JPH01149879A - Primer composition and usage thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition free from change in characteristics with time, outstanding in adhesivity and weatherability, useful for application on structural materials etc. alternative to glass, by incorporating a silicone primer composition with a specified proportion of specific benzotriazole. CONSTITUTION:The objective composition can be obtained by incorporating (A) a silicone primer composition with (B) 15-30wt.% based on the component A, of 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole. Preferably, the component A is comprised of (i) 10-80wt.% of an organic polymer from (an) acrylic and/or vinyl monomer containing 2-50wt.% of alkoxysilyl group and a second monomer copolymerizable therewith, (ii) 0-30wt.% of an acrylic polymer, and (iii) 5-30wt.% of an amide-modified reaction product produced by reaction between a) a reaction product from an amino-functional alkoxysilane, epoxy-functional alkoxysilane and silylating agent and b) a carboxylic acid halide.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a primer composition, particularly a silicone-based wear-resistant coating with excellent adhesiveness and durability, on the surface of a thermoplastic plastic molded product such as polycarbonate. This invention relates to a primer composition for molding and its usage.

(Prior art) Thermoplastic plastics, especially polycarbonate resins, have excellent transparency, are lightweight, and have excellent impact resistance, so they are widely used as structural materials in place of glass. The surface is easily scratched due to poor abrasion resistance, solvent resistance, and weather resistance, and it is easily attacked by organic solvents.
Moreover, it has the disadvantage of becoming discolored and deteriorating over time.

Therefore, it has been proposed to coat the surface of this molded product with a thermosetting resin, and among these, those coated with organopolysiloxane are said to have excellent wear resistance and solvent resistance. For this reason, organopolysiloxane is considered to be useful, but the coating with this organopolysiloxane coating has uniform adhesion to the surface of thermoplastics such as polycarbonate resin,
Since the weather resistance on the surface is insufficient, attempts have been made to use it in combination with other resins.
2) Acrylic resin primer having a functional group such as an amino group
3) Silicone primer made of a reaction product of an alkoxysilane having a functional group such as an amino group or a hydroxyl group and a cyclic acid anhydride (see JP-A-53-81533), 4) Epoxy 5) A silicone primer made of a mixture of silane hydrolyzate and aminosilane (see JP-A-54-63176); 5) Acrylic primer made of a functional group-containing thermoplastic acrylic resin and an ultraviolet absorber (Japanese Patent Application Publication No. 1983) -500
809), 6) an acrylic primer consisting of a thermosetting acrylic emulsion and an ultraviolet shielding compound (see JP-A-55-160033), 7) a reaction product of aminosilane, epoxysilane and acid anhydride. silicone-based primer (JP-A-56-16573
8) Thermoplastic acrylic primer consisting of a reaction product of an acrylic monomer, epoxy methacrylate, and a hydroxy-benzophenone ultraviolet absorber (see JP-A-57-23661), 9) Alkoxysilyl functionalization Colloidal silica-containing organopolysiloxane coatings containing aromatic ultraviolet absorbers are known.

However, the combined use of these resins does not necessarily give a satisfactory effect; for example, in the case of 1) and 2) above, although the adhesion to the substrate is considerably improved, active hydrogen groups such as amino groups If there is a substance containing , moisture will be absorbed from that part, resulting in poor water resistance and adhesion, and there will be little improvement in weather resistance. However, if active hydrogen groups remain, water-resistant adhesion will be insufficient, and since it contains amino groups, it will easily yellow, and weather resistance may actually worsen. , --COOH groups, it easily reacts with alkoxy groups, so the primer liquid becomes thicker over time and becomes difficult to apply, and has the disadvantage that adhesiveness decreases as the degree of polymerization increases. Regarding 5), weather resistance is considerably improved, but it is still insufficient for long-term weather resistance, and if applied thickly to improve weather resistance, the abrasion-resistant polyorganopolysiloxane coating becomes soft. Abrasion resistance decreases, and increasing the amount of UV absorber causes the coating to whiten or cause poor adhesion. The types of acrylic resins are limited, therefore it is not possible to select effective UV absorbers, the weather resistance improvement does not reach a satisfactory level, and furthermore, the adhesiveness is poor because the acrylic resin is thermosetting. There is a tendency to become Note that 7) has the same disadvantages as 3) and 4) above, and as for 8), since the ultraviolet absorber acts as a kind of radical stabilizer, it is difficult to make an acrylic polymer containing a large amount of it. , therefore, there is a disadvantage that weather resistance and adhesion are not sufficiently improved, and 9) also has the disadvantage that although weather resistance is improved, adhesion is not good.

