JPS62191802A - Transparent formed body and its production - Google Patents

Abstract

PURPOSE:To obtain the coating film of the titled body having a high hardness, and capable of withstanding against wearing of many times by forming a coating film which is composed of fine particles of silica having a mean particle size of 5-300mmu and cohering at least one part of the particles, and a polymer contg. an org. substance on the surface of the transparent base material. CONSTITUTION:The transparent base material is preferably exemplified with an inorg. glass, various kinds of plastics such as acrylic resin, diethylene glycol bisarylcarbonate polymer, etc. The material having dye affinity is more preferable. The fine particle of silica cohering at least one part of the particles is a particle in which some of sphere fine particles of silica coheres and has 5-300mmu mean particle size. The polymer contg. an org. substance is not specified, if the polymer does not injure transparency of the coating film, and is examplified by polyvinyl butyral and polyvinyl alcohol, etc. The coating film is obtd. by coating the base material by means of a conventional coating means followed by curing it with an usual heat treatment. Thus, the high quality lens having excellent properties such as dyeability, heat resistance, hot-water resistance and flexibility is obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention provides scratch resistance, abrasion resistance, impact resistance, chemical resistance,
The present invention relates to a transparent molded article that has excellent flexibility, heat resistance, hot water resistance, light resistance, weather resistance, dyeability, etc. and is suitable for optical applications such as eyeglass lenses and camera lenses, and a method for producing the same.

[Prior art] Transparent molded bodies, especially plastic molded bodies represented by plastic lenses, have become widely used in recent years because they have extremely excellent impact resistance and transparency, are lightweight, and can be easily dyed. Demand is increasing. However, plastic lenses have a disadvantage that their surface hardness is lower than that of inorganic glass and they are easily scratched. Many attempts to improve this drawback have been proposed. Tokuko Sho 57-273
No. 5 and Japanese Patent Publication No. 52-39691 disclose coating compositions containing fine silica particles on the surface of a plastic substrate.

[Problems to be solved by the invention] The technology disclosed in Japanese Patent Publication No. 57-2735N is
It has the characteristics of having high surface hardness and further being able to be dyed. However, when the amount of silica added is increased, the drawback of negative altitude number lenses is that cracks occur in the film or cracks occur in the base material after heat curing.

On the other hand, the technique disclosed in Japanese Patent Publication No. 52-39691 also has the drawbacks of being unable to be dyed, having poor flexibility, and having low heat resistance and hot water resistance, although the film has a fairly high hardness.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention described below. That is,
The first invention of the present invention consists of the following configuration.

The present invention relates to a transparent molded article characterized in that a coating made of the following components A and B is provided on the surface of a transparent base material.

A, at least a portion is agglomerated and the average particle size is 5 to 3
00mμ silica particles.

B. Organic material-containing polymer Furthermore, the second invention provides the above-mentioned A and B on the surface of the transparent base material.
This invention describes a method for producing a transparent molded article, which is characterized in that a liquid coating composition containing the ingredients is applied to form a coating film, and then a cured film is formed by heating.

Transparent substrates used in the present invention include inorganic glass, various types of plastic decks, such as acrylic resins, polycarbonates, di(meth)acrylate polymers of diethylene glycol bisallyl carbonate polymer A and copolymers thereof, and (halogenated) bisphenol A. Urethane modification (
Preferably used are meth)acrylate polymers and copolymers thereof. Furthermore, a base material having dyeability is particularly preferably used.

At least a portion of component A in the present invention aggregates,
And silica fine particles with an average particle diameter of 5 to 300 mμ are:
It is supplied as a colloidal dispersion of high molecular weight silicic anhydride in a solvent such as water and/or alcohol.

Such a colloidal dispersion of silica exists stably at various pH levels and can be supplied as a liquid, but acidic dispersions are preferred from the viewpoint of paint stability, coating hardness, etc.
Those having a pH value of ~6.9 are preferably used.

In addition, the average particle diameter of the silica fine particles is 5 to 300 m.
Although 15 to 100 μm is preferable from the viewpoints of stability of the sol, transparency of the coating, and prevention of cracks in the coating due to heating or cracking of the base material.

Furthermore, the silica fine particles in which at least a portion of them are aggregated as used in the present invention are those in which several spherical silica fine particles are aggregated to form one fine particle. Here, the spherical silica fine particles are produced by a known method and are not particularly limited. In addition, the proportion of aggregated silica particles in the total silica particles should be determined based on the film thickness, intended performance, common single material, etc., but in the case of negative altitude number lenses such as corrective lenses, edge cracking may occur. From this point of view, it is used at 10w/4% or more, preferably 20w/w% or more. In addition, partially agglomerated silica fine particles can be produced by aging spherical silica, wrinkling it, sub-adjusting the pH, etc.

