JPS60262833A - Coated synthetic resin material - Google Patents

Abstract

PURPOSE:To provide a coated synthetic resin matrial excellent in surface hardness, resistance to scuff, heat, and hot water, etc., well suited for optics, etc., by applying the coat of an inorg. rigid material onto the surface of a synthetic resin base through the film of a particular organosilicon compd. CONSTITUTION:A disilane compd. of formula I (wherein A is a bivalent hydrocarbon group where the main chain consists of 4 or more straight-chain atoms; R<1>, R<2> are alkyl, alkoxyalkyl; R<3>, R<4> are alkyl; l, m are 0, 1) (e.g., formula II, formula III) is prepd. The compd, is dissolved in an adequate solvent (e.g., methanol) and the soln, is hydrolyzed by adding an inorg. acid (e.g., hydrochloric acid) or ogr. acid (e.g., acetic acid). The hydrolyzate is applied onto the surface of a synthetic resin base and dried to form a film of an organosilicon compd. Then, a film of an inorg. rigid material (e.g., silicon dioxide, titanium dioxide) is formed on the resulting film to yield the intended coated synthetic resin material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin material having a coating having a surface hardness of 1 and excellent scratch resistance, heat resistance, etc. The coating is made of a specific organosilicon and an inorganic hard material, and has an optical The object of the present invention is to provide a synthetic resin material useful as a material.

In general, synthetic resins 1 have drawbacks such as being easily abraded and scratched due to low solvent resistance and surface hardness.In particular, synthetic resins 21 optical materials have the problem of loss of transparency due to abrasion and scratches. Therefore, in order to solve these problems, a method of forming a hard film on the surface of a synthetic resin base material has been used. Such hard coatings are roughly classified into organic type and inorganic type depending on their constituent components and coating method. The former is, for example, fever.

The main component is a curable substance that crosslinks with K, such as light or radiation, and after being applied to a synthetic resin base material, a hardening treatment is performed to form a hard film. The latter is a metal oxide formed by vacuum evaporation.

It is a coating of inorganic hard material such as fluoride. %, the latter is generally formed by forming a single layer or multilayer coating of inorganic compounds with different refractive indexes to an optical thickness for the purpose of antireflection.

However, compared to organic coatings, inorganic coatings not only have inferior surface hardness, but also have insufficient adhesion between the inorganic hard material and the synthetic resin base material, and the coating may peel off due to heat or hot water. There was a flaw.

In view of the above, the present inventors proceeded with development for the purpose of forming an inorganic hard film with high surface hardness and excellent abrasion properties on the surface of a synthetic resin base material, and as a result, identified a disilane compound. It was discovered that the desired purpose could be achieved by first forming an organic silicon film containing ash on the surface of the synthetic resin base material, and then forming an inorganic film by deep vapor deposition. , the present invention has been completed, that is, the present invention is a disilane compound represented by the general formula 1 on the surface of a synthetic resin base material (where A is a disilane compound having at least 4 or more atoms in a linear main chain). 2IdIll hydrocarbon group consisting of, R and R are the same or different furkyl group or alkoxyfurkyl group, R and R' are the same or different furkyl group, and m is 0 or 1) is hydrolyzed to [ The resulting material is a 4-mer composite-A+1 material which is coated with organosilicon containing component 'I' and further coated with an inorganic hard material on the coating film.

According to the present invention, by forming a specified organosilicon coating between the surface of the synthetic tree Rft material and the coating of the inorganic hard material, the reflection by the eIt film of the inorganic hard material is A synthetic resin material having a coating film with excellent adhesion, surface hardness, durability, etc. without impairing the prevention effect etc. can be obtained.

Therefore, in the present invention, the component obtained by hydrolyzing the specified disilane compound in the organosilicon coating film effectively interacts with the synthetic resin base material and the inorganic hard material to achieve high surface hardness and adhesion. is considered to be given.

The type of synthetic resin base material used in the present invention varies depending on the purpose and is not particularly limited. Synthetic resin lenses generally have high transparency, but low surface hardness, and poor scratch resistance and abrasion resistance.