(Structure of the Invention) The present invention relates to a primer composition that solves the above-mentioned disadvantages and a method of using the same.
-Hydroxy-3',5'-di-t-amylphenyl)benzotriazole, and after treating a plastic substrate with this composition, a colloidal silica-containing organopolysiloxane composition is It is characterized by applying a substance and curing this coating film.

That is, the present inventors have conducted various studies on improving the primer composition to improve the adhesion and weather resistance when coating thermoplastic resin molded articles such as polycarbonate with organopolysiloxane coatings. When 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole is added to the primer composition, this product does not change over time and has the effect of improving adhesion and weather resistance. If this material is applied to a plastic molded product and cured, then an organopolysiloxane wear-resistant coating containing colloidal silica is applied to the plastic molded product to improve weather resistance and adhesion. They found that the primer composition was excellent and did not cause yellowing, and conducted research on the types and composition ratios of each component in this primer composition, and completed the present invention.

The silicone-based primer composition constituting the primer composition of the present invention may be a known one, and therefore contains a reactive group in its molecule that chemically bonds with an inorganic material, such as a methoxy group, an ethoxy group, a silanol group, and an organic material. Reactive groups that chemically bond with the material, such as vinyl groups, epoxy groups,
Silane coupling agents containing methacrylic groups, amino groups, mercapto groups, etc., such as vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ
-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, etc., or these can be combined with methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc. Examples include alkyl acrylates such as alkyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate, glycidyl methacrylate, vinyl ethers such as vinyl acetate, ethyl vinyl ether, butyl vinyl ether, and hexyl vinyl ether, and those modified with styrene and ethylene glycol dimethacrylate. However, among these, organic copolymers of acrylic and/or vinyl monomers containing alkoxysilyl groups and other monomers as mentioned above that can be copolymerized with these monomers are used. It is said that those containing it as the main component are preferable. Regarding this organic copolymer, since the primer composition of the present invention is intended to form a silicone-based wear-resistant film on a molded article made of thermoplastic plastic such as polycarbonate, this organic copolymer may be used. Component A contains 2 to 50% by weight of an alkoxysilyl group-containing monomer, and the following acrylic polymer as component B and amino-functional alkoxysilane and epoxy-functional alkoxy as component C). It is preferable to use an amidated reaction product of silane and a silylating agent. This organic copolymer is said to be a copolymer of an acrylic and/or vinyl monomer containing an alkoxysilyl group and another monomer that can be copolymerized with these monomers. The acrylic monomer containing a silyl group has the general formula R1 (CH3).

R1 is a hydrogen element or a methyl group, R2 is a C1-C6 group selected from an alkyl group such as a methyl group or a propyl group, an alkenyl group such as a vinyl group or an allyl group, or an aryl group such as a phenyl group. Monovalent carbon hydrogen group, a is 1-
3, b is assumed to be O or 1;
-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltributoxysilane, 3-methacryloxypropyltriisopropenoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane , methacryloxymethyltributoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3
-acryloxypropyltributoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyl 1-ributoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyljethoxysilane, 3-methacryloxypropylmethyldibutoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethylmethyljethoxysilane, methacryloxymethylmethyldibutoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyljethoxy Examples include silane, 3-acryloxypropylmethyldibutoxycin, acryloxymethylmethyldimethoxysilane, acryloxymethylmethyljethoxysilane, and acryloxymethylmethyldibutoxysilane. density.

