JPH0619481B2 - Method for producing composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is directed to scratch resistance, abrasion resistance, impact resistance, chemical resistance,
The present invention relates to a molded article having excellent flexibility, heat resistance, dyeability, and light resistance. Lenses for eyeglasses,
Lens for optical equipment such as camera lens, windshield,
It is useful for window glass.

[Conventional technology]

Organic polymer molded products containing halogen atoms (excluding fluorine) have the features of high refractive index and flame retardancy in addition to the light weight and easy processability of ordinary plastics. In particular, taking advantage of the former feature of high refractive index, its use has rapidly progressed recently as a lens application, especially as a spectacle lens for vision correction.

However, organic polymer molded products containing halogen atoms (excluding fluorine) are easily scratched due to their low surface hardness, and have high surface reflection of light rays due to their high refractive index. Therefore, dust due to static electricity tends to adhere,
Since it contains halogen atoms, it has drawbacks such as poor weather resistance. Furthermore, they are easily soiled by household items such as ink, cosmetics, soy sauce, and easily affected by chemicals such as hair spray, hair tonic, and cologne. Further, in the case of spectacle lenses, there are many cases in which three-dimensional crosslinking is carried out for the purpose of improving heat resistance, and in such molded articles, dyeability with disperse dyes or the like is difficult or impossible in many cases.

A number of attempts have been made to improve the above-mentioned many drawbacks (Japanese Patent Laid-Open No. 59-48702, Japanese Patent Laid-Open No. 5702/1985).
9-78301, JP-A-59-78304, JP-A-59
-86635).

[Problems to be solved by the invention]

Japanese Unexamined Patent Publication No. 59-48702 discloses a technique relating to a composite having a hard coat layer of a cured product of a polyfunctional epoxy resin. In the lens obtained by this technique, the hardness of the hard coat film is insufficient. Therefore, in order to improve the surface hardness, it is necessary to further coat the outermost layer with a hard film such as SiO ₂ . The lens thus obtained has an antireflection property, but on the other hand, it deteriorates heat resistance and impact resistance, which is a big problem.

Also, JP-A-59-78301 and JP-A-59-7830
No. 4, which discloses a coating of a hard coat layer containing an organic silane compound as a main component, these materials have insufficient adhesion to a substrate, deep scratches and thick edges, and cause serious defects in use. is there. Furthermore, there are drawbacks such that the adhesiveness is further reduced by chemicals such as water and alcohol, which causes a blister phenomenon.

On the other hand, as a surface modification of an organic polymer molding containing a halogen atom, for example, polyvinyl chloride, JP-A-59-8663.
In No. 5, low temperature plasma treatment is performed to prevent migration of the plasticizer contained in the polymer to the surface. However, this patent has only a surface treatment, and there is a problem that it is not effective to improve the surface hardness because a treatment such as a hard coat is not performed after the treatment.
Japanese Unexamined Patent Publication (Kokai) No. 58-204031 discloses a method in which a plastic molded product is subjected to plasma treatment, then washed with a solvent, and then an inorganic hard film is formed on the surface by vacuum deposition or the like. However, the molded product obtained in this way has fatal defects such as cracking on the surface due to heating, or a great decrease in impact resistance.

Further, in JP-A-57-47330, an excellent antireflection effect is obtained by treating the surface of a transparent material containing a fine particle inorganic material having an average particle diameter of about 1 to 300 mμ in its surface layer with an activating gas. Techniques for obtaining transparent materials having are described. However, this technique is a technique of forming an antireflection film by activating gas treatment,
Further, as described above, a transparent material containing a fine-particle inorganic material having an average particle diameter of about 1 to 300 mμ in its surface layer was examined, and an organic polymer molded product containing a halogen atom (excluding fluorine) of the present application. Was not considered.

For the purpose of improving the adhesion between the base material and the organic polysiloxane composition, halogen-free organic polymer moldings such as diethylene glycol bisallyl carbonate polymer are treated with an alkali such as caustic soda solution. Almost no effect is recognized in the halogen-containing organic polymer molded product.

[Means for solving problems]

The inventors of the present invention have made extensive studies to solve the above problems, and as a result, arrived at the present invention described below.