The main targets are optical materials such as prisms, flats, and sheets. Examples of synthetic resin base materials for such optical materials include polyunsaturated esters such as polymethyl methacrylate, polymethacrylate, polyethylene terephthalate, poly7 acrylate, and polymethyl 7 acrylate; polystyrenes; polyvinyl chloride; epoxy Resin; Polyamides; Polycarbonate; Polyallyl carbonates such as polydiethylene glycol bis-7lyl carbonate; Polymers such as cellulose acetate plastics, or combinations of heptamers forming these polymers with each other or with other monomers. Examples include molded products made of copolymers.

Among them, polymethacrylic esters, polyacrylic esters, and polycarbonates.

By using highly transparent molded products made of polymers such as poly7lyl carbonates, the invention has high transparency and good appearance, without losing its optical properties, and has excellent surface hardness, scratch resistance, and abrasion resistance. Since a coated synthetic resin material with excellent properties can be obtained, it is extremely suitable as an optical material.

In the present invention, one step is to first form a film of A-like substance A obtained by hydrolyzing a disilane compound represented by the formula fl+ on the surface of the synthetic resin base material as described above. In the compound represented by formula (1), typical examples of divalent hydrocarbon groups represented by the characters in the formula are (a) CM, CH, CH, CH,, CH8CH, CH
, CHCH, etc. Real kylene group (b) CH, CH, OCH, CH, , CH, CH, C
H, OCH, CH, CH.

The general formula (C)f s )p OC(CHs )q
o) r (cHa) ether group represented by p (where p, q are 2 or 3, r is an integer of 0 or 1 or more) (however, p is 2 or 3) spiro group 10) CH, OH, C00CH, CH-CHCH, 0OCCH
,OH,.

A group (e) containing an epoxy group represented by 0 1 CM, CH, CH, 0COCH, CH, CH,.

General formula: % Formula % (8 is an integer of 0 to 4. t is 0 when s = 00 and 1 when i = 1 to 4), etc. Also, 2 (in 11, R and R are the same or different furkyl group or alkoxyfurkyl group, and are an alkyl group having 1 to 6 carbon atoms, especially 1 to 3 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, especially 1 to 3 carbon atoms. An alkoxyfurkyl group consisting of a furkyl group of 3 is preferable, and specific examples include a methyl group, an ethyl group, a purpyl group, and a methoxyethyl group.R,
R is the same or different furkyl group, and has 1 to 1 carbon atoms;
4 is preferred, specifically a methyl group.

Examples include ethyl group and propyl group.

Among the above-mentioned disilane compounds, in general formula f1), A is a divalent hydrocarbon group containing a hydrophilic group such as an epoxy group or a carbonate group, in particular, a group selected from (d) and (e). The organosilicon coating film as a constituent component is
It is particularly effective in exhibiting excellent adhesion and durability to the inorganic hard material coating film formed thereon.

These disilane compounds represented by the general formula (1) can be synthesized by various conventionally known methods. That is,
It can be synthesized by subjecting a compound having a substituent having an addable double bond to both ends of the compound to an addition reaction with an alkoxysilane shown below under a platinum catalyst. Alternatively, instead of an alkoxysiler/, the following or qo disilane addition reaction is carried out, and then ROH
Alternatively, it may be alkoxylated with furfur shown in ROM. The above reaction conditions are not particularly limited, but generally at a temperature of -20 to 160"C under normal pressure or increased pressure,
If necessary, the above reaction may be carried out in a polar nonaqueous solvent such as benzene, toluene, dimethyl ether, or the like. Further, it is preferable to use platinum black as the platinum catalyst since a colorless and transparent product can be obtained. For example, by reacting diethylene glycol bisallyl carbonate with triethoxysilane under a platinum catalyst, 1 (E!to), SICH8CH,CH,0COCH
, CH, OCH, CH, 01 COCH, CH, CH, S I (OEt) are obtained.