Furthermore, it is fully possible to agglomerate the spherical silica at the same time as the preparation, and in the present invention, I! The manufacturing method is not particularly limited.

It is preferable that these silica sol be contained in the coating film in an amount of 40 to 75% by weight.
-, more preferably 5 in terms of hot water resistance, heat resistance, etc.
0 to 65% weighting is used. That is, if the content is less than 40 ω%, the hardness decreases significantly during dyeing and hot water treatment, and it is difficult to obtain a material with a high surface hardness.

If it exceeds 75% by weight, there are problems such as whitening of the coating, cracking of the coating due to heat curing, cracking of the substrate, poor bonding ability with the substrate, and decreased dyeability.

The organic substance-containing polymer used as component B in the present invention may be any polymer as long as it does not impair the transparency of the coating. Examples of polymers that can be used include polyvinyl butyral,
Polyvinyl alcohol, cellulose, melamine resin,
Examples include ebogishi resin, polysiloxane resin, and acrylic resin.

Among them, thermosetting resins are preferably used from the viewpoint of surface hardness, heat resistance, hot water resistance, chemical resistance, etc., and polysoxane resins are particularly preferably used from the viewpoint of improving surface hardness. Typical examples of compositions for forming organopolysiloginane include organosilicon compounds represented by the following general formula (I) and/or hydrolysates thereof.

RR' Si (a is necessarily O or 1.) Specific representative examples of these organosilicon compounds include:
Methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyl 1-rimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, T-chloropropyltrimethoxysilane, T-chloropropyltriethoxysilane, T
~Chloropropyltriacetoxysilane, 3.3.3-
Trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, T~ruaminopropyl 1~rimethoxysilane γ-)l Minopropyltriethoxysilane, γ-mercaptopropyl 1~rimethoxysilane, γ-mercaptopropyl 1 - Lime 1 - Xie 1 - Xysilane, γ-mercaptopropyltriethoxysilane Propyl trime I - Xysilane, β-cyanoethyl 1
Noethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α- Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane xysilane, β
-glycidoxypropyltriane 1-xysilane, γ-glycidoxypropyl 1-lime)hexysilane, γ-glycidoxypropyltriane 1-xysilane, γ-glycidoxypropyltriplytriplysilane, γ-glycidoxypropyl 1 helibutoxysilane, γ-glycidoxypropyl 1-limethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, 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)Tilttripropoxysilane, β-(3,4-
epoxycyclohexyl)ethyltributoxysilane,
β-(3,4-epoxycyclohexyl>ethyltrimethoxye[·xysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, r-(3,
4-Epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane
- trialkoxysilanes such as epoxycyclohexyl)butyltriethoxysilane, triazyloxysilane or triphenoxysilanes or their hydrolysates, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiacetoxysilane, phenylmethyljethoxysilane, γ-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane lugetoxy Silane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methyloxysilane, methylvinyljethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldimethoxysilane,
α-glycidoxyethylmethyldimethoxysilane, α-
Glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane , β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldime-1-xysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Billmethyldiproboxysilane, γ-glycidoxypropylmethyldibu 1-xysilane, γ-glycidoxypropylmethyldimethoxy 1-xysilane, γ-glycid 1-xybinylmethyldiphenoY disilane, γ-glycidoxy Propylmethyldiacel-xysilane, γ-crisitoxypropylethyldimethoxysilane, γ-glycidoxypropylethyljethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyljethoxysilane, γ -Glycidoxypropylphenyldimethoxysilane, γ-glycidole, dialkoxysilanes such as dipropylphenyldiethoxysilane, diphenoxysilane, or diacyloxysilanes, or their hydrolysates are examples.

It is also possible to add one or more types of these 'Fi organosilicon compounds. In particular, for the purpose of imparting dyeability, it is suitable to use organosilicon compounds containing epoxy compounds and glycidoxy compounds. Further, from the viewpoint of curing speed, ease of hydrolysis, etc., as X, 01 to C7+ alkyl or alkoxyalkyl is preferably used.

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

Hydrolysis is carried out by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid, and stirring the mixture through a sieve.

Furthermore, it is also possible to easily control the degree of hydrolysis by adjusting the amount of pure water or acidic aqueous solution added. Upon hydrolysis, general formula (I)
It is particularly preferable to add pure water or acidic aqueous solution in an amount equal to or more than 3 times the mole of the X group in terms of accelerating curing.