From the viewpoint of reactivity and the like, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are preferred.

In addition, the vinyl-11-yl monomer containing this alkoxysilyl group is represented by the general formula (%), and R3 is the same type of monovalent hydrocarbon group having 1 to 6 carbon atoms as R2 or alkyloxy an alkyl group, a vinyl-functional alkoxysilane in which C is O or 1, or a vinyl-functional alkoxysilane in which R3 is the same as above and d is O or 1; is vinyltrimethodisilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, vinylmethyljethoxysilane, vinylmethyldibutoxysilane, vinylmethylbis(2-methoxyethoxy) ) silane,
3-12= 1-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyloxypropylmethyljethoxysilane, 3-vinyloxypropylmethyldibu-1-xysilane Among these, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinyloxypropyltrimethoxysilane are preferred from the viewpoint of ease of handling and reactivity.

Next, other monomers that can be coweighted with these alkoxysilanes include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate, and glycidyl methacrylate. , acrylamide, acrylonitrile, vinyl ethers such as vinyl acetate, ethyl vinyl ether, butyl vinyl ether, and hexyl vinyl ether, styrene, and ethylene glycol dimethacrylate. Re-1 and the like are not preferred because the primer compositions prepared therefrom undergo changes over time such as thickening and gelation.

This organic copolymer is a copolymer of the above-mentioned monomer containing an alkoxysilyl group and other monomers that can be copolymerized with it, and this copolymer is a copolymer containing these monomers. It can be easily obtained by adding a radical polymerization catalyst selected from peroxides such as dicumyl peroxide and benzoyl peroxide, or azo compounds such as azobisisobutyronitrile to a solution and reacting under heating. However, in this organic copolymer, if the content of heavy substances containing alkoxysilyl groups is less than 2% by weight, the resulting film will not be thermosetting, and therefore a large amount of light stabilizer cannot be immobilized. In addition, if the content exceeds 50% by weight, the resulting primer layer will become too hard and the adhesive strength will be significantly reduced, so it is necessary to contain 2 to 50% by weight of the monomer containing an alkoxy group. It is said that

In addition, if the composition ratio of this organic copolymer in the primer composition is less than 1-0% by weight in the primer composition, it becomes thermoplastic and the heat resistance decreases, and if it is more than 80% by weight, the adhesion is poor. Therefore, it needs to be 10 to 80% by weight, but this preferable range is 20 to 80% by weight.

Next, the acrylic polymer as component B) added to this organic copolymer includes poly(methyl methacrylate-1~),
Poly(alkyl methacrylate-1~) such as poly(butyl methacrylate) and poly(butyl acrylate-1-)
, poly(alkyl acrylate), or their copolymers, which increase the viscosity of the primer solution without reducing adhesion, and when added, this material increases the adhesion in the primer solution. This prevents the viscosity of the primer solution from being too low, resulting in a coating film that is too thin to contain a large amount of light stabilizer. Ru. Note that this addition is not an essential requirement, and there is no need to add it if the organic copolymer as component A) has a sufficiently high viscosity, but even if it is added, it must be added at 30% by weight. If added in excess of this amount, the thermosetting properties of the composition will deteriorate, so the amount added should be 30% by weight or less.

In addition, the product obtained by amidation of the reaction product of the amino-functional alkoxysilane as component C), the epoxy-functional alkoxysilane, and the silylating agent added to this organic copolymer can be used as a waterproof primer composition. This alkoxysilyl group imparts good adhesion and crosslinks with component A) to form component 2 (D), which will be described later.
-(2'-Hydroxy-3',5'-di-t-amylphenyl)benzo1-lyazole is immobilized in the membrane.

