JP2008001870A - Silicone-containing resin coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone-containing resin coating composition having good adhesiveness to a substrate resin and to provide a produced article by coating the surface of the resin substrate with the composition. <P>SOLUTION: The silicone-containing resin coating composition is used for coating the resin substrate. The surface of the resin substrate to be a protection mode is coated with the silicone-containing resin coating composition as a silicone-containing resin composition in an uncured state. The surface of a clean resin substrate is then coated with the silicone-containing resin coating composition by a suitable, well-known and commercially practicable step such as brushing, spraying or electrodeposition and cured by receiving photochemical action irradiation such as UV (ultraviolet) light or particle irradiation such as electron beams to afford the produced article having a silicone-containing resin coating layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to silicon-containing resin coating compositions and manufactured articles coated with them. Specifically, the present invention relates to a silicon-containing resin coating composition that protects the surface of a resin substrate and a manufactured article coated with the same.

  Such coating compositions are sometimes referred to as silicon hardcoat resins or organo-polysiloxanes made by condensation of hydroxyorganosilicon compounds formed by hydrolysis of organosilicon halogen compounds. Preferred silicon-containing coating compositions include products in which colloidal silica is combined with various acrylicoxy or glycidoxy functional compounds such as acryloxy functional or glycidoxy functional silanes or silyl acrylates.

Transparent wear-resistant coatings made of synthetic resin containing silicon are used for transparent plastic coatings that do not scatter or are more resistant to splatter than glass, but they are used every day as a cause of polishing such as dust, cleaning equipment and everyday weather. It is exposed to scratches and abrasions caused by contact. Examples of such conventional technical documents include the following.
JP 2004-344873 A

However, conventionally, direct application of a silicon-containing resin coating composition to the surface of a resin substrate has been almost unsuccessful due to poor adhesion between the substrate resin and the cured silicon-containing resin coating composition.
Therefore, an object of the present invention is to provide a cured silicon-containing resin coating composition having good adhesion to a base resin, and a manufactured article in which the composition is directly coated on the surface of a resin base.

The resin coating composition for coating a resin substrate according to claim 1 contains silicon.
The coating composition of claim 2 is characterized in that, in claim 1, the silicon-containing resin coating composition comprises a condensation product of colloidal silica and a silyl acrylate represented by the following formula. However,

Wherein R4 is a C (1-13) monovalent organic group, R5 is a C (1-8) alkyl group, R6 is selected from hydrogen, R4 groups or combinations thereof, and R7 is 2 A valence C (1-8) alkylene group, a is a natural number of 0-2, b is an integer of 1-3, and a + b is 1-3.)
The coating composition according to claim 3 is the coating composition according to claim 1 or 2, wherein the silicon-containing resin contains 5 to 500 parts by weight of acryloxy functional silane or glycidoxy functional silane with respect to 100 parts by weight of colloidal silica. It is characterized by.
A coating composition according to claim 4 is characterized in that, in claim 1 or 2, the silicon-containing resin contains acryloxy functional silane or glycidoxy functional silane with respect to 100 parts by weight of colloidal silica. .
The coating composition according to claim 5 is characterized in that in any one of claims 1 to 4, the coating composition further contains a photoinitiator that accelerates curing of the silicon-containing resin.
The manufactured article of claim 6 is obtained by coating the silicon-containing resin coating composition of any one of claims 1 to 5 on the surface of a resin substrate.
The manufactured article of claim 7 is characterized in that, in claim 6, the manufactured article has a coating layer thickness of 1 to 10 microns.

  INDUSTRIAL APPLICABILITY The present invention can provide a cured silicon-containing resin coating composition having good adhesion to a base resin, and a manufactured article having a resin base surface coated with the composition.

  The silicon-containing resin coating composition of the present invention is applied as a silicon-containing resin composition in an uncured state on the surface of the resin substrate that is to be a protective mode, and then the silicon-containing resin coating composition is applied by brushing, spraying, or It is coated on the surface of a clean resin substrate by a suitable and well-known and commercially feasible process such as electrodeposition, and is cured by photochemical action irradiation such as ultraviolet (UV) light or particle irradiation such as electron beam. And an article having a silicon-containing resin coating layer.

