JPS6039291B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent abrasion resistance, flexibility, dyeability,
The present invention also relates to a composition that provides a dyed product with a coating film with good durability and little browning caused by various chemicals, adhesives, etc.

Plastic molded products are used in a wide range of applications due to their advantages such as light weight, easy workability, and impact resistance, but one of their major drawbacks is that they have low surface hardness and are easily scratched.

This deficiency is particularly serious in fields where plastics are widely used and require transparency. For example, in applications such as lenses and windows, it is more susceptible to scratches than regular glass. To solve this problem, it has been proposed to cover with a coating material that has good scratch resistance. Among these, coating materials have been proposed that are made by heat curing of various silicone resin compositions, particularly silane compounds having or not having various functional groups, such as hydrolysates of tetraalkoxysilanes and trialkoxyalkylsilanes. Among these, compositions for coating materials that can improve surface hardness, can be dyed with disperse dyes, and have good bending resistance have been reported (Japanese Unexamined Patent Publication No. 53-11136, Tokuseki Showa 51-
58425). When this composition is used for sunglass lenses, for example, sunglasses that can be dyed after coating can be obtained, and can be dyed as desired at any time according to the customer's request, resulting in products of high value as fashion products.
However, the durability of the dyed products in this case is not necessarily satisfactory. Durability here refers to both the durability of the coating film itself and the stability of the color of the dyed product. To test the durability of the coating, there are accelerated tests using various light resistance testers or weather resistance testers using carbon arc, xenon arc, etc. as light sources, accelerated heating tests using drying, green heat, etc., as well as outdoor peeling tests. These tests are widely used as a means of determining the durability of actual products. The effectiveness of the present invention is also determined based on these test results. Color stability largely depends on the selected beam material, but particularly important are the dye migration and beam transfer properties that are currently observed in disperse dyes. In particular, the color of the thighs due to the extraction of dyes when in contact with various chemicals is of practical importance. For example, dyed items may appear brown if they are exposed to cosmetics such as hairspray, lotion, cologne, insect repellents, alcoholic beverages such as wine or whiskey, etc. Furthermore, adhesive tapes and adhesive stickers sometimes use various high-boiling solvents, especially alcohol, to adjust the tackiness of the adhesive, but if there is a thigh color caused by these solvents, it will leave a mark and cause the problem of dyed products. Significantly reduces product value. Furthermore, the brown color caused by plasticizers contained in vinyl chloride and the like is also important.

For example, if it comes into contact with packaging film for a long time, it may turn silver. Silver colors based solely on hot water dye extraction are also important for their durability in humid locations (eg, baths, swimming pools, etc.). In other words, with conventional techniques, although it is possible to dye optical materials such as plastic lenses, dyes tend to fall off and have poor stability in terms of light fastness, chemical resistance, etc., and improvements to these drawbacks have been desired. It is. The composition described in the present invention exhibits the above-mentioned excellent properties regarding durability and color stability, and is particularly suitable for applications requiring fashionability, such as plastic lenses such as sunglass lenses and corrective lenses, various showcases, and cosmetics. It provides a covering material that is passed through a case or the like.

The coating composition of the present invention consists of components A, B, C and D below.

A: A hydrolyzate of a silane compound having in its molecule at least one glycidyl group or methylglycidyl group and two or more alkoxyl groups bonded to a silicon atom.

Hydrolyzate of B8-(3,4-epoxycyclohexyl)ethyltrialkoxysilane.

C Average particle size of about 1 to 10 yen.

D An aluminum chelate compound represented by the general formula AI・Xn・Y3-n.

(Here, X is a lower alkoxyl group, Y is M'COC
Ligands (M1, M2
, M and M4 are lower alkyl groups), and n is 0, 1 or 2. ) As the compound forming the hydrolyzate of component A, a compound represented by the following general formula is preferably used.

(where RI is an alkyl or alkoxyalkyl group having 1 to 4 carbon atoms, R2 is an alkyl or aryl group having 1 to 6 carbon atoms, R3 is hydrogen or a methyl group, m is 2 or 3, a is an integer from 1 to 6, and is 1 or 2.

) Examples of these compounds include y-glycidoxypropyltrimexoxysilane, y-glycidoxypropyltriethoxysilane, y-glycidoxypropylmethyldimethoxysilane, y-glycidoxypropylmethyldiethoxysilane and -glycidoxyethoxypropylmethyldimethoxysilane, etc.

