JPS60186570A - Composition for coating - Google Patents

Abstract

PURPOSE:The titled compostion for forming a non-fogging film on the surface of glass such as lens, mirror, etc. and a film having high surface hardness and improved corrosion resistance on the surface of plastic, containing an alkoxysilane and a cationic photopolymerization initiator. CONSTITUTION:(A) An alkoxysilane [e.g., one selected from polysiloxanes obtained by subjecting partially one or more of tetraalkoxysilane, trialkoxysilane and dialkoxysilane shown by the formula RnSi(OR')4-n (R is 1-6C alkyl, cycloalkyl, phenyl, vinyl or aryl; R' is 1-4C alkyl; n is 0, 1, or 2) to polycondensation], and (B) 0.01-10wt% (based on the component A) of cationic polymerization initiator (e.g., triarylsulfonium salt, etc.) are dissolved or dispersed into (C) an organic solvent, to give the desired composition.

Description

[Detailed description of the invention]

Field of Application of the Invention: The present invention relates to a coating composition (particularly, a composition suitable for forming a coating film of an organonlan having a surface (20H group). The coating composition is anti-m flG
For the purpose of forming a corrosion-resistant coating film on glass surfaces such as lenses and mirrors for the purpose of forming a plastic surface (=, also for the purpose of forming a corrosion-resistant coating film with high surface hardness) For the purpose of forming metal surfaces (
There are 81 rivers in total. Conventional technology: Coating films mainly composed of organosilane polymers have high surface hardness and are excellent in solvent resistance and corrosion resistance.
Many coating compositions based on organosilanes have been proposed.Most of them are based on organosilanes with substituents having polymerizable unsaturated bonds. There are so many 1]11 proposals that even cite the literature.These coating compositions are thermally cured or photocured (secondarily, polymerization of the phase bond of the substituent By selecting the organosilane, a coating film with characteristics can be formed.However, these coating compositions +:
Oi-C is No. 11 (11) whose main component, organosilane, is difficult to manufacture and difficult to obtain. Available at cheap price
11 Organosilanes include alkoxyranes, and a thermosetting coating composition consisting of a polymer obtained by hydrolyzing an alkoxysilane monomer and/or an alkoxyrane and a resin content of zero acrylic resin is Unexamined Japanese Patent Application Publication No. 51-33128,
Japanese Patent Application Publication No. 58-167650, Japanese Patent Publication No. 59-522
No. 1 Publication 0 (-proposed-C) These (in 2, what replaces coating II) are anti-greasy components, and alcoquine silanes are used as filling valves 1 to modify the coating film. Although it is possible to obtain a coating film with high surface hardness, it is not possible to obtain satisfactory solvent resistance and glass surface (= antifogging properties when formed).On the other hand, Conventionally, a coating composition is coated with an organic solvent solution of alkoxysilane, which has been used for the purpose of forming a glass substrate surface (25iOJi') for parts such as semicircular bodies. As a method, there is a method in which a heat-resistant substrate such as glass or metal is coated and heat treated at a relatively low temperature of 200 to 300°C to form a coating film of alkoxysilane having a 20H group on the surface. 1977
-8258 Publication) Coating 1 formed by the method
Because TOJI has 011 groups on the surface, when formed on the glass surface, it exhibits excellent 1υJ5 properties, and
<T> When the layer surface iR1 is formed. It has 7 and 6 properties, and has a high Table 1 hardness, so it has excellent M abrasion resistance. However, when applied to plastic surfaces, [)
In addition to item 11, it is expected that a coating film with excellent solvent resistance will be formed, but as mentioned above! Processing 711
iii Iu: In many cases, the heat resistance of the plastic to be coated exceeds 1%i degree.