The silicon-containing resin coating composition of the present invention includes the following components (A) to (D).
(A) Colloidal silica (SiO ₂ ): 100 parts by weight (about 294 parts by weight of Nalco 1034 dispersion)
Nalco 1034 is a dispersion of 34% by weight colloidal silica and 66% by weight water.

The Nalco 1034 dispersion is used in an amount sufficient to make 100 parts by weight of silica. As the colloidal silica, either a basic type or an acidic type can be used, but an acidic type having a low sodium content is preferably used.

(B) Acrylicoxy functional silane or glycidoxy functional silane: 5 to 500 parts by weight, preferably 50 to 200 parts by weight The acrylicoxy functional silane or glycidoxy functional silane serves to impart high abrasion resistance to the coating layer. However, it may be inferior in adhesiveness with the resin substrate by itself. Therefore, it is preferable to mix the following substances.

(C) Non-silyl acrylate material: 10 to 500 parts by weight, preferably 50 to 200 parts by weight Non-silyl acrylate material is added for the purpose of imparting adhesiveness to the silicon-containing resin coating composition. A particularly preferred acrylate material is water miscible hydroxy acrylate. Non-hydroxy acrylates can be used but are not preferred because of their low miscibility in water. The reason for requiring water miscibility is that it is useful as a viscosity reducing agent for coating compositions.

(D) UV sensitive photoinitiator:
As the photoinitiator, a radical type initiator can be used alone, but in order to improve the abrasion resistance of the silicon-containing resin coating layer, it is preferable to use a mixture of a radical type and a cationic type initiator. When acidic colloidal silica is used as the component A, it is preferable to use such a mixed photoinitiator. The radical initiator is used for curing the acrylicoxy functional part of the coating composition, and the cationic initiator cures the siloxane part. By combining the initiator in this way, the coating layer is hardened and wear resistance is also imparted.

  In the cationic photoinitiator, the amount of these photoinitiators is about 0.05 to 5.0% by weight, preferably 0.1 to 1.5%, based on the total amount of components A, B and C. It is preferable to set it as weight%. In a radical type photoinitiator, it is preferable to set it as about 0.5-5 weight% with respect to the total amount of component A, B, and C, Preferably it is about 1-3 weight%.

As described above, the silicon-containing resin coating composition is
It is prepared by mixing (A) colloidal silica, (B) acryloxy or glycidoxy functional silane, and (C) non-silyl acrylate. This mixture of (A) to (C) is catalyzed by combining it with an effective amount of an ultraviolet sensitive catalyst which is preferably a mixture of radical and cationic UV catalysts. The catalyzed composition is then coated onto the selected resin substrate by known techniques and cured by receiving UV radiation.

Component B is an acid hydrolyzate of acryloxy functional silane, a hydrolyzate of glycidoxy functional silane, or a mixture thereof.
Acrylicoxy functional silanes have the following general formula:

  In the formula, R3 and R4 are the same or different monovalent hydrocarbon radicals including halogenated species of these radicals. Preferably, R3 and R4 are lower alkyl radicals such as methyl, ethyl, propyl, but may include other saturated or unsaturated species including vinyl, aryl, and the like. R5 is a divalent hydrocarbon radical having 2 to 8 carbon atoms. R6 is hydrogen or a monovalent carbon hydrogen radical. The lowercase letter b is an integer from 1 to 3, c is an integer from 0 to 2, and d is an integer equal to the formula 4-bc. In embodiments of the invention, typically b = 3, c = 0, and d = 1.

Specific examples of the acryloxy functional silane include the following.
3-methacryloxypropyltrimethoxysilane 3-acryloxypropyltrimethyloxysilane 2-methacryloxyethyltrimethoxysilane 2-acryloxyethyltrimethyloxysilane 3-methacryloxypropyltriethoxysilane 3-acryloxypropyltriethoxy Silane 2-methacryloxyethyltriethoxysilane 2-acryloxyethyltriethoxysilane Such an acryloxy functional silane can be obtained from the following company.
For example, 3-methacryloxypropyltrimethoxysilane can be obtained from Union Carbide or United Chemical Technologies, Inc., USA.

  As component B of the coating composition, glycidoxy functional silane may be used instead of the acrylicoxy functional silane. Alternatively, a combination of both types of acryloxy functional silane and glycidoxy functional silane can also be used.