Amino-functional alkoxysilanes used herein include N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, -aminoethyl)-3-aminobu 16=ropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(4-aminobutyl)-3-aminopropyltrimethoxysilane, N-(4-aminobutyl)-
3-aminopropylmethyldimethoxysilane, N-(6
-aminohexyl)-3-aminopropyltrimethoxysilane, N-(6-aminohexyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)aminomethylstyryltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
-aminoethyl)-aminomethylstyrylmethylzume 1
~xysilane etc., but among these, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane is preferred.

In addition, examples of the eboxy-functional alkoxysilane used here include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyljethoxysilane, 2-(3
, 4-epoxycyclohexyl)ethyl 1-rimethoxysilane, 5.6-epoxyhexyltrimethoxysilane, 5.6-nipoxyhexylmethyldimethoxysilane,
7.8-Epoxyoctyltrimethoxysilane, 9.1
Examples include 0-epoxydecyltrimethoxysilane, among which 3-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, etc. This product protects the ○H group produced by the reaction between the ○H group and the alkoxysilyl group and prevents the reaction product from changing over time. be.

The reaction between the amino-functional alkoxysilane, the epoxy-functional alkoxysilane, and the silylating agent can be carried out by dropping the epoxy-functional alkoxysilane into a mixture of the amino-functional alkoxysilane and the silylating agent, and causing a heating reaction. Alternatively, an amino-functional alkoxysilane and an epoxy-functional alkoxysilane may be reacted, and a silylating agent may be added to the reaction product to cause the reaction. In this reaction, the blending ratio of amino-functional alkoxysilane and epoxy-functional alkoxysilane is such that if the molar ratio of epoxy group/amino group is 0.3 or less, the number of alkoxy groups involved in crosslinking in one molecule is too small. The curability becomes weaker, the spread of the entire molecule disappears, the surface adhesion becomes weaker, and the adhesiveness becomes inferior. If this becomes 1.2 or more, it can be amidated in the amidation described later = N - H
It is preferably within the range of 0.3 to 1.2, since most of the groups are lost and the water-resistant adhesion deteriorates.

This reaction product is then said to have been amidated, but this amidation is an acid halogen of a carboxylic acid, exemplified by acetic acid chloride, acetic bromide, propionic acid chloride, acetic acid chloride, acetic anhydride, isopropenyl acetate, etc. If the amount of the reactant thus obtained added to the organic copolymer is less than 5% by weight, the adhesion to the substrate will be insufficient. If the amount exceeds 30% by weight, the crosslinking density in the primer layer will become too high, resulting in increased hardness of the resulting film and poor adhesion.
-30% by weight is required.

Next, the 2-(2'-hydroxy-3', 5'-di-t-amylphenyl)benzotriazole added to the silicone-based primer composition described in 2. It is a type of light stabilizer that protects the skin from UV rays, and is a known light stabilizer that is widely used for this type of use, such as salicylic acid ultraviolet absorbers such as phenyl salicylate, hydroxybenzophenone, and 2-hydroxy- Benzophenone UV absorbers such as 4-methoxybenzophenone, 2-(2'
Benzotriazole UV absorbers such as -hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5''-t-butylphenyl)benzotriazole, 2-methylhexyl-2-cyano-
Cyanoacrylate-1-based ultraviolet absorbers such as 3,3'-diphenylacrylate and ethyl-2-cyan-3,3'-diphenylacrylate can be added in small amounts, but will precipitate if added in large amounts. , the above-mentioned 2-(2'-hydroxy-3'
, 5'-G1. This is based on the inventors' belief that if benzotriazole (amyl phenyl) is used selectively, it can be added in large quantities and has a large photostabilizing effect.

If the amount of this substance added in the primer composition of the present invention is less than 15% by weight, good weather resistance will not be imparted to the intended plastic molded product, and if it is more than 30% by weight, the amount of this substance will be trapped in the primer film. Since this may cause poor appearance such as whitening or poor adhesion, it is necessary to keep the content in the range of 15 to 30% by weight.