In the present invention, in order to form a good organosilicon film, prior to coating the surface of the synthetic resin base material with the disilane compound described above, the disilane compound is hydrolyzed and K is partially condensed and polymerized. It is preferable to use the form. Generally, it can be prepared by dissolving a disilane compound in a suitable solvent, adding a weakly acidic aqueous solution containing an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid or acetic acid, followed by stirring and hydrolysis. In this way, the coating liquid may contain furfur, furfurukidial alcohol, unreacted water, or solvent produced as a by-product of the above hydrolysis, but after hydrolysis, the above components are heated and/or under reduced pressure. It is also possible to remove by distillation and then add a suitable solvent. Finally, the coating solution containing the disilane compound as a component has a concentration of 20 to 40% by weight when converted into a state in which the disilane compound is completely hydrolyzed and polycondensed (hereinafter referred to as "converted once"). 111! 6. If the above concentration is less than 20%, it is possible to form a uniform film of organic silicon on the shallow depressions of the synthetic mBk substrate. Excellent scratch resistance and abrasion resistance ((,4
If the amount is 0% or more, the viscosity increases and it becomes difficult to apply the coating uniformly to the surface to be coated. In addition, as the above-mentioned suitable mortar, low M flucols such as methanol, ethanol, and butanol having 1 to 4 carbon atoms; acetic acid,
i) Lower carboxylic acids such as methyl acid or their alkylnisdales; ethers such as Serunlup and dioxane; ketones such as 7-setone; methylene chloride derivatives;
Hydrocarbons: One or more aromatic hydrocarbons such as benzene and toluene.

It is also effective to add other specified compounds to the uninvented disilane compound represented by the above formula (1) in order to improve the surface resistance of the resulting film. Such additives include: ('')ht, IR-8t(OR)8-n...self......
...Organoalkoxysilane compound represented by +21 (where R is a hydrocarbon group, an alkyl group, or an aryl group having one of a vinyl group, a methacripoxy group, a mercapto group, an epoxy group, and an amino group as a functional group) A component obtained by hydrolyzing a furkyl group, n is 0 or 1, and R7 is an alkyl group or an alkoxyfurkyl group, 81 (OR) 4 ...... ...
...A component obtained by hydrolyzing the tetraflufukidisilane compound shown in (3) (wherein R is an alkyl group or an alkoxyfurkyl group), colloidal silica, an epoxy compound, and a melamine derivative. At least one type is recommended.

Among the organoalkoxysilane compounds represented by the general formula (2) of bd above, those in which R6 has 1 to 4 carbon atoms and R has 1 to 4 carbon atoms are generally used. Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Phenyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrifate, xysilane, vinyltrismethoxyethoxysilane, γ-glycidoxypyltrimethoxysilane, γ-glycidoxypylmethoxysilane , γ-methacryloxypyltrimethoxysilane, r-mercapdobu-pyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-pyltrimethoxysilane, and the like. Further, the tetraflufukidisilane compound represented by the general formula (3) is generally used when R has 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetrap-boxysilane,
Examples of colloidal silica include silica fine powder with a particle size of 1 to 100 mμ, which is produced by various conventionally known methods, as it is, or in the form of a colloidal solution obtained by dispersing it in a polar solvent. Available in For the composition of the present invention, a Freud's solution prepared by dispersing the colloidal silica in a polar solvent, such as water, methanol, or a furfur solvent such as impropatol, is preferably adjusted to be weakly acidic. Examples of the epoxy compound include polyolefin epoxy resins, alicyclic epoxy resins, epoxy novolak resins, and polyglycidyl ethers of polyvalent furfur, which are manufactured by various conventionally known methods. Examples of melamine derivatives include commercially available mixtures of furkyl etherified methyl p-lumamine such as hexamethoxymethyl melamine with nitrified cotton, or precondensates with polyhydric alcohols such as 1,4-butanediol, which are conventionally known. It can be prepared and used according to the method.

The total amount of additives as described in E is (disilane compound,
For organoalkoxysilane compounds and tetraalkoxysilane compounds, use 10 to 1000 parts by weight, especially 50 to 200 parts by weight, based on the disilane compound (based on the weight converted to the state obtained by hydrolyzing into the base metal and condensation polymerization). is preferred.