  The glycidoxy functional silane is represented by the general formula:

Wherein R7 and R9 are the same or different monovalent hydrocarbon radicals as described above for R3 and R4. R9 is a divalent hydrocarbon radical having 2 to 8 carbon atoms.
Lowercase letter e is an integer from 1 to 3, f is an integer from 0 to 2, and g is an integer equal to 4-ef. Specific examples that can be suitably used as the glycidoxy functional silane include the following.
3-glycidoxypropyltrimethoxysilane 2-glycidoxyethoxytrimethoxysilane 3-glycidoxypropyltriethoxysilane 2-glycidoxyethyltriethoxysilane These glycidoxy functional silanes are, for example, US Petratch Systems Available from Petrarch Systems.

  Component C becomes an acrylate compound that increases the abrasion resistance of the cured product when used with the colloidal silica. This acrylate compound is non-silyl functional and is distinguished from the above acryloxy functional silane. These acrylates are esters of acrylic acid, but it is preferable to use water-mixable hydroxyacrylates.

Preferred examples of the acrylate that can be used in the present invention include the following.
2-hydroxyethyl acrylate 2-hydroxy methacrylate 3-hydroxypropyl acrylate 3-hydroxypropyl methacrylate 2-hydroxy-3-methacryloxypropyl acrylate 2-hydroxy-3-acryloxypropyl acrylate 2-hydroxy-3-methacryloxypropyl methacrylate Acrylate Diethylene glycol diacrylate Triethylene glycol diarylate Tetraethylene glycol diacrylate Trimethiol propane triacrylate Tetrahydrofurfuryl methacrylate 1-6-hexanediol diacrylate

  A catalytic amount of component D photoinitiator is added to the mixture of (A) to (C). Effective photoinitiators include radiation sensitive aromatic halonium, sulfonium or phosphonium salts. Such a cationic photoinitiator can be represented by the following general formula:

  In the above formula, X is a radical selected from I, P, or S. M is a metal or metalloid and Q is a halogen radical selected from Cl, F, Br or I. R10 is hydrogen or a monovalent hydrocarbon radical having 1 to 12 carbon atoms. The lowercase letter h is an integer from 4 to 6, and n is an integer of 2 or 3.

  M, Q, and h are applied to a plurality of ion species, but are preferably selected from SbF6-, AsF4-, BF4-, and PF6-. Specific examples of cation catalysts include tetrafluoroborate, hexafluorophosphoric acid, hexafluoroarsenate and difluoroindonium salts of hexafluoroantimonate; and tetrafluoroborate, hexafluorophosphate, hexa Includes triphenylsulfonium salts of fluorophosphate, hexafluoroarsenate and hexafluoroantimonate.

  As a mixing ratio of the cationic photoinitiator, 0.1 to 1.5 parts by weight of the cationic photoinitiator is usually used for every 100 parts by weight of the mixture of the components A, B and C. Is preferred. However, depending on the individually desired desired process parameters, such as cure speed and ultimate abrasion resistance, the amount of photoinitiator can be about 0.05 to about 100 parts per 100 parts of component A, B and C mixture. It can be varied within the range of 5 parts by weight.

  These cationic photoinitiators are particularly useful for initiating cross-linking reactions upon exposure to ultraviolet radiation. Therefore, a good hard coating layer with excellent adhesion can be obtained by applying the coating composition to a resin substrate and exposing it to radiation as provided by a UV lamp.

  In addition, as the photoinitiator, a radical photoinitiator that is effective for crosslinking or self-polymerization of the acryloxy functional part of the silane contained in the coating composition can also be used. Radical type photoinitiators include benzoin ethers, alpha-acyloxime esters, acetophenone derivatives, benzyl ketals and ketone amine derivatives. Specific examples of radical photoinitiators include ethyl benzoin ether, isopropyl benzoin ether, dimethoxy-phenyl acetophenone and diethoxy acetophenone.

  The photoinitiator combination includes about 10 to 90% by weight of a cationic photoinitiator such as diphenylindonium hexafluoroarsenate, and the rest is a radical photoinitiator such as ethylbenzoin ether. You can also

  It is effectively catalyzed by making a silicon-containing resin coating composition in which about 0.5 to 5.0 parts by weight of a photoinitiator is mixed with respect to 100 parts by weight of a mixture of the above components A, B and C. A hard coating layer sufficient for coating a resin substrate is formed.

