2 (en) Coated molded article and method for producing the same
JP2004035613A (en) Surface-protected transparent plastic molding and primer composition for organosiloxane resin composition

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed