JP2599452B2 - Primer composition and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a primer composition, in particular, an adhesive to the surface of a thermoplastic molded article such as polycarbonate.
The present invention relates to a primer composition for forming a silicone-based wear-resistant coating having excellent durability and a method of using the same.

(Prior art) Thermoplastics, especially polycarbonate resins, are widely used as structural materials instead of glass because of their excellent transparency, light weight and excellent impact resistance. Due to poor abrasion resistance, solvent resistance and weather resistance, the surface is easily scratched, easily susceptible to organic solvents, and colored and deteriorated with aging.

For this reason, it has been proposed to coat the surface of this molded article with a thermosetting resin, and among these, those coated with an organopolysiloxane have excellent wear resistance and solvent resistance. Therefore, organopolysiloxane is considered to be useful, but coating with this organopolysiloxane-based coating film has insufficient uniform adhesion to thermoplastic resin surfaces such as polycarbonate resin and insufficient weather resistance on the surface. For this reason, attempts have been made to use this resin in combination with other resins. For this resin, 1) a thermoplastic acrylic primer (see
2) Acrylic resin primer having a functional group such as an amino group (see JP-A-53-138476); 3) an alkoxysilane having a functional group such as an amino group or a hydroxy group; Silicone primer comprising a reaction product with a cyclic acid anhydride (JP-A-53-81533)
4) Silicone primer comprising a mixture of a hydrolyzate of epoxysilane and aminosilane (see JP-A-54-63176); 5) A functional group-containing thermoplastic acrylic resin and an ultraviolet absorber Acrylic primer (see Japanese Patent Publication No. 55-500809), 6) Acrylic primer comprising a thermosetting acrylic emulsion and an ultraviolet shielding compound (see Japanese Patent Application Laid-Open No. 55-160033), 7) aminosilane, epoxy Silicone primer composed of a reaction product of silane and acid anhydride (JP-A-56
No. 16573), 8) a thermoplastic acrylic primer comprising a reaction product of an acrylic monomer with epoxy methacrylate and a hydroxybenzophenone ultraviolet absorber (see JP-A-57-23661), 9) alkoxysilyl Colloidal silica-containing organopolysiloxane-based coatings containing a functional aromatic ultraviolet absorber are known.

However, the combined use with these resins does not always give a satisfactory effect. For example, in the above cases 1) and 2), although the adhesiveness to the substrate is considerably improved, active hydrogen groups such as amino groups are used. In the presence of a compound containing water, there is a disadvantage that the water resistance is deteriorated due to the absorption of moisture from that part, and the weather resistance is hardly improved. However, if active hydrogen groups remain, the water-resistant adhesiveness becomes insufficient, and because it contains an amino group, it is liable to turn yellow, and the weather resistance may be rather poor.In addition, OH groups, -COOH Since it contains a group, it easily reacts with an alkoxy group, so that the primer solution thickens with the passage of time and becomes difficult to apply, and there is a disadvantage that the adhesion decreases due to an increase in the degree of polymerization. In the case of 5), the weather resistance is considerably improved, but it is still insufficient for long-term weather resistance. If the coating is made thick to improve the weather resistance, the other abrasion-resistant polyorganopolysiloxane coating film becomes soft. However, increasing the amount of the UV absorber results in whitening of the coating or poor adhesion, and 6) is an emulsion, which is an emulsion, and thus has a disadvantage in terms of solubility in water. The type of agent is limited, so it is not possible to select an effective UV absorber,
The improvement in weather resistance does not reach a satisfactory level, and the adhesiveness tends to be poor because the acrylic resin is thermosetting. Note that 7) has the same disadvantages as 3) and 4) described above, and 8) is difficult to produce an acrylic polymer containing a large amount of the ultraviolet absorber because it becomes a kind of radical stabilizer in 8). Therefore, there is a disadvantage that the improvement of the weather resistance and the adhesion becomes insufficient, and also in the case of 9), the weather resistance is improved but the adhesion is not good.

In addition, in order to improve the weather resistance in particular, it is necessary to include a large amount of an ultraviolet absorber in the primer, but the conventional primer has a drawback that when a large amount of the ultraviolet absorber is included, the transparency is deteriorated. . Therefore, the present inventors have previously added 2- (2 ′) to the silicone-based primer composition.
-Hydroxy-3 ', 5'-di-t-amylphenyl)
It has been proposed to improve the weather resistance by including benzotriazole as an ultraviolet absorber (Japanese Patent Application Laid-Open No. Sho 62).
However, when this ultraviolet absorber is added to a silicone-based primer composition at 30% by weight or more and stored for a long period of time, there is a disadvantage that the ultraviolet absorber is precipitated.

(Constitution of the Invention) The present invention relates to a primer composition which solves such disadvantages and a method for using the same, and the composition comprises A)
10 to 80% by weight of an organic copolymer of an acrylic and / or vinyl monomer containing 2 to 50% by weight of an alkoxysilyl group and another monomer copolymerizable with these monomers;
B) 0 to 30% by weight of an acrylic polymer; C) a reaction product of an amino-functional alkoxysilane with an epoxy-functional alkoxysilane and a silylating agent is converted into an acid halide, acid anhydride or acid isopropenyl ester of a carboxylic acid. A silicone-based primer composition comprising 5 to 30% by weight of a reactant amidated by reacting with a compound and 15 to 35% by weight of 2- (2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, and its use is characterized in that after treating a plastic substrate with this composition, a colloidal silica-containing organopolysiloxane composition is applied and the coating is cured. Things.

That is, the present inventors have conducted various studies on the improvement of the primer composition for improving the adhesion and weather resistance of a thermoplastic resin molded article such as polycarbonate when coating an organopolysiloxane-based coating film. When 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole is added to the silicone primer composition having the above composition, this composition has no change with time and has no adhesive property and weather resistance. Since this product has an excellent improvement effect, it is applied to a plastic molded product, cured, and then coated with an organopolysiloxane-based wear-resistant coating containing colloidal silica. The primer composition was found to have excellent properties and no yellowing. The type of each component that, to complete the present invention investigated the for such composition ratio.

In the present invention, the silicone-based primer composition that constitutes the primer composition is an acrylic and / or vinyl-based monomer containing an alkoxysilyl group and another monomer as described above that can be copolymerized with these monomers. And an organic copolymer of the above as a main component. In addition, regarding this organic copolymer, since the primer composition of the present invention forms a silicone-based abrasion-resistant film on a molded article of a thermoplastic plastic such as polycarbonate in particular, this organic copolymer is used. Containing 2 to 50% by weight of an alkoxysilyl group-containing monomer as component A), the following acrylic polymer as component B), and amino-functional alkoxysilane and epoxy-functional alkoxy as component C). It is assumed that a product obtained by amidating a reaction product with a silane and a silylating agent is blended.

This organic copolymer is a copolymer of an acrylic and / or vinyl monomer containing an alkoxysilyl group and another monomer copolymerizable with these monomers.
The acrylic monomer containing the alkoxysilyl group has a general formula Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, an alkyl group such as a propyl group, a vinyl group, an alkenyl group such as an allyl group, an aryl group such as a phenyl group having 1 to 1 carbon atoms. 6 monovalent carbon hydrogen groups, a is 1 to
3, b is 0 or 1, which includes 3 methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltributoxysilane, 3-methacryloxypropyltriisopropenoxysilane. , Methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltributoxysilane, 3-
Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltributoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyltributoxysilane, 3-methacryloxy Propylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldibutoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethylmethyldibutoxysilane, 3 Acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldibutoxysilane, Examples thereof include riloxymethylmethyldimethoxysilane, acryloxymethylmethyldiethoxysilane, and acryloxymethylmethyldibutoxysilane. Among them, 3-methacryloxypropyltrisilane is used because of its ease of handling, crosslink density, and reactivity. Methoxysilane and 3-methacryloxypropylmethyldimethoxysilane are preferred.