(Resin substrate)
As the resin substrate to be coated with the silicon-containing resin coating composition of the present invention, the type of the resin is not particularly specified, and among them, acrylic, polycarbonate, polyethylene, polypropylene, vinyl chloride, nylon, epoxy, etc. Preferably used.

Next, the following are illustrated as an example of a silicon content resin coating composition.
(Example 1)
In a 500 cc three-necked flask, 175 g of Nalco 1034A colloidal silica dispersion (about 59.5 g, silica, component A) was added. Next, 47 g of methacryloxypropyltrimethoxysiloxane (MPTMS. Component B) (Petrac Systems, USA) was added over 20 minutes and added dropwise at 25 ° C. After a further 40 minutes of mixing, a mixture of 68 g 2-hydroxyethyl acrylate and 25 g diethylene glycol diacrylate (component C) was added.
Next, 1 g of diphenyliodohexafluoroarsenate and 2.5 g of ethylbenzocin, both of which are photoinitiators, were blended into the slightly cloudy solution (component D).
This catalyst mixture is coated on a polycarbonate plate and air-dried for 40 minutes.
It was cured under ultraviolet light for 6 seconds under nitrogen to obtain a transparent hard coating layer having good adhesion.

(Example 2)
To 750 g of colloidal silica (Nalco 1034A. Component A), 118 g of 3-methacryloxypropyltrimethoxysilane (MPTMS) (A-174, manufactured by Union Carbide) was added at 25 ° C. After stirring for 15 minutes, 240 g of 3-glycidoxypropyltrimethoxysilane (GPTMS) (manufactured by Petrac System) was added dropwise over 30 minutes while keeping the temperature at 30 ° C. or less (component B). .
Next, this mixed liquid was stirred at 25 ° C. for 1 hour, and 300 g of 2-hydroxyethyl acrylate, 88 g of diethylene glycol diacrylate, 88 g of tetrahydrofurfuryl methacrylate (component C), 4.4 g of bis-tolyl iodonium hexa Mixed with fluoroarsenate and 1.5 g ethyl benzoin ether (component D).
The composition was then coated on an acrylic plate and cured under ultraviolet light for 3 seconds to obtain a transparent coating layer having good abrasion resistance.

(Example 3)
A mixture of 45 g MPTMS (A-174) and 10 g OPTMS (A-187) (component B) was added to 150 g Nalco 1034A (component A) at 25 ° C. over 30 minutes. After mixing for 4 hours, excess water and endogenous solvent were removed under reduced pressure.
Next, the thick residue was 100 g 2-hydroxy-3-methacryloxypropyl acrylate (HMPA), 40 g diethylene glycol diacrylate (component C), 1.2 g triphenylsulfonium hexafluoroarsenate and 4 g Mixed with ethoxyacetophenone (DEAP) (component D). This was coated on polycarbonate and cured by irradiation with ultraviolet light for 9 seconds in a nitrogen atmosphere.

Example 4
To 300 g of colloidal silica (Nalco 1034A, component A), 90 g of 3-acryloxypropyltrimethoxysilane, followed by 20 g of 3-glycidoxypropyltriethoxysilane, at 20 ° C. (component) B). Further, after stirring for 30 minutes, excess water was removed under reduced pressure. The clear residue was mixed with 40 g 2-hydroxy-3-methacryloxypropyl acrylate (HMPA) and 40 g diethylene glycol diacrylate (DEGDA) (component C).
Then, under nitrogen, in the presence of catalytic amounts of triphenylsulfonium-hexafluoroarsenate and diethoxyacetophenone (component D), UV light was irradiated on the polycarbonate for 6 seconds to cure.

(Example 5)
A mixture of 150 g of colloidal silica (Nalco 1034A. Component A) and 45 g of 3-methacryloxypropyltriethoxysilane (Component B) was mixed at 25 ° C. for 2 hours.
Next, 20 g of HMPA and 20 g of DEGDA were added (component C), and 0.6 g of tri-phenylsulfonium hexafluoroarsenate and 1 g of diethoxyacetophenone were added (component D).
Next, this was coated on an acrylic plate and drained for 30 minutes.
As a result of ultraviolet light irradiation under nitrogen for 10 seconds, a transparent high abrasion resistant coating layer having good adhesion was obtained.