The primer composition of the present invention includes the above-mentioned silicone-based primer composition and the above-mentioned 2-(2'-hydroxy-3
', 5'-di can also be obtained by mixing a predetermined amount of monoamyl phenyl) benzotriazole. An organic solvent diluted solution of this primer composition, for example, alcohols such as methanol, ethanol, isobutanol, ethoxyethanol, diacetone alcohol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, etc. Apply a solution diluted with esters, aromatic compounds such as toluene, or a mixed solvent of these.
This organic solvent is evaporated at room temperature or under heating to a thickness of 1.
A coating film of ~10 μm, preferably 2 to 5 μm may be formed. In addition, this organic solvent diluted liquid cannot thicken the coating film if the viscosity is less than 5O8, and 30C8
If it is more than 5 to 3, the handling and application method will be difficult.
It is preferable to use a material in the range of 0 cS, but it is optional to add a fluorine-based or silicone-based surfactant to smooth the coating film, and further promote the curing of the coating film. It is also optional to add a crosslinking curing catalyst containing an alkoxysilyl group to this to achieve this.

Plastic molded products such as plastic films and substrates coated with the cured film of the primer composition of the present invention obtained in this way have excellent initial adhesion, heat resistance, hot water resistance,
It is said to have excellent weather resistance, and is coated with a known colloidal silica-containing organopolysiloxane composition, such as -formula %, on which R5 is a carbon atom having 1 to 6 carbon atoms. Monovalent hydrocarbon radicals or alkyloxyalkyl radicals, m being 0, 1 or 2, alkoxysilanes such as methyltrimethoxysilane, methyltributoxysilane, methyltributoxysilane,
Methyltris(2-methoxyethoxy)silane, ethyltrimethoxysilane, ethyl 1-liethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, natrame 1 - Add silica fine particles of 1 to Loomμ to a hydrolyzate or cohydrolyzate of xysilane, tetraethoxysilane, tetrabutoxysilane, tetrakis(2-methoxyethoxy)silane, etc. with water or methanol, ethanol, isobutanol, diacetone alcohol Apply 10 to 80% by weight of colloidal silica dispersed in alcohol such as
When heated and cured at 40°C, the primer composition of the present invention is applied to the surface of this plastic molded product, so the synergistic effect of this primer coating and organopolysiloxane improves adhesion, durability, and wear resistance. This gives them the advantage of being highly functional.

Next, examples of the present invention will be given. Parts and % in the examples indicate parts by weight and % by weight, and the performance evaluation of the coating film obtained in this example is based on the measurement results according to the following method. It is something that

[Abrasion resistance]

100 with a load of 500g using a taper type abrasion tester.
After rotation, the haze (%) was measured using a haze meter.

〔hardness〕

A pencil hardness test was conducted.

〔Adhesiveness〕

A base grain (10×10) tape peel test was conducted, and the state of complete adhesion was expressed as 100/100.

〔Heat-resistant〕

After being maintained at 100° C. for 100 hours, the appearance, hardness, and adhesiveness were measured, and those with no change were judged to be "no abnormality."

[Hot water resistance]

After being immersed in hot water at 75°C for 100 hours, the appearance, hardness, and adhesion were measured, and those with no change were judged to be "no abnormality".

〔Weatherability〕

The time until the coating film peeled off and the hardness decreased was measured using a Sunshine Weatherometer and UVC○N (manufactured by Atlas, Inc., USA).