During hydrolysis, alcohol and other substances are produced, so it is possible to hydrolyze without a solvent, but in order to make the hydrolysis more uniform, hydrolysis is performed after mixing the organosilicon compound and a solvent. It is also possible. Depending on the purpose, alcohol etc. after hydrolysis can be heated and
It is also possible to remove an appropriate amount under 7' or reduced pressure and use it, or it is also possible to add an appropriate solvent afterwards.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as heluene and xylene.

Furthermore, two or more of these solvents can be used as a mixed solvent if necessary. Depending on the purpose, it is also possible to accelerate the hydrolysis reaction and heat it above room temperature to advance reactions such as precondensation, and to suppress the precondensation, the hydrolysis temperature can be lowered to below air temperature. Needless to say, it is also possible to lower the height.

In the present invention, a coating composition consisting of silica fine particles, at least a portion of which is aggregated, and an organic substance-containing polymer is applied to the surface of a transparent substrate, and the coating composition is heated and cured. It is possible to pre-treat each type of zelkova to the base material for the purpose of improving water resistance. Particularly effective means for the present invention include activated gas treatment,
Examples include chemical treatment.

In curing the coating composition of the present invention, various curing agents can be used in combination for the purpose of accelerating curing, enabling low-temperature curing, etc. As the curing agent, various epoxy resin curing agents or various organosilicon 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 S/B compounds or metal alkoxides, organic carboxylates of alkali metals, and carbonic acid. Examples include various salts such as salt. It is also possible to use a mixture of two or more of these curing agents.

Among these curing agents, the aluminum chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoints of stability of the coating material, coloration of the film after coating, etc.

The aluminum chelate-1 compounds mentioned here are, for example, those of the general formula A I Y, Z3. This is an aluminum compound represented by:

However, in the formula, Y is OL (L is a lower alkyl group), Z is a ligand derived from a compound represented by the general formula M COCH2C0M" (Ml and M2 are both lower alkyl groups) and the general formula % formula % lower at least one ligand derived from a compound represented by an alkyl group), and n is 011 or 2.
It is.

Particularly useful as curing agents of the present invention, the general formula A I Y,
As the aluminum chelate compound represented by Z3-n, various compounds can be mentioned, and aluminum acetylacetate is particularly preferable from the viewpoint of solubility in the composition, stability, effect as a curing catalyst, etc. aluminum bisethyl acetoacetate, aluminum di-n-butoxide monoethyl acetoacetate, aluminum chelate 1so-propoxide monomethyl acetoacetate, and the like.

It is also possible to use a mixture of two or more of these.

As a method for applying the coating composition to be applied to the transparent M shrine of the present invention, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating, and flow coating can be easily used. It's rlhi.

The coating of the present invention (Jl) is applied by the above-mentioned coating method and cured, but the curing is mainly done by heat treatment. It can be used over a much wider range than in the case of compositions, with sufficiently good results being obtained between 50 and 250'C.

In the present invention, the thickness of the coating is not particularly limited. However, from the viewpoint of maintaining adhesive strength and hardness,
．． It is preferably used between 1 and 20 microns. More preferably, it is 0.4 to 10 microns. In addition, when applying the film, it is used after being diluted with various solvents for workability, film thickness adjustment, etc. Examples of the R agent include water, alcohol, ester, ether, and halogenated hydrocarbon.

Good implementation of this invention! ! ! In particular, Table 1
Due to its excellent Tii hardness and dyeability, it is useful for optical lenses such as sunglass lenses and prescription glasses lenses. It is particularly useful for negative altitude number lenses such as optical lenses such as CR-39.

Examples are given below to clarify the 4'4F characteristics of the present invention, but the present invention is not limited to these examples.
Work. The number of parts in the formula is based on weight 4.

Example 1 (1) T-glycidoxypropyl-rimethoxysilane, T-glycidoxypropylmethyljethoxysilane co-hydrolyzate Preparation 1 In a reactor equipped with a rotor, γ-glycidoxy 12.4 parts of probyltrimethoxysilane and 99.7 parts of γ-glycidoxypropyl methoxysilane were charged, and while stirring using a magnetic stirrer, 0.05 parts of
2 parts of a normal hydrochloric acid aqueous solution was added dropwise while maintaining the liquid temperature at 10°C, and after the addition was completed, stirring was continued for an additional 30 minutes to obtain a hydrolyzate.