(Example 6)
30% of colloidal silica (Nalco 1129. Component A), 2-hydroxyethyl methacrylate (HEMA. Component C) and 3-glycidoxypropyltriethoxysilane (GPTMS. Component B) in the weight indicated in the table below. Three types of hard coating compositions were obtained by mixing at a ratio. Each of these three types of silicone resin coating compositions includes 0.04 parts diphenyliodonium hexafluoroarsenate and 0.04 parts ethylbenzoin ether as a proportion based on the total mixture weight. The mixture (component D) was added. The catalyzed composition was flow coated onto an acrylic plate and air dried for 30 minutes. After the coated acrylic plates were air-dried, they were irradiated with ultraviolet light for 3 seconds to obtain a cured coating layer.

(Example 7)
Another silicon-containing resin coating composition was made by mixing 2 parts by weight of colloidal silica (Nalco 1034A, component A) and 1 part of water. To this mixed solution, 1 part of 3-methacryloxypropyltriethoxysilane (component B) was added dropwise at 25 ° C. After stirring for 2 hours, the resulting mixture was further mixed with 2 parts 2-hydroxyethyl acrylate (component C), 0.15 parts dephenyliodonium hexafluoroarsenic and 0.3 parts ethyl benzoin ether (components). D) was added. The catalyzed mixture was coated on an acrylic plate and air dried for 30 minutes to cure the coating layer by UV irradiation. Multiple samples were all cured to a high abrasion resistant coating layer that exhibited good adhesion. All the samples were cured by ultraviolet irradiation for 6 to 9 seconds, and Δ% H500 was 4 to 7.

The silicon-containing resin coating composition of the present invention essentially removes volatile components from a silicon-containing polyacrylate mixture containing the following components at a temperature of 25 to 100 ° C. and a pressure of 1 to 760 torr. Can also be made.
(E) (i) about 5 wt% to about 20 wt% alkoxysilyl acrylate,
And (ii) C (3-5) branched aliphatic alcohol, or colloidal silica substantially composed of a mixture of C (3-5) branched aliphatic alcohol and C (1-5) linear alcohol A mixture of about 80 wt% to about 95 wt% colloidal silica alcohol dispersion, as described above, wherein the colloidal silica is present in the colloidal silica alcohol dispersion from about 5 wt% to about 70 wt%. 100 parts by weight of reaction product at a temperature of about 20 ° C. to about 100 ° C.
(F) from about 10 to about 400 parts by weight of at least one multifunctional reactive acrylic monomer;
And (G) an effective amount of a gelation inhibitor in which sufficient water is present in the colloidal silica alcohol dispersion to affect hydrolysis of the alkoxyl acrylate.

  Examples of the C (3-5) branched water-miscible alcohol include isopropanol, isobutanol, t-butanol and neopentanol.

  The gelation inhibitor includes aerobic and anaerobic gelation inhibitors. A preferred aerobic gelation inhibitor is methylhydroquinone.

  Examples of anaerobic gelation inhibitors that can be used include 2,2,6,6-teraxamethylpipeaidinyloxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy ( 4-OH TEMPO), galvinoxyl, 2,2-d / phenyl-1-picryl-hydrazyl hydrate, vanfield radical, 1,3,5-triphenylveradadyl, Loelsch's radical 1-nitroso 2-naphthol and bis (2,2,6,6-tetramethyl-4-piperidinyloxy) sebacate.

  The effective amount of the aerobic or anaerobic gelation inhibitor is preferably 10 ppm to 10,000 ppm based on the weight of the reactive acrylic monomer used in the curable silicone containing the polyacrylate hardcoat composition. As mentioned.

  Some of the above alkoxysilyl acrylates are represented by the following formula:

  Wherein R4 is a C (1-3) monovalent organic radical, R5 is a C (1-8) alkyl radical, R6 is selected from hydrogen, an R4 radical or mixtures thereof, and R7 is a divalent C (1- 8) An alkylene radical, a is a natural number of 0 to 2, b is an integer from 1 to 3, and the total a + b is 1 to 3. Alkoxysilyl acrylates include compounds of the following formula:

  Examples of the polyfunctional reactive acrylic monomer include compounds represented by the following formula.

  In the formula, R6 is the same as defined above. R8 is a polyvalent organic radical, and n is an integer having a value of 2-4.