The vinyl monomer containing the alkoxysilyl group has a general formula Wherein R ³ is a monovalent hydrocarbon group or alkyloxyalkyl group having 1 to 6 carbon atoms of the same kind as R ² , c is a vinyl functional alkoxysilane having 0 or 1, or a general formula Where R ³ is the same as above and d is 0 or 1 is a vinyl-functional alkoxysilane. These include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldibutoxysilane, vinylmethylbis (2- Methoxyethoxy) silane, 3-vinyloxypropyltrimethoxysilane, 3-
Vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyloxypropylmethyldiethoxysilane, 3-vinyloxypropylmethyldibutoxysilane, and the like are exemplified. From the viewpoint of reactivity, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinyloxypropyltrimethoxysilane are preferred.

Next, as other monomers copolymerizable with these alkoxysilanes, alkyl methacrylates such as methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, methyl acrylate,
Alkyl acrylates such as ethyl acrylate and butyl acrylate, glycidyl methacrylate, acrylamide, acrylonitrile, vinyl acetate, vinyl ethers such as ethyl vinyl ether, butyl vinyl ether and hexyl vinyl ether, styrene, ethylene glycol dimethacrylate, etc. are exemplified.Alkoxysilyl For example, 2-hydroxyethyl methacrylate, which can react with a group, is not preferred because a primer composition made therefrom causes a change with time such as thickening and gel purchase.

This organic copolymer is a copolymer of the above-mentioned alkyloxysilyl group-containing monomer and another monomer copolymerizable therewith, and this copolymer is obtained by converting these monomers. A radical polymerization catalyst selected from peroxides such as dicumyl peroxide and benzoyl peroxide or azo compounds such as azobisisobutyronitrile is added to the contained solution and easily obtained by reacting under heating. However, in this organic copolymer, when the content of the monomer containing an alkoxysilyl group is 2% by weight or less, the formed film is not thermosetting, so that a large amount of a light stabilizer can be immobilized. If this is not possible, and if it is contained in an amount of 50% by weight or more, the resulting primer layer will be too hard and the adhesion will be greatly reduced. It is necessary to do.

In addition, the weight percentage of the organic copolymer in the primer composition is less than 10% by weight in the primer composition, which becomes thermoplastic and lowers the heat resistance, and when it is more than 80% by weight, the adhesion becomes poor. Although it is necessary to be 10 to 80% by weight, this preferable range may be 20 to 80% by weight.

Further, the acrylic polymer as the component B) added to the organic copolymer includes poly (alkyl methacrylate) such as poly (methyl methacrylate), poly (butyl methacrylate), and poly (butyl acrylate);
Examples thereof include poly (alkyl acrylate) and copolymers thereof, which increase the viscosity of the primer solution without lowering the adhesiveness. Since it acts as a thickening agent with a certain viscosity, it is prevented that the viscosity of the primer solution is too low, so that the coating film when applied is too thin to contain a large amount of the light stabilizer. . This addition is optional, and it is not necessary to add the organic copolymer as component A) as long as the organic copolymer has a sufficiently high viscosity. Since the addition of the above deteriorates the thermosetting property of the composition, the addition needs to be 30% by weight or less.

The product obtained by amidating the reaction product of the amino-functional alkoxysilane, the epoxy-functional alkoxysilane, and the silylating agent as the component C) added to the organic copolymer is water-resistant to the primer composition. In addition to imparting good adhesiveness and crosslinking with the component A) by the alkoxysilyl group, 2)
-(2'-hydroxy-5'-t-butylphenyl) benzotriazole is immobilized in the membrane.

The amino-functional alkoxysilanes used herein include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (4-aminobutyl) -3-aminopropyltrimethoxysilane, N-
(4-aminobutyl) -3-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) -3-aminopropylmethyldimethoxysilane,
Examples thereof include N- (2-aminoethyl) aminomethylstyryltrimethoxysilane and N- (2-aminoethyl) -aminomethylstyrylmethyldimethoxysilane. − (2-
Aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane are preferred.

The epoxy-functional alkoxysila used herein includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3
-Glycidoxypropylmethyldiethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 7,8-epoxyoctyltrimethoxysilane,
Examples thereof include 9,10-epoxydecyltrimethoxysilane. Among these, 3- and 3-epoxydecyltrimethoxysilane are preferred in view of reactivity and operability.
Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyldimethoxysilane is preferred.

Examples of the silylating agent used here include hexamethyldisilazane, N, N-bis (trimethylsilyl) formamide, N, N'-bis (trimethylsilyl) urea, and the like. The reaction between the alkoxysilane and the epoxy-functional alkoxysilyl group protects the generated OH group and prevents the reaction between the OH group and the alkoxysilyl group, thereby preventing the reaction product from changing over time.

The reaction of the amino-functional alkoxysilane with the epoxy-functional alkoxysilane and the silylating agent may be carried out by dropping the epoxy-functional alkoxysilane into a mixture of the amino-functional alkoxysilane and the silylating agent, and performing a heating reaction. May react an amino-functional alkoxysilane with an epoxy-functional alkoxysilane, and add a silylating agent to the reaction product to cause a reaction.
In this reaction, if the molar ratio of epoxy group / amino group is less than 0.3, the number of alkoxy groups involved in crosslinking in one molecule is too small, and the curability of amino-functional alkoxysilane and epoxy-functional alkoxysilane is too small. Is weakened, the whole molecule is not spread, the surface adhesiveness is weakened, and the adhesiveness is deteriorated. When it becomes 1.2 or more, it can be amidated in amidation described later = N-H group almost disappears and water resistant adhesion Therefore, it is preferable to be in the range of 0.3 to 1.2.

The reaction product was then assumed to be amidated, and this amidation was performed in acetic chloride, bromide acetate,
Propionic acid chloride, acetic chloride, acetic anhydride, an acid halide of a carboxylic acid exemplified by isopropenyl acetate, etc., may be reacted with an acid anhydride, acid isopropenyl ester compound, the reactant thus obtained If the amount of the organic copolymer added to the organic copolymer is less than 5% by weight, the adhesion to the substrate becomes insufficient. 5
It is required to be in the range of ~ 30% by weight.

Next, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole added to the silicone-based primer composition is used for protecting the plastic substrate and the primer layer applied thereto from light. A known light stabilizer widely used in this type of application, for example, a salicylic acid-based ultraviolet absorber such as phenyl salicylate, hydroxybenzophenone,
Benzophenone-based ultraviolet absorbers such as -hydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
Benzotriazole-based ultraviolet absorbers such as (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2-methylhexyl-2-cyano-3,3'
-Diphenyl acrylate, ethyl-2-cyan-3,
A cyanoacrylate-based ultraviolet absorber such as 3'-diphenyl acrylate can be added in a small amount but precipitates when added in a large amount. However, as the light stabilizer, the above-mentioned 2- (2'-hydroxy-5'-t-
If (butylphenyl) benzotriazole is particularly selectively used, a large amount can be added. This is based on the present inventors' confirmation that the light stabilizing effect is large.

In addition, if the addition amount of this in the primer composition of the present invention is less than 15% by weight, good weather resistance is not given to the target plastic molded product, and if it exceeds 35% by weight, this is trapped in the primer film. If the amount is more than the above amount, appearance defects such as whitening may occur or adhesion may be poor. Therefore, it is necessary to set the amount to 15 to 35% by weight.