(2) Preparation of coating composition Add one part of isopropyl alcohol to the cohydrolyzate of (1) above.
99.6 parts of silica, 11.9 parts of acetylacetone, and 136 parts of silicone surfactant were added and mixed, and 401% of the silica was agglomerated silica sol (average particle size 10 to 15 mμ).
〉Isopropyl alcohol classified silica sol 383
．． After adding 3 parts of aluminum acetylacetonate and 6.45 parts of aluminum acetylacetonate and stirring thoroughly, a coating composition was obtained.

(3) Preparation of coated product Using a CR-39 (diethylene glycol bisallyl carbonate polymer) -6,00 diopter lens as a transparent base material, the coating composition prepared in (2) above was pulled up at a pulling speed of 100 m/min. Dip coating was carried out under the following conditions, followed by preliminary curing at 82°C for 12 minutes, and further
After heating for 4 hours, a coated product was obtained.

(4>) Dyeing of the coated product A disperse dye bath consisting of three colors of red, blue, and yellow was prepared for the coated product of (3) above, and the dye bath was kept at 93°C and dyed for 10 minutes.

(5) Performance evaluation The performance of the obtained transparent molded body was tested according to the following method. The results are shown in Table 1.

(a) Steel wool With steel wool having a hardness of #0000, rub the coated surface 50 times with a fine stroke of 1.5 to 9 to judge the degree of damage.

○: There are almost no scratches and the rubbed surface does not whiten.

Δ: Fine scratches appear on the rubbed surface and whitening occurs.

X: The surface of the rubbed surface is turned over.

(b) Apply cellophane adhesive tape (trade name: "Cellotape" manufactured by Nichiban Co., Ltd.) firmly by inserting 100 gongs reaching the base material at 1 mm intervals on the adhesive coating surface using a steel knife.
The film was rapidly peeled off in a direction of 90° to examine whether or not the coating film peeled off.

Good ones were marked as ○.

(c) Appearance The obtained transparent molded product was visually inspected for cracks at the edges.

(d) Dyeing properties The dyed lenses obtained in (4) above were rotated under a fluorescent lamp to examine the uniformity of the dyeing.

O: Uniformly dyed.

X: Not uniformly dyed.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the silica fine particles were changed to non-agglomerated silica sol (average particle diameter 10 to 15 mμ). The test results are shown in Table 1.

Table 1: Effects of the Invention 1 The transparent molded article improved by the present invention has the following effects.

■ A high-hardness coating film that can withstand repeated abrasion from steel wool, etc. can be obtained.

■ Excellent dyeability.

■ Excellent heat resistance and hot water resistance.

■ Excellent easiness. 1 ■ Negative height for corrective lenses [Applicable to J number lenses, there is no cracking on the edges, and high quality lenses can be obtained.

Claims (8)

[Claims] (1) A transparent molded article characterized in that a coating consisting of the following components A and B is provided on the surface of a transparent base material. A, at least a portion is agglomerated and the average particle size is 5 to 3
00mμ silica fine particles B, organic substance-containing polymer (2) The transparent molded article according to claim (1), characterized in that silica fine particles are present in an amount of 40 to 75% by weight. (3) The transparent molded article according to claim (1), wherein the organic substance-containing polymer is a thermosetting resin. (4) The thermosetting resin is a polymer obtained from an organosilicon compound represented by the following general formula (I) and/or a hydrolyzate thereof. Transparent molded body. RR^1_aS_iX_3_-_a(I) (where, R is an organic group having 1 to 10 carbon atoms, R^1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms,
is a hydrolyzable group, and a is 0 or 1. ) (5) The method for producing a transparent molded body according to claim (4), wherein the organic group represented by R is an organosilicon compound having an epoxy group or a glycidoxy group. (6) A method for producing a transparent molded article, which comprises applying a liquid coating composition containing the following components A and B to the surface of a transparent substrate, and forming a cured film by heating. A, at least a portion is agglomerated and the average particle size is 5 to 3
00μm silica particles. B, organic substance-containing polymer (7) A method for producing a transparent molded article according to claim (6), wherein the organic substance-containing polymer is an organosilicon compound represented by the following general formula (I) and/or a hydrolyzate thereof. . RR^1_aS_iX_3_-_a(I) (where, R is an organic group having 1 to 10 carbon atoms, R^1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms,
is a hydrolyzable group, and a is 0 or 1. ) (8) The method for producing a transparent molded body according to claim (7), wherein the organic group represented by R is an organosilicon compound having an epoxy group or a glycidoxy group.