  Some of the reactive acrylic monomers that can be used include, for example:

Silicon ester acrylate oligomer of the following formula (EBECRYL 350, manufactured by UCB Radcure) Aliphatic urethane diacrylate triacrylate:

Tetraacrylate of the formula:

  Other arelates having at least 3 or more reactive groups include dipentaerythritol monohydroxypentaacrylate, hexafunctional polyurethane acrylate, and silicon acrylate oligomer (Ebecryl 1360, manufactured by UCB Radicure).

The coating composition can include one or more multifunctional reactive acrylic monomers. Preferably, a mixture of two multifunctional reactive acrylic monomers, in particular diacrylate and triacrylate, is used. Furthermore, a trace amount of monoacrylate can be used. The coating composition is UV curable or electron beam curable.
These compositions can include up to 50% by weight of the non-acrylic UV curable unsaturated organic monomer of the UV curable hard coating composition. For example, such materials include N-vinyl pyrrolidone, styrene and the like.

When the coating composition comprises a mixture of acrylic monomers, the weight ratio of the diacrylate to polyfunctional acrylate, such as trifunctional acrylate, can be from about 10/90 to about 0/10. preferable.
Usable diacrylate and triacrylate mixtures include
A mixture of hexanediol diacrylate and pentaerythritol triacrylate, a mixture of hexanediol diacrylate and trim-ethylol propane triacrylate, a mixture of diethylene glycol diacrylate and pentaerythritol triacrylate, and diethylene glycol diacrylate and trimethylol propane triacrylate A mixture of acrylates is included.

  The coating composition contains an ultraviolet reaction product of one polyfunctional acrylic monomer, but the coating containing a photoreactive product of two polyfunctional acrylic monomers is a product of diacrylate and triacrylate Is preferred.

  The coating composition can also include a photosensitizing amount of photoinitiator, i.e., an amount of photoinitiator effective to affect the photocuring of the coating composition in air or in an inert atmosphere, such as a nitrogen atmosphere. . Generally this amount is from about 0.01% to about 10% by weight of the photocurable coating composition, preferably from about 0.1% to about 5%.

Examples of photoinitiators that can be preferably used in a non-oxidizing atmosphere such as nitrogen include the following.
Benzophenone and other acetophenones, benzyl, benzaldehyde and O-chlorobenzaldehyde, xanthone, thioxanthone, 2-chlorothioxanthone, 9,10-phenanthrenenequinone, 9,10-anthraquinone, methyl benzoin ether, ethyl benzoin ether, isopropyl benzoin Ether, 1-hydroxycyclohexyl phenyl ketone, α, α-diethoxyacetophenone, α, α-dimethoxyacetophenone, 1-phenyl-1,2-propanediol-2-o-benzoyloxime, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide and α, α-dimethoxy-α-phenylacetophenone.

  The coating composition can include UV absorbers or stabilizers such as resorcinol monobenzoate, 2-methylresorcinol dibenzoate. Further, other UV absorbers include benzophenone, benzotriazole, cyanoacrylate and triazine. Stabilizers comprising hindered amines can be present from about 0.1 to 15% by weight, preferably from about 3 to about 15% by weight, based on the weight of the coating composition excluding any additional solvent present.

  The coating composition of the present invention can also contain various matting agents, surfactants, surface wear resistance agents, thixotropic agents and the like. Surfactants can also include anionic, cationic and nonionic surfactants.

(Example 8)
A mixture of 99 g of colloidal silica in pH 3-5 isopropyl alcohol containing 30% SiO ₂ , 13 g methylacryloxypropyltrimethoxysilane and 0.2 g galvin oxyl was stirred at 60-70 ° C. for 2 hours. Heat. After heating, 36.2 g of hexanediol diacrylate is added and the mixture is stripped with nitrogen bleed under vacuum (30 torr). As a result, 76 parts by weight of radiation curable purple oil having a viscosity of 56.5 cps was prepared.

  A blend of 10 g of purple oil, 10 g of trimethylolpropane triacrylate, 1.2 g of Vicure (registered trademark) 55 methylbenzoyl formate ester from Akzo Chemical Co, and 30 g of isopropanol is placed on a polycarbonate substrate as a resin substrate. Flow coated and UV cured at 20 ft / min in air. A friction test in which the cured coating layer was rubbed with steel wool also showed abrasion resistance with no scratches and a yellowness index of 0.8.