Furthermore, in the coating liquid containing a disilane compound in the present invention, a silicone-based or fluorine-based surfactant is added to improve the smoothness of the resulting film and to form a uniform film on the next inorganic hard material. It is possible to add

In addition, various other additives such as ultraviolet ray absorbing agents, antioxidants, dyes and pigments, and formic acid as anti-gelling agents,
Organic carboxylic acids such as acetic acid can also be used. In addition, the coating liquid may contain compounds known as curing catalysts, such as hydrochloric acid, sulfuric acid, acetic acid/sodium acetate mixtures, in order to lower the curing temperature and shorten the curing time of the coating, if necessary.
Perchlorine salts such as tin chloride, perchloric acid, ammonium perchlorate, zinc perchlorate, magnesium perchlorate, 7cetylacetonate metal salts such as flumium 7cetyl 7cetonate, naphthenic acid metal salts, p-toluene Preferably, sulfonic acid, benzoic acid, alkali metal phosphate, sodium thiocyanate, etc. are used. The amount used is 0.01 to 5% by weight based on the amount of components for film formation.

In the present invention, the method of forming an organosilicon film on the surface of a synthetic resin base material is not particularly limited, and a coating liquid containing a disilane compound as a constituent component is applied to the surface of the synthetic resin base material according to a generally known method. A coating method is adopted. For example, a method of coating a synthetic resin base material by dipping it in a coating solution,
Spray the coating liquid onto the surface of the synthetic resin base material, brush,
Generally, a method of coating with a roller or the like is employed, and after coating, it is air-dried with dry air or air C15 and usually heat-treated to cure and form a film.

The heating temperature varies depending on the type of synthetic resin, but is preferably 50°C or higher, preferably 70°C or higher, or a temperature at which the synthetic resin base material does not undergo thermal change, generally 1.50°C or lower. The curing time is approximately 1 hour at a heating temperature of 130℃, 70~8
A rough guideline is approximately 2 to 4 hours at 0°C. The organosilicon coating formed by curing can have a thickness of about 0.1 μm to 50 μm, but a thickness of 1 μm to 20 μm is particularly suitable for obtaining the desired effect. Note that since the surface condition of the synthetic resin base material greatly affects the properties of the resulting coated film, it is preferable to clean the surface by degreasing and washing with a solvent or the like. In addition, if the adhesion of the organosilicon coating of the present invention is insufficient depending on the synthetic resin fabric, for example, for plastic molded products such as polycarbonates and styrene polymers (for example, apply 1 part of sodium hydroxide aqueous solution and 1 weight particulate acid). Known methods such as reagent treatment with a potassium/M acid solution, discharge treatment with plasma, etc., or primer coating are effective because they improve the adhesion between the synthetic resin fabric and the organosilicon coating. It is further preferable that the layer modified by the treatment be dissolved on the treated surface using a solvent that does not substantially dissolve the synthetic resin fabric.Also, the synthetic resin base material is coated with an organosilicon coating solution. The organosilicon film containing a disilyl compound can be dyed with a disperse dye etc. beforehand, and the organosilicon film containing the disilyl compound can be dyed with a disperse dye etc., so the organosilicon film is formed and the inorganic compound layer is formed by dyeing. Good too.

Next, in the present invention, it is important to form a hard inorganic material film on the silicon film formed on the surface of the synthetic resin base material. Any known method can be used without particular limitation as a method for forming a coating of an inorganic hard material. For example, vacuum evaporation method.

Dry brating methods such as ion brating method and sputtering method are common.