That is, the present invention is a halogen (excluding fluorine)
And after treating an organic polymer molding comprising a polymer of an adduct of a mono- or di (meth) acrylate having a hydroxyl group and an isocyanate compound or a copolymer thereof with an activated gas containing at least 15% by volume of oxygen. The present invention relates to a method for producing a composite, which comprises coating and curing an organic polysiloxane composition.

The amount of halogen atoms contained in the organic polymer molded product is preferably 1 to 75% in terms of weight%. That is, when it is less than 1% by weight, there is no effect of incorporating a halogen atom in view of flame retardancy and improvement of refractive index, and it is meaningless to apply the present invention. If it exceeds 75% by weight, an organic polymer molded article satisfying impact resistance and weather resistance cannot be obtained.
Again, there is little point in applying the invention.

There is no problem if the organic polymer molded product contains not only one type of halogen atom but also two or more types.
Further, there is no problem even if fluorine is contained within the range satisfying the above conditions.

In the present invention, a polymer of an adduct of a mono- or di (meth) acrylate containing a halogen (excluding fluorine) and a hydroxyl group and an isocyanate compound or a copolymer thereof is used as the organic polymer molded article.

The present invention requires that the above-mentioned organic polymer molded product is treated with an activated gas containing at least 15% by volume or more of oxygen. The gas other than oxygen used here is not particularly limited, and specific examples of the gas that can be mixed are nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor, ammonia, and one. Examples include carbon oxide, chlorine, nitric oxide, and nitrogen dioxide. These can be used not only with one kind but also with two or more kinds together with oxygen. In addition, it is natural that pure oxygen can be used, but oxygen such as air can
It is also possible to use a naturally occurring gas as long as it contains at least a volume percentage. That is, when the treatment gas is treated with an activated gas that does not contain oxygen gas in an amount of 15% by volume or more, a sufficient treatment effect cannot be obtained, and problems such as poor adhesion occur. From the viewpoint of shortening the processing time, 25% by volume or more is more preferable. Further, it is possible to raise the temperature of the molding target for the same purpose.

Further, as a method of converting the above-mentioned processing gas into the activated gas in the present invention, for example, corona discharge, direct current under reduced pressure, low frequency, high frequency or high voltage discharge by microwave is used. That is, the activated gas as referred to in the present invention is the ions, electrons or excited gas produced in this manner under normal pressure or reduced pressure. Among them, high voltage discharge using high frequency is preferably used from the viewpoint of productivity and reproducibility.

The present invention is to coat an organic polymer molding containing halogen, which has been treated with the above-mentioned activated gas, with an organic polysiloxane composition and cure it. Here, the organic polysiloxane composition means a general formula ( III) It is obtained by coating and curing a coating composition comprising an organosilicon compound represented by and / or a hydrolyzate thereof.

(Here, R ³ and R ⁴ are each a hydrocarbon group having an alkyl group, an alkenyl group, an allyl group, or a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group, and R ⁵ has a carbon number. 1 to 8 alkyl groups, alkoxyalkyl groups, and acyl groups, and f and g are 0 or 1.).

Specific representative examples of these organosilicon compounds include:
Tetraalkoxysilanes such as methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate, and their hydrolysates, and further methyltrimethoxysilane, methyl Triethoxysilane, methyltrimethoxyethoxysilane,
Methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane Ethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxy Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane N-beta (aminoethyl) -
γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α -Glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α -Glycidoxypropyltriethoxysilane,
β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxy Silane, β
-Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ -Glycidoxybutyltriethoxysilane,
(3,4-Epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyl Trimethoxysilane, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes or triphenoxysilanes or their hydrolysates, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenyl Methyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropyl Methyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methyl Vinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β- Glycidoxyethylmethyldimethoxysilane,
β-glycidoxyethylmethyldiethoxysilane, α-
Glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl Diphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ -Glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dialkoxysilanes or diacyloxysilanes or their hydrolysates are examples. Is.

These organosilicon compounds may be added alone or in combination of two or more. Particularly, for the purpose of imparting dyeability, it is preferable to use an organic silicon compound containing an epoxy group.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and further accelerate the curing.

Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. In the hydrolysis, -O of the general formula (III) is used.
It is particularly preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 3 times and equal to or less than that of the R ⁵ group in terms of curing acceleration.

Alcohol is generated during the hydrolysis, so it can be hydrolyzed without a solvent. However, in order to make the hydrolysis even more uniform, it is necessary to mix the organic silicon compound with the solvent and then perform the hydrolysis. Is also possible. It is also possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use depending on the purpose, and to add an appropriate solvent after that.
Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene.
Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary. In addition, depending on the purpose, it is possible to accelerate the hydrolysis reaction and to heat it to room temperature or higher in order to further advance the reaction such as precondensation, or to lower the hydrolysis temperature to room temperature or lower in order to suppress precondensation. It goes without saying that it is possible to do it.

The curing of the coating composition of the present invention can be achieved by heating and / or drying only the composition, irradiating with ultraviolet rays or irradiating with electron beam, etc. The curing agent can be used together. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds or metal alkoxides, and various organic carboxylates and carbonates of alkali metals. Examples include salt. These curing agents can be used as a mixture of two or more kinds. Among these curing agents, the following aluminum chelate compounds are particularly useful for the purpose of the present invention from the viewpoints of the stability of the coating material and the presence or absence of coloring of the coating film after coating.

The aluminum chelate compound referred to here is the general formula Al
It is an aluminum chelate compound represented by X _n Y _3-n .

As the aluminum chelate compound particularly pointed useful general formula AlX _n Y _3-n as the curing agent of the present invention may increase the variety of compounds, the solubility of the composition, stability, and the effect as the curing catalyst From the viewpoint of, aluminum acetylacetonate, aluminum bisethylacetate monoacetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate,
Aluminum-di-iso-propoxide-monomethylacetoacetate and the like. It is also possible to use a mixture of two or more of these.

In the coating composition of the present invention, it is possible to use various kinds of surfactants for the purpose of improving the flow at the time of coating, improving the smoothness of the coating film, and reducing the friction coefficient of the coating film surface. Yes, especially block or graft copolymers of dimethyl siloxane and alkylene oxide,
Further, fluorine-based surfactants are effective. In addition, it disperses dyes and pigments and fillers, dissolves organic polymers to color the coating film, coatability, adhesion to the substrate,
It is also possible to easily improve the practicality as a coating agent by improving the physical properties.

Further, for the purpose of improving weather resistance, it is possible to easily add an ultraviolet absorber or an antioxidant as a method for improving heat deterioration.

Further, silica sol, which is a colloidal dispersion of high molecular weight silicic acid anhydride in an organic solvent such as water and / or alcohol, is preferably used for the purpose of further improving the surface hardness and improving the antistatic property.

Curing of the coating composition of the present invention is mainly carried out by heat treatment, but the heating temperature can be used in a considerably wider range than in the case of the conventional thermosetting resin composition, and 50 to 250 ° C. is sufficient. Good results are obtained.

The organic polymer molding of the present invention comprising a polymer of an adduct of a mono- or di (meth) acrylate containing a halogen (excluding fluorine) and a hydroxyl group and an isocyanate compound or a copolymer thereof is used in at least 15 volumes of oxygen. As a coating means of the coating composition to be coated on the base material treated with the activated gas containing more than 1%, the usual coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating and flow coating are easy. Can be used for.

The composite obtained according to the present invention is more flame-retardant than general plastics, has a high refractive index, and has a durable and hard surface, so that not only thin lenses for vision correction but also It can be preferably used for lenses for cameras, binoculars and the like, and also for protective covers for various images and displays.

The following examples are given to clarify the gist of the present invention.
The invention is not limited to these examples. The number of parts in the formula depends on the weight.

Example 1 (1) Preparation of coated substrate Tetrabrom bisphenol A ethylene oxide 2
To 1 mol of a hydroxyl group-containing compound obtained by esterifying 1 mol of acrylic acid to a mol addition product, 0.9 mol of hexamethylene diisocyanate was added, and 70 parts of a monomer containing a polyfunctional acrylate monomer and 30 parts of styrene were added to isopropyl peroxide. The base material which was cast-polymerized by using as a polymerization initiator was subjected to activation gas treatment by the method described below.