The primer composition of the present invention is obtained by adding the above-mentioned 2- (2′-hydroxy-
Although it can be obtained by mixing a predetermined amount of (5'-t-butylphenyl) benzotriazole, the treatment of a plastic substrate with this primer composition is carried out on the surface of a plastic film, substrate or the like which has been previously cleaned. Organic solvent diluent such as methanol, ethanol, isobutanol, ethoxyethanol, alcohols such as diacetone alcohol, methyl ethyl ketone, ketones such as methyl isobutyl ketone, ethyl acetate, esters such as isobutyl acetate, Aromatic compounds such as toluene and the like, and a solution diluted with a mixed solvent thereof are applied, and the organic solvent is evaporated at room temperature or under heating to a thickness of 1 to 10 μm,
Preferably, a coating film having a thickness of 2 to 5 μm may be formed. In addition, this organic solvent diluent has a viscosity of 5 cS or less, the coating film cannot be thickened, and if it is 30 cS or more, it becomes difficult to handle and apply the coating solution. It is optional to add a fluorine-based or silicone-based surfactant to smooth the coating film, and to promote the curing of the coating film, a crosslinking curing catalyst containing an alkoxysilyl group is added thereto. The addition is optional.

The plastic film provided with the cured film of the primer composition of the present invention thus obtained, a plastic molded article such as a substrate has excellent initial adhesiveness, heat resistance, hot water resistance, and weather resistance. the ones known colloidal silica-laden organopolysiloxane composition onto the primer coat, shown, for example, by the general formula _{^{R 5 m Si (OR 6)}} 4-m, R 5 is a monovalent hydrocarbon having 1 to 6 carbon atoms A hydrogen group or an alkyloxyalkyl group, m is 0.1 or 2 alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyltrimethoxysilane, Ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane Emissions, dimethyl diethoxy silane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane,
Hydrolysates or co-hydrolysates such as tetrabutoxysilane and tetrakis (2-methoxyethoxy) silane,
When coated with 10 to 80% by weight of colloidal silica obtained by dispersing silica fine particles of 1 to 100 mμ in water or an alcohol such as methanol, ethanol, isobutanol, diacetone alcohol, and then heat-cured to 50 to 140 ° C. Since the surface of the plastic molded product is coated with the primer composition of the present invention, the primer coating and the organopolysiloxane have excellent adhesion, durability and abrasion resistance due to the synergistic action of the organopolysiloxane. The advantage is given.

Next, examples of the present invention will be described. In the examples, parts and% indicate parts by weight and% by weight, and the performance evaluation of the coating film obtained in this example shows the measurement results by the following methods. It is a thing.

(Abrasion resistance)

Using a Taber abrasion tester, 500g load, abrasive paper CS
After 100 rotations at -10, the haze (%) was measured with a haze meter, and 5% or less was regarded as good.

[Hardness] A pencil hardness test was performed according to JIS K5,400, paragraph 6.14.

〔Adhesiveness〕

A cross cut (10 × 10) tape peeling test was performed, and the state of complete adhesion was represented by 100/100.

〔Heat-resistant〕

After heating at 100 ° C. for 100 hours, the appearance, hardness and adhesiveness were measured, and those having no change were judged as “no abnormality”.

(Warm water resistance)

After immersion in hot water of 75 ° C for 100 hours, the appearance, hardness, and adhesiveness were measured.
It was determined.

〔Weatherability〕

The time until the coating film peeled off and the hardness was reduced was measured with a Sunshine Weatherometer and UVCON (manufactured by Atlas, USA).

Synthesis Examples 1-4, Comparative Synthesis Example 1 Synthesis of Component (A)] γ-methacryloxypropyltrimethoxysilane KB
M503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or vinyltrimethoxysilane / KBM1003 (trade name, manufactured by the company), and methyl methacrylate, ethyl acrylate, vinyl acetate, glycidyl methacrylate as monomers copolymerizable therewith Ethylene glycol dimethacrylate and azobisisobutyronitrile (hereinafter AIBN) as polymerization catalyst
) And diacetone alcohol as a solvent in the amounts shown in Table 1 and charged into a 500 ml separable flask with a Dimroth condenser.
After heating and stirring at 80 to 90 ° C. for 5 hours under a nitrogen stream, an organic copolymer having the viscosity as shown in Table 1 and the monomer content containing an alkoxysilyl group (No.
V) was obtained.