The thickness of the inorganic hard coating is not particularly limited as it varies depending on the purpose, but it is generally 0.1 μm to 10 μm. As the inorganic hard substance forming the coating of the present invention, any inorganic substance that can be deposited on the surface of a synthetic resin base material by the above-mentioned dry brating method can be used without any restriction, and it can be selected as appropriate depending on the purpose. good. For example, to impart scratch resistance, silicon oxide (SjOx, x=1~
2), aluminum chloride, etc. are generally used. Further, in order to impart antireflection properties, K may be a single layer of a low refractive index material, or a low refractive index material and a high refractive index material may be alternately laminated to an optical thickness. Examples of inorganic hard substances constituting such an antireflection film include metal oxides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, cerium oxide, yrene oxide, tantalum oxide, and hafnium oxide: fluoride Metal fluorides such as magnesium, cerium fluoride, lithium fluoride, lanthanum fluoride, sodium fluoride, and neodymium fluoride are
can be lost. Other materials include aluminum, gold, and silver.

Metals such as chromium and inorganic compounds other than those mentioned above, such as zinc sulfide, can also form films with good adhesion on the organosilicon film of the present invention. In addition, if the adhesion between the inorganic hard material coating and the organosilicon coating is insufficient, after forming the organosilicon coating, 1) preliminarily subject the coating to plasma discharge treatment to form an inorganic compound layer. This method is effective in improving the adhesion between the inorganic hard material coating and the organosilicon coating.

The nucleated synthetic resin material of the present invention obtained by pressing in this manner has an organic silicon coating obtained by hydrolyzing a disilyl compound as an intermediate layer between the synthetic resin base material and the inorganic hard coating. By forming the organosilicon film, the surface hardness, scratch resistance, heat resistance, and hot water resistance are superior to the case where the organosilicon film is not present. EXAMPLES Examples and comparative examples will be shown below to specifically explain the present invention, but the present invention is not limited to these examples.

The performance of the coating formed on the surface of the synthetic resin base material was evaluated by the following method.

(11 Adhesion test ° 1111 on the surface of the sample with a sharp cutter knife
1 X l After 100 squares of 11 were attached, commercially available cellophane tape was attached and then quickly peeled off.The film was marked as ○, with no peeling at all, and with some parts peeling off. A case where the metal part was completely peeled off was indicated as Δ, and a case where all the metal parts were peeled off was indicated as ×.

(2) Scratch resistance test Scratch resistance tester manufactured by Fukuda Machinery Co., Ltd.: #000
0 steel wool was attached and the sample surface was reciprocated 10 times under a load of 1 Kp, and the degree of damage on the surface was visually observed. Evaluation was made on a five-point scale from A to E, with E being an easy condition.

(3) Hot water resistance test The film was left in boiling water (80°C warm water was used for polymethyl methacrylate K) for 2 hours, and the appearance of the film was visually observed. Cracks, peeling, and blisters on the film.

If there is no whitening and the appearance is good, mark it as ○.

If it was defective, it was marked as ×. In addition, the adhesion test described above was conducted and evaluated using the same criteria.

Example 1 Poly7 produced by injection polymerization as a synthetic resin optical material
A plate-like body of lylded ethylene glycol carbonate was used. First, as a pretreatment, the plate-shaped body was washed with 77 tons of water, thoroughly air-dried to a clear state, immersed in a 5% NaQl (aqueous solution) for 5 minutes, thoroughly rinsed with water, and air-dried again.

The treated plate was immersed in a coating solution having the composition shown in Table 1, thoroughly air-dried at room temperature, and then heated and cured at 120 DEG C. for 3 hours to obtain an organosilicon coating with a thickness of 2 to 3 .mu.m. Next, the organosilicon-coated poly-7-lylene glycol carbonate plate was vacuum-deposited using a commercially available vacuum evaporation apparatus under conditions of 10 Torr.
A silicon oxide film of 0.03 μm was formed. The evaluation results of the coatings are shown in Table 1.

The organosilicon coating solution is prepared by mixing and dissolving the compositions shown in Table 1 in equivalent amounts in the solvent isopropylfluorol so that the equivalent amount is 30% by weight, and then hydrolyzing the flufoxy group of the above composition. After adding the required equivalent amount of 005N hydrochloric acid at room temperature and aging for one day, sodium acetate/acetic acid el (1/l) was added as a curing catalyst.