The disadvantage is that the body deteriorates. Problems to be solved by the invention: This defense states that the coating film of alkoxysilane having 11 former 2011 groups can be formed with a low grade of 1, especially (Niblastic's heat resistance temperature good). It is an object of the present invention to provide a composition for coating a cypress silane and a cation. This is a coating composition comprising a system polymerization initiator.In the present invention C2, the alkoxysilane has the following general formula (1) % formula % (1) R is the same kind of alkyl group having 1 to 6 carbon atoms, cycloalkyl group, phenyl group, vinyl group and allyl group, R' is the same kind of alkyl group having 1 to 4 carbon atoms, and n is O Tetraalcoquine silanes, trialkoxysilanes where n is 1, dialkoxysilanes where n is 2, 11 and the above-mentioned alkoxysilanes, 1+!II alone or in partial condensation. In the present invention (2), cationic photopolymerization initiation 11 is a cationic photopolymerization initiator that generates radicals from irradiation with actinic rays (2). Any of the photopolymerization initiators can be used.Function: As a result of extensive research by the present inventors regarding the condensation polymerization of - and alkoxysilanes, the inventors have discovered a surprising fact (2. j is cationic photopolymerization [) (1) presence of initiator (2) irradiation with actinic rays (C2), lower?
i, A If -f'' t- It was discovered and completed that condensation polymerization occurs rapidly.The present invention (2) In the present invention, a high-pressure mercury lamp or a metal halide lamp is used to form a coating film of the coating composition. 20()~5
By irradiating ultraviolet rays of 00+un as actinic rays, the catimene-based photopolymerization initiator in raw NBR was
Desorption of the alcogine group of the alcogine silanes in the container (acts twice, converting the alkoxysilane treatment 1 into oil compound IIvi and (2, coating with the surface iM mouth 20FI ; +) In the present invention, the alcoginsilanes which are the main components of the coating composition have the general formula (in 11)) mocha,
Alkyl group having 1 to 6 carbon atoms, cycloargyl group, phenyl group, vinyl, I41. : and allyl group difference (τI
I is f111, ■t' is carbonic acid, y, fjj is the same as an alkyl group of numbers 1 to 4, for example, detramethquine νran, detraethoxyl silane, tetraisopropoxysilane, etrabutoxysilane, dimethoxy General formulas such as jetoxysilane, dimethoxydiisopropoxysilane, diethoxydiisoprobogycinlan, diethquindibutquinsilane (tetraalkoxysilanes where n in 11 is 0, methyltrimethoxysilane, methyltriethoxysilane, Methyltriisopropoquine silane,
Ethertryptoxylan, Ethertryptoquinsilane,
Trialkoxysilanes in which n is 1 in the general formula (1) such as cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltriethoxysilane, allyltriethoxysilane, dimeboul dimethoxysilane, dimethyljethoxysilane, General formulas such as diethyldietoginsilane, dietherdyptogine ν-lan, phenylethylshedoxinlan (dialcoquinones in which n in 11 is 2, and IVi of the above alkoxysilane alone or in combination of two or more) One or more of the polysiloxanes found in the polysiloxane group obtained by condensation polymerization of the mixture can be used.
Use polysilochitins that are stable against hydrolysis caused by Polysiloxanes can also be produced by subjecting alkoxysilane monomers, organic acids such as acetic acid, and lower alcohols such as methanol, ethanol, isopropanol, n-butanol, etc. to a reflux-de-C heating reaction. In organic solvents, acidic acids such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphoric acid, organic acids such as acetic acid, or alkaline catalysts such as sodium hydroxide, potassium hydroxide, and ammonium hydroxide. % as a partially reduced compound of the alkoxysilane (dihydrolyzed (dihydrolyzed) etc.
i can be in danger. In the present invention, the following Ar, -8
-X...Mountain...River (2) Ar. Triarylsulfonium salts represented by, for example, triphenylsulfonium 1xafluorophosphate, etc., have the following general formula (3): (=, Ar4. Ar2 and X have the same meanings as above.) Diaryliodonicum salts represented by, for example, diphenyliodonicum hexafluorophosphate, etc., are represented by the following general formula (4) % formula % (4) (where ζ:, Ar, and X represent the same meanings as above). ) Aryldiazonium salts represented by ■) -methoxybenzenediazonium hexafluorophosphate, etc., unsaturated nitrosamines, cyclopentadienylmanganese tricarbonyl,! Bis(purpuroalkylsulfonyl)methane silver salt, Lewis lIF5 dimebylylium salt, etc. can be exemplified. 0.01~1
0 city) within the range of 11%. In the present invention (2), the coating composition is usually used after being dissolved or dispersed.
The solvent is (Samurai C: Although not limited, it is preferable to use a solvent that can dissolve both the alkoxysilane and the cationic photopolymerization initiator. For example, methanol, ethanol, in-propyl alcohol, etc. tools, butanol, 11-alcohols, methyl acetate, enalacedate, acetic acid esters, mesylacetoacetate, ethyl acetoacetate, AT m esters, acetylacetone, β-diketones, etc. It is possible to mention the production of a single solvent or a mixture of two or more species. In the present invention, the coating II formed