Synthesis Example 5 Synthesis of Component (C)] 222 g of N-β (aminoethyl) -γ-aminopropyltrimethoxysilane / KBM603 (trade name of Shin-Etsu Chemical Co., Ltd.) was placed in a two-separable flask equipped with a Dimroth condenser. And 242 g of hexamethyldisilazane as a silylating agent were charged and heated to 120 ° C. under a nitrogen stream, and γ-glycidoxypropylmethyldiethoxysilane.KB
E402 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise and reacted, and the mixture was heated and stirred at 120 ° C. for 5 hours, and then the low-boiling components were removed at 100 ° C. under reduced pressure to obtain a viscosity of 1,387 cS and a refractive index of 1 .
862 g of a viscous compound having a specific gravity of 1.048 and 4618 was obtained.

Then, 862 g of the reaction product and 862 g of toluene were charged into a 2-separable flask equipped with a Dimroth condenser, and 141 g of acetic anhydride was added dropwise thereto at room temperature under a nitrogen stream to cause a reaction, followed by heating and stirring at 110 ° C. for 2 hours. Then, 141 g of methanol was added dropwise at 50 ° C., and the mixture was stirred while heating at 50 ° C. for 1 hour, and then the low-boiling components were removed at 100 ° C. under reduced pressure to obtain an extremely viscous compound.

When the infrared absorption spectrum of this reaction product was measured, no absorption due to an OH group or NH group was observed in a region of 3,000 cm ^-1 or more, and a strong absorption due to an amide group was observed at 1,650 cm ^-1. It was recognized, but the one diluted to 25% with ethyl cellosolve had a viscosity of 6.4 cS and a specific gravity of 0.964 (hereinafter abbreviated as Sample No. VI), and the viscosity was 6.5 cS even after one month. And there was almost no change in viscosity.

On the other hand, when the above reaction was carried out in the same manner as above except that hexamethylsilazane as a silylating agent was not used, a sample No. VII having a viscosity of 7.8 cS and a specific gravity of 0.965 was obtained. The previous reaction product has a remarkably high viscosity of 16,300 cS, which is due to the fact that the OH group generated by the ring opening reaction of the amino group and the epoxy group reacts with another alkoxy group intramolecularly or intermolecularly to increase the molecular weight. It is estimated that there is.

Further, the above reaction was carried out without using hexamethyldisilazane, and KBM603 and KBE402 were added together with acetic anhydride for 100%.
Sample N
When o.VIII was made, it was found by infrared absorption spectrum analysis that absorption due to NH groups was observed at 3,300 to 3,400 cm ^-1 , and the ring-opening reaction of epoxy and the amidation reaction of amino group were considered to be competitive reactions. It is understood that this means that there are considerable amino groups that are directly amidated in order to be.

Incidentally, in the above, only No. KBM603 and KBM402 were reacted in the same manner as above to prepare Sample No. IX, which had an initial viscosity of 6.0 cS, but increased to 14.6 cS one month later. .

Synthesis Examples 6 to 7 [Production of Colloidal Silica-Containing Organopolysiloxane Composition] 164 g of methyltriethoxysilane / KBE-13 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 46 g of isobutanol were charged into 1 separable flask. Colloidal silica, kept at 5 ° C or less while stirring under ice-cooling, and kept at 5 ° C or less
SNORTEX-O [Nissan Chemical Co., Ltd. product name, SiO ₂ 20
%)] And add 138 g under ice cooling for 2 hours,
After stirring at 8 ° C. for 8 hours, 36 g of ethyl cellosolve, 2,
1.8 g of 4-dihydroxybenzophenone and 0.1 g of polyether-modified silicone KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, followed by 1.5 g of a 10% aqueous potassium propionate solution, and the pH is adjusted with acetic acid. The composition was adjusted to 6 to 7 to prepare a colloidal silica-containing organopolysiloxane composition-I for overcoating.