(weight ratio) was prepared by adding 2% by weight to the converted amount.

The fluid silica is 08CAL (product name: 8102 301KM%) manufactured by Catalysts and Chemicals.

Particle size 10-20 mμ, solvent inpropyl furfur)
EXAMPLE 2 A film was formed in the same manner as in Example 1 for /I65 except that the compound shown in Table 2 was used as the disilane compound. The evaluation results of the coating are also shown in Table 2.

A coating was formed in the same manner as in Example 3 and /I65 except that silicon oxide was replaced with aluminum oxide. The performance of the film is as follows: initial adhesion O1, scratch resistance A, hot water resistance (
Both appearance and adhesion were rated K)O.

Example 4 In Example I, a commercially available polymethyl methacrylate plate was used as the synthetic resin optical material, first washed with methanol and thoroughly air-dried to a clear state, and then prepared as shown in Table 1/I.
65, and heat cured at 80°C.
A film was formed in the same manner except that the treatment was carried out for 4 hours. The performance of the film is as follows: initial adhesion ○, scratch resistance B, hot water resistance (
Both appearance and adhesion were ○.

Example 5 2, 2 manufactured by cast polymerization as a synthetic resin optical material
1-bis(4-(2-methacryloxy)-ethoxy-3
, 5-dibu-ρmophenyl]propane (hereinafter abbreviated as TB) and styrene (the weight ratio of TB/styrene is 2/3).
After washing with 7 tons of water and thoroughly air-drying it to a clear state, a mixed gas of argon/oxygen (flow rate of 3
0d/deception/1゜1/deduction) Pressure 0.7tom, output 200
W, for a treatment time of 1 minute, and then washed for 5 minutes using an ultrasonic cleaner using 7 setone as a solvent, and air-dried again. In Example I, a coating was formed in the same manner as in Example I except that the coating liquid shown in Table 1/165 was used and the plate-shaped body treated as described above was used. The performance of the film was: initial adhesion ○, scratch resistance A, and hot water resistance (both appearance and adhesion) O.

Example 6 Instead of Table 1-/I65 of Example 1, 50 parts by weight of polyethylene glycol diglycidyl ether (Evolite 200E, manufactured by Kyoeisha Yushi) or hexamethoxymethylmelamine, and 50 parts by weight of 1,4-butanediol A coating solution was prepared in which the same amount of the preliminary wire hardware consisting of the silkworm part was added, and a coating was formed in the same manner as above. The performance of the film is initial adhesion O1 scratch resistance A
, hot water resistance (appearance, adhesion) was ○.

Comparative Example 1 Polydiethylene glyfur bis7lyl carbonate plate and TB produced by cast polymerization as a synthetic resin optical material
/Styrene copolymer plate and K were each washed with 7 setsone and sufficiently air-dried to a quenchable state, and then 0.2 ~
A 0.3μ silicon oxide coating was obtained.

In all cases, the properties of the coatings were as follows: initial adhesion was good, scratch resistance was good, and hot water resistance was good (K for both external and VB adhesion).

Comparative Example 2 An aluminum oxide coating was obtained in the same manner as in Comparative Row 1 except that aluminum chloride was used instead of silicon oxide. The performance of the film is as follows: initial adhesion ○, scratch resistance, hot water resistance (both appearance and adhesion K)
Met.

patent applicant Tokuyama Soda Co., Ltd.

Claims (4)

[Claims] (1) On the surface of the synthetic resin base material, a general formula (where A is a divalent hydrocarbon group whose main chain is linear and has at least 4 atoms, R1 and RB are the same or different furkyl groups or Alkoxyfurkyl group, R
and R are the same or different furkyl groups, and m is 0 or 1). Synthetic resin material having a coating characterized by being coated (2) A synthetic resin material having a coating according to claim 1, wherein in the general formula, A is a hydrocarbon group containing an epoxy group. (3) A synthetic resin material having a coating according to claim 1, wherein in the general formula, A is a hydrocarbon group containing a carbonate group. (4) Synthetic resin material having a coating according to claim 1 used as an optical material