[Improved performance such as flexibility, adhesion 141, heat cycle resistance, etc. 4
Various polymeric compounds can be added to the coating composition (2, desired C2 for the purpose of 1'). For example, side chains (20H group A polymer compound having polyethylene glycol,
Polymer compounds having an OH group at the end such as polypropylene glycol, bisphenol A diglycidyl ether,
l, 4 butanediol digrindyl ether, 3.4
- Epoxy 11″f1 such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate
fat, fugonoxy] t, 1 fat, alkyd resin, side chain (20H group or amide blockage, polymer compounds such as poly-2-hydroxyethyl methacrylate, etc.) Molecular compounds can be added.Addition of these polymer compounds 9'h (,:,
In the coating composition (2I~30th,' fy
? % range. In addition, the epoxy 4 and 1 fats are preferably added to a cationic photopolymerization initiator (one that further polymerizes by combining 2 and 111). In the present invention (2), for coating Depending on the circumstances, the composition may contain other than the above-mentioned polymer compounds (nitric acid forming agents, such as phosphorus compounds, boron compounds, arsenic compounds, lead compounds, etc.).
111 Lead compounds, etc., other than silicon compounds m'j 'Q
In4+ compounds, such as Ti, i'a, Sn
, Alcogides, chelates, and acylated metals such as Zr are further added and used. The coating composition of the present invention (3M) is applied uniformly to the surface of a substrate that has been subjected to a dehydration treatment, such as glass, plastron, or metal.
After dry heating for 0.5 to 5 minutes at a temperature of 80 to 100 °C, use a high-pressure mercury lamp or metal halide lamp to irradiate with ultraviolet rays of 200 to 500 nm as actinic rays.
= irradiation for 300 seconds (from the second step, the desired cope ink ribs are formed immediately. The method of applying the coating composition is a method that can be applied in two strokes). There is no particular restriction on the method, and any of the dipping method, spray method, spinner method, roll coating method, ultrasonic atomization method, screen marking method, etc. can be adopted.・) and comparative examples: Below, the scope of the present invention will be described in Examples and Comparative Examples (from 2nd and further (2nd detailed C: explained.However, it will not occur)) according to the following implementations and examples.
It is not limited to the number of tatami mats. In the Examples and Comparative Examples listed in 'F, parts and % are based on mhq unless otherwise specified. Including 5 ingredients for coating! 4. Sample CI) Reaction vessel with stirrer and reflux condenser (-, 1186 parts rough tetramethoxine, 7643 parts ethanol, intoxication:
206 parts and 3 parts of 35% hydrochloric acid were added, and the reaction was completed by heating and maintaining under reflux for 10 hours while stirring. After adjusting the amount of solvent, 1 degree converted to Sin is 5.0
% alkoxysilane solution, and further (2, 5 in 22.5% (2 equivalent P, converted to alkoxysilane content)
0. was added and dissolved to obtain a solution [:Ia]. Solution [Ia): 100 parts, cationic photopolymerization initiation reaction 11FC-510() riazylsulfonium salt: 3
MIJ-Sales Product): 0.2 part was added and dissolved to prepare a coating composition and used as a sample. Solution (Ia) in which P2O5 was added and dissolved in sample [1 piece] + 100 parts of cationic Bi'811 initiator: UVE-101
4() riazylsulfoniuno, ji,...: CJE
A composition for T, I ---7-ing was prepared by adding and dissolving 05 parts of the following products (sold by the company), and a sample [■''] was prepared. 0. (Ill) Preparation of Sample CII (2) Reaction vessel used (2, Methyl-J-toxysilane: 207x1s, Detraethquinsilane: 25 parts, (1 sheet, Water-ethanol: 250
@(S and 20% salt intoxication; prepare 015 parts, 1.?
15 parts of cold water was added to the boiling water at 70°C (two times), mixed with oil, and heated at 70°C (two times).
Time saving 14iL, te 1. t, and an alkoxysilane solution was obtained. rll Rara Hikimata Alkoxysilane Melt: lOO sound IS
(2. Cationic photopolymerization initiation wound 1: IJVE-10
14 (written as Mi). A coating composition was prepared by dissolving 5 parts of ( ) and preparing a sample [m]. Sample [IV') The warped kernel used for sample CDcoN circumference adjustment was charged in a container (2, 7225,115 parts of trabutkin, and 163 parts of dehydrated ethanol), and further (=20% Mml acid: 0.1
5 parts and 22 parts of water were added to obtain an alkoxysilane solution CIVa at a temperature of 70°C (maintained for 24 hours). Obtained alkoxysilane solution: 0 parts of ICl, 4 parts of epoxy resin (Sheptaloxide #2021, sold by Daicel) and cationic photopolymerization 1hl initiator: l.'C
-510 (above): 0.2 part was added and dissolved to prepare a coating composition, which was used as sample (IV). c■a]: 100 parts, cationic photopolymerization +31-1
Starting agent: DEMPI! "a (allyl diazonium salt:
(Sold by ABM Chemical Co.): 0.1 part, Hexylkis(methginmebul) melamine: 3 parts, γ-Glydoxybrobylmebul diethoxysilane: 3 parts, and aluminum acetonate: 0.1 part were added. A coating composition was prepared by mixing and dissolving and preparing a sample [■]. Comparative sample (Ia:) During the preparation process of the sample CD? 1) The obtained solution (Ia) was used as a comparative sample [■a]. Comparative Sample 0la) The alkoxine run solution obtained in the preparation process of sample J (+11) was used as a comparative sample [disintegration]. Sample Ultra) A commercially available ultraviolet curable acrylic coating agent was
There were 9 samples [111a]. Formation of Coating Film Two glass plates and a polycarbonate resin plate (2) The prepared coating composition was applied to a uniform thickness of 2 coats, and then 120 w firn of metal halide was applied from the hard cloth surface to a distance of '1 (J cm). Actinic light was irradiated for 30 seconds using a lamp to form a coating Bφ.As the ratio Q1, in the case of glass lv, 300 ° C.
A coating film was formed by thermal MJj treatment for 3 hours at °C. Evaluation of coating ++-1: The coke/ink film formed by the above method was subjected to the potency test described above. The test results for the coating film are shown in Table 1. (1) Surface hardness: The pencil hardness was measured according to JIS-G-3320f2. Judgment was made by observing with a 20x magnifying glass and determining whether the pencil was scratch-free. (2) Adhesion: JIS-D-0202+2 groups,
A gopin cellophane peeling test was conducted. Judgment is 100
/100 was marked with a circle, and those in which peeling was observed even in one part were marked with an x. (3) Anti-fogging The substrate on which the coating film was cooled to 5°C was taken out of the surrounding air at 20°C and 70% relative humidity and observed for the occurrence of fog. Those that were not observed were marked with an ○, and those where the occurrence of 5s was observed were marked with an formed)
(The board was immersed in oil for 1 minute and the appearance was observed. Appearance (= No abnormalities were marked Q, and those with abnormalities were marked X. (5) Cold and heat resistance: Coating film J & 4 formed
1y. The temperature of 70℃ (22 hours) and the operation of holding at a temperature of 120℃ (22 hours) were repeated for 5 cycles, and an appearance cherry blossom festival was performed. Judgment was made for the appearance (2) where no abnormality was observed. ○ marks 1. Those with abnormalities are marked X. (6) Salt water resistance = 5% NaC at 40°C: / water soluble salt (19
After soaking for 6 hours, appearance and observation were performed. Appearance (2 abnormalities observed were marked Q, and those with abnormalities were marked X. Effects of the invention: Non-explosion 1 → (2) The coating composition was , a cationic photopolymerization initiator, and optionally M≦additives, which are then placed on a substrate and irradiated with actinic rays (Secondly, a coating film of organosilane is formed. Obtained The coating film is a conventional coating film formed by heat curing in the high jM hair range (comparative example 2 and/or the coating film has OH groups on the surface.Low/I1.1 range) The coating film formed by thermosetting (see Comparative Examples 7 and 9) has a density of =
＜'s 1 bar equivalent to the photocurable coating film of the present invention.
As shown in Comparative Examples 2 and 4, the deviation when obtaining Pl and performance is as follows: (If the board is made of plus boot stock, etc., the compensation heat wetness is 41
< 4 It is necessary to heat cure the coating composition under the conditions described above. It is possible to form organosilane coating films on non-heat resistant substrates such as plastics, which not only greatly reduces the time required for the curing process of the coating film. The present invention provides a transparent organonlan coating film with high surface hardness and excellent adhesion, anti-fogging properties, wash resistance, heat cycle resistance, and salt water resistance on glass, metal, etc. It provides a coating composition that can be photocured (2) on the surface of a plus bouquet in an extremely short period of time, and its H2 industry significance is extremely high.Patent applicant: Japan c! Company agent (6286) Haruyuki Ito (7125) Yoshimi Yokoyama

Claims (1)

[Claims] 1. Alcogine silanes and cationic photopolymerization f
Coating composition 2 containing a lH agent The alkoxysilane is a tetraalkoxysilane, a trialcoxinlan, or a dialcoginlan represented by the following general formula (1)% formula (1) and one or more selected from the group consisting of polysiloxanes in which 14 or 2 a+i or more of the alkoxysilanes described above are partially reduced. The coating composition according to claim 1, wherein the cationic photopolymerization initiator has a diameter of 14゛ selected from the group consisting of triarylsulfonium salts, diaryliodonium salts, aryldiazonium salts, and unsaturated nitrosamines. Product 4: Coating composition according to claim 1, which is obtained by dissolving or dispersing alkoxysilanes and a cationic photoinitiator in an organic solvent.