In the above, a 10% aqueous solution of tetramethylammonium benzoate was used instead of the aqueous solution of potassium propionate.
A colloidal silica-containing organopolysiloxane composition for overcoating is treated in the same manner as above except that 3.0 g is used.
I made II.

Examples 1 to 6, Comparative Examples 1 to 5 12.0 g of the organic copolymer (samples I to V) produced in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 described above, polymethyl methacrylate 2.0 having an average molecular weight of 150,000 g, 5.0 g of the reaction product prepared in Synthesis Example 5 (sample VI), 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole.
Tinuvin-PS, 2- (2'-hydroxy-3 ', 5'-
Di-t-amylphenyl) benzotriazole / tinuvin-328 (all trade names manufactured by Ciba-Geigy) or 2,4-dihydroxybenzophenone 1.0 to 3.1 g, MIBK2
2.5 g, isobutyl acetate 20.0 g, ethyl cellosolve 16.0 g and isopropanol 18.0 g, diacetone alcohol 4.0
g was mixed as shown in Table 2 to prepare a primer composition.

Then, a polycarbonate sheet having a cleaned surface was immersed in the primer composition, pulled up, air-dried, and heat-treated at 80 ° C. for 10 minutes.The polycarbonate sheet having a cured film of the primer composition with a thickness of 2.5 μm on the surface. Was obtained. The surface was coated with the colloidal silica-containing organopolysiloxane compositions I and II obtained in Synthesis Examples 6 and 7 by a dipping method, air-dried, and then heat-treated at 120 ° C. for 2 hours. 3μm cured film of siloxane composition
Was obtained, and the performance of this coating film was evaluated. The results shown in Table 3 were obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kunio Yamazaki, Inventor 14-2 Kita-Showadai-cho, Takatsuki-shi, Osaka (72) Inventor Tomoki Nakamura 3-10-1, Miwa-cho, Toyonaka-shi, Osaka (72) Inventor, Goro Shimaoka Osaka 6-1-5, Akasakadai, Sakai City, Prefecture (72) Inventor Hitoshi Kobayashi 2-5.4-4 Higashi Tokiwadai, Toyono-cho, Toyono-gun, Osaka (72) Inventor Yukio Maeda 1-2-5-2, Higashiizumioka, Toyonaka-shi, Osaka (56) References JP-A-57-42737 (JP, A) JP-A-60-81256 (JP, A) JP-A-61-51036 (JP, A)

Claims (2)

(57) [Claims] 1. An organic copolymer of A) an acrylic and / or vinyl monomer containing 2 to 50% by weight of an alkoxysilyl group and another monomer copolymerizable with the monomer.
10 to 80% by weight, B) 0 to 30% by weight of an acrylic polymer, C) a reaction product of an amino-functional alkoxysilane with an epoxy-functional alkoxysilane and a silylating agent is converted into an acid halide of a carboxylic acid, an acid anhydride Amidated by reacting with a compound or an acid isopropenyl ester compound 5
30 parts by weight of a silicone primer composition and 15 to 35 parts thereof
1% by weight of 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole. 2. i) applying a solution of the primer composition according to claim 1 in an organic solvent to a plastic substrate; ii) evaporating the solvent to cure the coating; iii) then applying the coating on the coating. General formula R ⁴ _m Si (OR ⁵ ) _4-m (where R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ is 1 to 4 carbon atoms)
6, a monovalent hydrocarbon group or an alkyloxyalkyl group, m
Is applied with a colloidal silica-containing organopolysiloxane composition obtained by adding colloidal silica to a hydrolyzate or co-hydrolyzate of an alkoxysilane represented by 0, 1 or 2), and iv) at a temperature of 50 to 140 ° C. A method of coating a plastic substrate with a wear-resistant coating, characterized by curing the coating film.