Examples of compounds forming the hydrolyzate of component B include 3-
Examples include (3,4-epoxycyclohexyl)ethyltrimethoxysilane and 8-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

An effective example of fine silica particles as component C is silica sol.

Silica sols are colloidal dispersions of high molecular weight silicic anhydride in organic solvents such as water and/or alcohols.
For purposes of this invention, average particle diameters of about 1 to 10 mm are used, with particles having a diameter of about 5 to 3 mm being particularly preferred. Various compounds can be used as the aluminum chelate compound of component D. From the viewpoint of catalytic activity, solubility in the composition, and stability, preferred examples include aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, and aluminum bisethyl. Examples include acetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-j-propoxide monomethylacetoacetate, and the like.

Mixtures of these compounds can also be used. Furthermore, at least one compound selected from the following group can be used as component E, if necessary.

(1'R4 Stem R5$iOtsu-(a+b) hydrolyzate of the compound.

Here, R4 and R5 are alkyl, alkenyl, aryl,
methacryloxypropyl or alkyl halide,
Z is an alkoxyl group or an acyloxy group, a and b are each 0, 1 or 2, and a+b is 0, 1
Or 2. '2' Polyfunctional epoxy compound Compounds forming the hydrolyzate of '1) above include tetrasilicate such as methyl silicate, ethyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate. Alkoxysilanes, methyltrimethoxysilane, vinyltrimethoxysilane, pinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, y-chloropropyltrimethoxysilane, and 3,3, Examples include trialkoxy or triacyloxysilanes such as 3-trifluoropropyltrimethoxysilane, and dialkoxysilanes such as dimethyldimethoxysilane and phenylmethyldimethoxysilane.

The above polyfunctional epoxy compound (2) is widely used as a coating material and a molding material. These compounds are preferably polyglycidyl esters or polyglycidyl esters. The polyglycidyl ether is preferably a reaction product between a polyfunctional phenol and epichlorohydrin, or a reaction product between an aliphatic or alicyclic polyhydric alcohol and epichlorohydrin, and has a molecular weight of 1000 or less. Examples of polyfunctional phenols used for this include 2,2-di(P-hydroxyphenyl)propane (bisphenol A), di(P-hydroxyphenyl)methane (bisphenol F), etc. There is.

The aliphatic or alicyclic polyhydric compound used therein is preferably an alcohol having 15 or less carbon atoms.

These alcohols include (poly)ethylene glycol
(poly)propylene glycol, neobentyl glycol, glycerol, trimethylolethane trimethyl. Examples include alcohol propane, bentalystol, diglycerol, sorbitol, 1,4-dihydroxymethylcyclohexane, and hydrogenated bisphenol A. As polyglycidyl esters, reaction products of aliphatic, cycloaliphatic and aromatic polybasic acids having up to 8 carbon atoms or their anhydrides and epichlorohydrin are preferred and used in these reactions. Examples of polybasic acids include succinic acid, glutaric acid, adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, isophthalic acid, and terephthalic acid.

The {1} silane hydrolysates of component A, component B, and component E described above can be obtained by hydrolyzing the corresponding silane compounds with pure water or a dilute aqueous solution of hydrochloric acid or sulfuric acid.

Hydrolysis can also be carried out without using a solvent, using only the alcohol or carboxylic acid generated during the reaction of water and silanes. It is also possible to add or replace other solvents. When hydrolyzing two or more types of silanes, it is possible to hydrolyze each silane separately and mix them, but there is also a method of co-hydrolyzing the mixed silanes, or a method of hydrolyzing one silane and then adding the other silane. In addition to this,
A sequential hydrolysis method in which hydrolysis is continued can be applied.

Next, before describing the mixing ratio of each of the above components, the calculated solid weight used as a reference will be defined below.

The calculated solid weight W of the hydrolyzate (component A, component B, and component E {1}) is based on the weight of the silane compound QkSj(OS)4-k (molecular weight Mo) used before hydrolysis is Wo If , then it is a quantity defined by the following equation.

WW.・KasaHere, M is a formula quantity expressed as QkS; 0 (4-me/2).

Note that Q and S mean corresponding organic groups in the silane compounds used in component A, component B, and component EO described above, and k' is 0, 1, or 2. The calculated solid weight of component E■ is the amount used.