The above procedure was repeated except that 99 g of a colloidal methanol mixture containing 30% by weight of SiO ₂ , 13 g of methylacryloxypropyltrimethoxysilane, and 0.2 g of galvinoxyl was heated at 65 ° C. for 1 hour. Repeated. Next, 36.2 g of hexanediol diacrylate was added and the solution was stripped, resulting in a yellow gel.

  The above procedure was repeated using a colloidal silica methanol mixture, except that 30% by weight of isopropanol was added prior to stripping. A radiation-cured oil having a viscosity of 146 cps was obtained.

Example 9
A mixture consisting of 520 g of IPAST made by Nissan Chemical Co., Ltd. (low pH mixture of 156 g of SiO ₂ isopropanol solution containing about 14.9 g of water), 68.3 g of methylacryloxypropyltrimethoxysilane and 0.75 g of 4-OH TEMPO , 83 ° C., 3 hours, and then cooled to room temperature. Next, 183.1 g of hexanediol acrylate was added. The mixture was stripped at room temperature for 30 torr for 1 hour while blowing nitrogen through the mixture. After stripping for 1 hour, the pot temperature was raised to 63 ° C. to obtain 412.2 g of 41 radiation curable oil having a viscosity of 53 centipoise.

  The pretreatment before coating does not require a solvent resin or primer, and a known spray, dipping, flooring, spin coating or the like is applied as a method for coating the resin substrate with the silicon-containing resin coating composition. The The thickness of the coating layer is preferably adjusted so that the thickness after photocuring has a thickness of about 1 micron to about 10 microns.

In addition, an alcohol dispersion having 25 carbon atoms of an alkoxysilyl acrylate such as 3-methacryloxypropyltrimethoxysilane (product M8550-KG manufactured by United Chemical Technology Co., Ltd.) and colloidal silica such as isopropyl alcohol. Simple mixtures can also be used.
Further, when 1 volume of about 30% by weight of isopropyl alcohol dispersion of colloidal silica (IPA-ST manufactured by Nissan Chemical Co., Ltd.) and 1-4 volumes of M8850-KG are mixed well for about 1 minute, a base coat of cured polyurethane or When applied to a polyurethane / acrylic mixture, a good silicon-containing resin coating layer can be obtained.

  From the cross-sectional observation of the coating layer with a scanning electron microscope, it was observed that most of the colloidal silica was concentrated in a region within 1 to 2 microns of the coating layer.

When applied to a resin substrate as described above, the coating composition of the present invention provides a manufactured article in which a coating layer having excellent bonding and resistance to corrosion, abrasion, and the like is formed.
For example, a general marking agent widely used for spraying exposed surfaces by mischief can be easily removed by simply rubbing the surface of the object with steel wool, thereby removing the surface of the cured silicone resin top coat. You can drop the spray without damaging it.

The present invention can provide a cured silicon-containing resin coating layer having good adhesiveness on a resin substrate, and can provide a manufactured article obtained by coating a general resin substrate such as acrylic, polycarbonate, and polyethylene with a cured silicon-containing resin coating layer. It can be used and its industrial utility value is extremely high.

Claims (7)

A silicon-containing resin coating composition for coating a resin substrate. The coating composition according to claim 1, wherein the silicon-containing resin coating composition comprises a condensation product of colloidal silica and a silyl acrylate represented by the following formula.

Wherein R4 is a C (1-13) monovalent organic group, R5 is a C (1-8) alkyl group, R6 is selected from hydrogen, R4 groups or combinations thereof, and R7 is 2 A valence C (1-8) alkylene group, a is a natural number of 0-2, b is an integer of 1-3, and a + b is 1-3.) The silicon-containing resin is 100 parts by weight of colloidal silica.
The coating composition according to claim 1 or 2, comprising 5 to 500 parts by weight of an acryloxy functional silane or a glycidoxy functional silane. The silicon-containing resin is 100 parts by weight of colloidal silica.
The coating composition of Claim 1 or 2 containing an acryloxy functional silane or a glycidoxy functional silane. The coating composition according to claim 1, wherein the coating composition further comprises a photoinitiator that accelerates curing of the silicon-containing resin. A manufactured article obtained by coating the silicon-containing resin coating composition of any one of claims 1 to 5 on the surface of a resin substrate. The manufactured article according to claim 6, wherein the coating layer has a thickness of 1 to 10 microns.