Synthesis Examples 1 to 5, Comparative Synthesis Example 1 [Synthesis of component A] γ-Methacrylpropyl trime 1 - xysilane KBM503
[Part name manufactured by Shin-Etsu Chemical Co., Ltd.] or vinyl 1-helimethoxysilane KBM1003 (product name manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl methacrylate, ethyl acrylate, vinyl acetate, chrycidyl methacrylate and ethylene as monomers that can be copolymerized with it. Glycol dimethacrylate, azobisisobuticoni-1helyl (hereinafter abbreviated as AIBN) as a polymerization catalyst, and diacetin alcohol as a solvent were blended at the times shown in Table 1, and this was mixed with Zimrow I. When charged in a 500n+Q separable flask with a type condenser and heated and stirred at 80 to 90°C for 5 hours under a nitrogen stream, an organic compound with a viscosity and a monomer content containing an alkoxysilyl group as shown in Table 1 was obtained. Copolymers (No., I to ■) were obtained.

=27- Table 1 Synthesis Examples 6 to 9 [Synthesis of component C] In a 2Q separable flask equipped with a Dimroth type condenser, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane KBM603 [Shin-Etsu Chemical Co., Ltd. Co., Ltd. part name) and 242 g of hexamethyldisilazane as a silylation agent and heated to 120°C under a nitrogen stream. Part name manufactured by Shin-Etsu Chemical Co., Ltd.] 496g was added dropwise to react, heated and stirred at 120°C for 5 hours, and then the low-boiling seafood was removed at 100°C under reduced pressure, and the viscosity was 1.387cS and the refractive index was 1. 461.
8. 862 g of a viscous compound with a specific gravity of 1.048 was obtained.

Next, 862 g of this reaction product and 862 g of toluene were charged into a 2Q separable flask equipped with a Dimroth type condenser, and 141 g of acetic anhydride was added thereto at room temperature under a nitrogen stream.
was added dropwise to react, heated and stirred at 110°C for 2 hours, then 141 g of methanol was added dropwise at 50°C, heated and stirred at 50°C for 1 hour, and then low-boiling components were removed at 100°C under reduced pressure. , a very viscous compound was obtained.

When the infrared absorption spectrum of this reaction product was measured, no absorption due to OH groups or NH groups was observed in the region of 3,0OOan-' or more. ], , 650
A strong absorption due to the amide group was observed in cm-', but when this was diluted to 25% with ethyl cellosolve, the viscosity was 6.4 cS and the specific gravity was 0.964 (hereinafter referred to as sample Nα■). This product still has a viscosity of 6.0 after one month.
There was almost no viscosity change at 5 cS.

On the other hand, when the above reaction was carried out in the same manner as above except that hexamethylsilazane was not used as the silylating agent, sample N with a viscosity of 7.8 cS and a specific gravity of 0°965 was obtained.
o■ was obtained, but in this reaction, the viscosity of the reaction product before amidation was extremely high at 16,300 cS, which is because the OH group generated by the ring-opening reaction between the amino group and the epoxy group is mixed with other alkoxy groups. It is presumed that the molecular weight is increased by intramolecular or intermolecular reactions.

In addition, sample Nα■ was prepared in the same manner as described in 1 above except that hexamethyldisilazane was not used and KBM603 and KBE402 were reacted together with acetic anhydride at 100°C. is 3°300-3,400(1)-1 by infrared absorption spectrum analysis.
Absorption due to NH groups was observed in , which is interpreted to mean that there are a large number of amino groups that are directly amidated because the ring-opening reaction of epoxy and the amidation reaction of amino groups become competitive reactions. Ru.

In addition, in the above, KBM603 and KBM 4.0
Sample &X was prepared by reacting only 2 in the same manner as above, and this sample had an initial viscosity of 6. OcS, but the viscosity had increased to 14.6 cS after one month.

Synthesis Examples 10 to 11 [Manufacture of organopolysiloxane composition containing colloidal silica] Methyl 1 to ethoxylan KBE-13 [Part name manufactured by Shin-Etsu Chemical Co., Ltd.] 164 was placed in an IQ separable flask.
g and 46 g of isobutanol were charged, and the temperature was maintained at 5°C or lower while stirring under water cooling, and the temperature was then lowered to 5°C or lower. % content) was added and stirred for 2 hours under water cooling and further stirred at 20 to 25°C for 8 hours,
Ethyl cellosolve 36g, 2.4-dihydroxybenzophenone 1.8g, polyether modified silicone/KP
-341, (part name manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 g was added, and then 1.0 g of a 10% potassium propionate aqueous solution was added.
5 g was added, and the pH was adjusted to 6 to 7 with acetic acid to prepare a colloidal silica-containing organopolysiloxane composition-■ for top coating.