Component A and component B are used in various ratios, but the calculated solid weight of component B is approximately 1 for the sum of the calculated solid weight of component A, component B, and optionally added component E.
It is preferably in the range of 0 to 80%.

If the amount is less than this, the chemical resistance and durability which are the objectives of the present invention will be insufficient, and if it is too much, the dyeability will be insufficient. Component C is preferably used in an amount of 5 to 50 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the total amount of component A, component B, and optionally added component E.

If the amount of component C is small, the hardness tends to be low, whereas if it is too large, coating film defects such as cracking will occur. A variety of solvents can be used in the coating compositions described above.

This solvent is appropriately selected depending on the coating method, heating method, type of base material, etc. used, but it must contain water of about 1% or more, preferably about 2% or more by weight. is important in stabilizing the coating composition. If the water content is less than 1%, the viscosity of the coating composition increases due to the reaction of the hydrolyzate of the silane compound, making it difficult to control the coating thickness. Furthermore, since a reaction occurs in the solution before coating, curing during the coating film formation stage is incomplete and the coating film hardness is not increased. The moisture in the coating composition may be generated due to insufficient hydrolysis of silanes, may be generated due to a condensation reaction of a hydrolyzate of silanes, or may be added separately from outside the system.

Various other additives can be added to the coating composition of the present invention.

For example, various surfactants are effective for controlling the fluidity of the coating film during the coating stage, increasing the surface smoothness, and reducing the coefficient of friction of the surface. Examples of these effects include graft copolymers of linear polysiloxanes with alkylene oxides. Furthermore, ultraviolet absorbers, antioxidants, etc. can be used.

Various other organic polymers can be used to improve the physical properties, adhesion, and paintability of the coating film. The coating composition of the present invention can be applied to a variety of substrates, but transparent plastic substrates such as polyacrylate, especially polymethyl methacrylate, polycarbonate, diethylene glycol bead allyl carbonate, etc. are particularly suitable. . As the coating method, a commonly used coating method can be applied.

For example, dip coating, spin coating, roll coating, curtain flow coating, spray coating, etc. can be applied. Curing of the coating composition is accomplished by heating.

The applicable temperature is limited depending on the temperature used, but from 50 to
A range of 250 qo gives good results. The coating composition of the present invention can significantly reduce the shedding of dye from dyed materials in optical materials such as dyed plastic lenses, and can significantly improve stability such as light fastness and chemical resistance. It has the remarkable effect of improving the pseudo-damage resistance and delamination I property of the coating film. Example 1 '1} Preparation of a y-glycidoxypropylmethyldiethoxysilane hydrolyzed composition in a reactor equipped with a rotor.
-Glycidoxypropylmethyldiethoxysilane 386
．． Add 3g of 0.05N hydrochloric acid aqueous solution while keeping the temperature at 100% and using a magnetic bath roller.
．． Gradually drip the foundation.

The time required for dropping was 83 minutes. After the dropping was completed, cooling was stopped, and a hydrolyzed composition of y-glycidoxypropylmethyljethoxysilane was obtained (hereinafter abbreviated as H-GMS). The properties of the obtained solution were as follows: epoxy equivalent: 306
The viscosity (at 10°C) was 17.5 centipoise, and the moisture content by gas chromatography was 5.1% by weight. (2} Preparation of silane hydrolyzed composition
Mix 210 g of 8-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in an S24 cone and lower the liquid temperature to 1o.
Keep it at o0.

46 g of 0.01N hydrochloric acid aqueous solution was gradually passed through the tube while shaking the tube. After finishing the application, cooling was stopped and a silane hydrolyzed composition was obtained. Glue Preparation of Paint Add 1000 g of methanol-dispersed colloidal silica (“Methanol Silicazo'V” solid content 30%, manufactured by Nissan Chemical Co., Ltd.) to 499 g of the above-mentioned silane hydrolyzed composition, and methanol 3
94g, 9 bases of diethylene glycol dimethyl ether,
3 g of a silicone surfactant was added and wetted, and 3 pieces of aluminum acetylacetonate were added to this mixed solution and mixed with a punch to obtain a paint.

'4' Application and Evaluation Diethylene glycol bisallyl carbonate polymer resin (product of Riken Lens Industries Co., Ltd., CR-39) was prepared by soaking the paint in the previous section in a caustic soda aqueous solution and washing it.
It was coated on a plano lens (plano lens) with a side diameter of 75 mm and a rib thickness of 2.1 mm using a dipping method at a pulling rate of 10 k/min, and was heated and cured in a hot air dryer at 93 qC for 4 hours.