A plasma treatment apparatus for surface treatment (PR501A, manufactured by Yamato Scientific Co., Ltd.) was used as an activation gas treatment apparatus, and an oxygen flow rate of 100 ml / min and an output of 50 W were applied for 10 minutes to obtain a surface-treated substrate. .

(2) Preparation of coating composition (a) Preparation of γ-glycidoxypropylmethyldiethoxysilane hydrolyzate A reactor equipped with a rotor was charged with 248 g of γ-glycidoxypropylmethyldiethoxysilane. While maintaining the temperature at 10 ° C., 36 g of a 0.05N hydrochloric acid aqueous solution is gradually added dropwise while stirring with a magnetic stirrer. After completion of dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropylmethyldiethoxysilane.

(b) Preparation of paint To the above-mentioned silane hydrolyzate, epoxy resin (“Epicoat 827”, product of Ciel Chemical Co., Ltd.) 116.2 g, diacetone alcohol 137.0 g, benzyl alcohol 68.6 g,
Acetylacetone 54.0g, Silicone surfactant 3.5
96 g of colloidal silica dispersed in methanol (average particle size 12 ± 1 mμ, solid content 30%)
And aluminum acetylacetonate 28.9g,
After thoroughly stirring, a coating composition was prepared.

(3) Preparation of coating base material The base material obtained in (1) above is coated with the coating composition prepared in (2) above on both sides of the base material under a pulling rate of 10 cm / min, and then 82 Preliminary drying was performed at / 12 ° C. for 12 minutes and further at 93 ° C. for 4 hours to obtain a composite.

(4) Test results The composite was tested according to the method described below. The results are shown in Table 1.

(A) Friction resistance test Steel wool # 0000 with coating film surface under load of 1.5 kg 1
The state of occurrence of scratches on the surface of the base material after rubbing 0 times is examined. The judgment was made as follows.

A ... Almost no scratches were observed.

B ... A slight scratch is observed.

C ... Many scratches are observed on the entire surface. The uncoated substrate was C or less.

(B) Adhesiveness Draw 11 parallel lines on the surface of the coating film at equal intervals of 1 mm and draw the same number of parallel lines intersecting them at right angles to make 100 squares. These lines cut the coating to the extent that it reaches the substrate. A cellophane adhesive tape (product name "Cellotape" manufactured by Nichiban Co., Ltd.) was strongly adhered to the eye-opening, and was rapidly peeled in the direction of 90 degrees to examine the presence or absence of coating film peeling.

(C) Dyeing property A dyeing bath in which a disperse dye is dispersed in water was dyed at 93 ° C. for 5 minutes.

Further, this composite was dipped in hot water at 90 ° C. for 2 hours, and then the adhesion was tested in the same manner as in the above (4) and (b), but the result was good. Similarly, a light resistance test with a fade meter was performed by irradiating for 100 hours, and a good result was obtained.

Examples 2 to 3 and Comparative Examples 1 to 2 All were performed in the same manner as in Example 1 except that the gas composition and amount in the activated gas treatment were changed as shown in Table 1. The results are shown in Table 1.

Example 4 The same procedure as in Example 1 was carried out except that the coated substrate as described below was used.

(1) Preparation of coated substrate A cast polymerized substrate was treated in the same manner as in Example 1 except that styrene was changed to divinylbenzene, and then activated gas treatment was performed by the method described below to obtain a coated substrate. It was The treatment method is in air at room temperature, voltage 6000 V, frequency 50 cycles, distance between electrode and roll 2 mm,
Corona discharge was performed under the condition of a speed of 15 m / min. The results are shown in Table 2.

[Effects of the Invention] The composite obtained according to the present invention has the following effects.

(1) A composite having good adhesion and high surface hardness can be obtained.

(2) It has excellent durability against water.

Claims (1)

[Claims] 1. An organic polymer molding comprising a polymer of an adduct of a mono- or di- (meth) acrylate containing a halogen (excluding fluorine) and a hydroxyl group and an isocyanate compound or a copolymer thereof and containing at least oxygen. 15
A method for producing a composite, which comprises coating an organic polysiloxane composition and curing it after treating with an activating gas containing at least a volume percentage.