Furthermore, an organopolysiloxane composition containing colloidal silica for top coating was prepared in the same manner as above except that 1 to 3.0 g of an aqueous solution of 0% tetramethylammonium benzony was used in place of the aqueous solution of potassium propionate. made.

Examples 1 to 10, Comparative Examples 1 to 7 12.0 g of the organic copolymers (samples ■ to ■) prepared in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1, with an average molecular weight of 1.
50,000 polymethyl methacrylate-h2. og, reaction products made in Synthesis Examples 6 to 9 (Samples ■ to X) 1.0 to
5.0 g, 2-(2'-hydroxy-3',5'-
Di-t-amylphenyl) benzotriazole tinuvin-328゜ [trade name manufactured by Ciba Geigy] or 2.4
-dihydroxybenzophenone 1.0-4. ,Og,M.
22.5 g of IBK, 20.0 g of isobutyl acetate, 16.0 g of ethyl cellosolve and 18. o
A primer composition was prepared by mixing 4.0 g of diacetone alcohol and 4.0 g of diacetone alcohol as shown in Table 2.

Then, a polycarbonate L-board whose surface had been cleaned was immersed in this primer composition, pulled up and air-dried at 80°C]
When heat-treated for 0 minutes, a polycarbonate plate having a cured film of the primer composition with a thickness of 3 μm on the surface was obtained. Siloxane composition■
When ~■ was applied by dipping and air-dried and then heat-treated at 120°C for 2 hours, a polycarbonate plate coated with a cured film of the organopolysiloxane composition with a thickness of 3 μM was obtained. When performance was evaluated, the results shown in Table 3 were obtained.

Claims (1)

[Scope of Claims] 1. Silicone-based primer composition and 15 to 30% by weight of 2-(2'-hydroxy-3',5'-di-t-
(amylphenyl)benzotriazole. 2. The silicone primer composition is mainly composed of an organic copolymer of an acrylic and/or vinyl monomer containing an alkoxysilyl group and another monomer copolymerizable with these monomers. A primer composition according to claim 1, which is a primer composition. 3. The silicone primer composition is composed of A) an acrylic and/or vinyl monomer containing 2 to 50% by weight of an alkoxysilyl group and another monomer copolymerizable with these monomers; Copolymer 10-80
B) 0 to 30% by weight of an acrylic polymer; C) The reaction product of an amino-functional alkoxysilane with an epoxy-functional alkoxysilane and a silylating agent is converted into an acid halide, anhydride or an acid of a carboxylic acid. Reactant 5- amidated by reacting with isopropenyl ester compound
30% by weight of the primer composition according to claim 1. 4, i) Silicone primer composition and its parts 15-3
0% by weight of 2-(2'-hydroxy-3',5'-di-
t-amylphenyl)benzotriazole in an organic solvent is applied to a plastic substrate, ii) the solvent is evaporated to cure the coating, and iii) the coating is then coated with the general formula R^4_mSi(OR). ^5)_4_-_m (R^4 is a monovalent carbon hydrogen group having 1 to 6 carbon atoms, R^5 is a monovalent hydrocarbon group or alkyloxyalkyl group having 1 to 6 carbon atoms, m is 0, A colloidal silica-containing organopolysiloxane composition prepared by adding colloidal silica to a hydrolyzate or cohydrolyzate of an alkoxysilane represented by 1 or 2) is applied, and iv) this coating film is formed at a temperature of 50 to 140°C. A method of coating a plastic substrate with an abrasion-resistant coating, the method comprising curing a plastic substrate with an abrasion-resistant coating.