The coated lenses were tested as described below. The results are shown in Table 1. 'A' Abrasion Resistance Test 'a' Steel Wool Scratch Hardness The surface of the coating was rubbed with steel wool #0000 to examine its resistance to scratches.

The judgment was made as follows. A...It won't get scratched even if it is rubbed strongly.

B: If you rub it quite strongly, it will get a little scratched. C
...Even weak friction can cause damage. Further, the intermediate values are expressed as, for example, B to C.

Note that the diethylene glycol bisallyl carbonate polymer stain, which was not coated at all, was graded C.

'b} /Gunda Ablation Test Carborundum #600, 0.0 Satoshi adhered to a pad made of wool felt (made by Nippon Felt Co., Ltd., 20 JRW, 2 ribs thick) with a diameter of 3 sides. Place it on the convex surface of the lens,
While rotating the lens at a rate of 8 times/min, apply one more pad.
Move back and forth at a rate of 43 times/minute.

After this was carried out for 14 minutes, the increase in haze on the lens surface was examined. '.

}The appearance was examined with the naked eye for transparency, presence of uneven coating, etc.

1. Draw 11 parallel lines at equal intervals on the adhesive coating surface, and draw the same number of parallel lines that intersect with these at right angles to form a square ION.

These lines cut through the coating to the extent that they reach the substrate.
Strongly adhere cellophane adhesive tape (product name: "Cello Tape", manufactured by Nichiban Co., Ltd.) on top of this goblin, and
The coating film was peeled off rapidly in the degree direction and the presence or absence of peeling of the coating film was examined. 8
A disperse dye was used as the dye.

Miketone Polyester Red F (Mitsui Tosho Co., Ltd. product) 0.812g, Dianic Yellow Station-E (Mitsubishi Kasei Co., Ltd. product) 0.4375g, Karon Polyester Blue TS (Japanese version) Yakuhin Co., Ltd. product) 3.750
Place each female in a 1 liter beaker, add 6 g of Rapizol B-80 (product of NOF Corporation), add about 1 female of water, and thoroughly knead with a glass rod.

Thereafter, the mixture was further dispersed and dissolved in warm water of about 8,000 ml to obtain a stain. Using this beam bath, beam coating was carried out at 80°C for 13 minutes. Evaluation was performed by measuring the total light transmittance of the dye lens. Teflon ring (inner diameter 12.65 mm) sealed with silicone grease on the concave surface of the chemical resistance test lens.
Place the skin (3.35cm thick) and apply approximately 0.0cm of chemicals inside this ring. Enter mother c.

After the chemicals were injected, they were further covered with a glass plate sealed with silicone grease and left for 24 hours at a temperature of 2,000. ○...No change at allx...Slight change x×...Significant change×××...Significant change in skin Weather resistance test Otsu City, Shiga Prefecture Outdoor exposure tests were conducted for one month from July 24, 1972, and for one month from August 28, 1972 in Florida, United States.

All tests were conducted on a slope of 45o south. After exposure, the presence or absence of abnormalities such as cracks in the paint film, wavy, uneven, soggy skin, and whitening was examined. Comparative Example 1 {1) Preparation of Paint 68.7 g of H-GMS from Example 1 was mixed with methanol and IJ Kasol 140. 4g diethylene glycol dimethylenal, 10.5g, methanol 21.1g, and silicone surfactant 0.36g were added and mixed while pouring into a barrel.

Add aluminum acetylacetonate 4.2 to this mixture.
g was added and mixed with Hashiyo to prepare a paint. '2} Coating and Evaluation A performance test of the coating film was conducted according to Example 1 using the above-mentioned coating material.

The results are shown in Table 1. Comparative Example 2 [1] 3-(3,4-epoxycyclohexyl)ethyl. Preparation of trimethoxysilane hydrolysis composition 168g of 3-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was charged into a reactor equipped with a rotor, the liquid temperature was maintained at 20q0, and the mixture was stirred with a magnetic stirrer. While adding 0.01 N hydrochloric acid aqueous solution 37. Gradually drip the foundation.

After the dropping was completed, the process was stopped and a hydrolyzed composition of 8-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was obtained (hereinafter abbreviated as H-BCE). (2' Preparation of paint Add 389 g of methanol silica sol to 162 g of the above H-BCE.
g, methanol 51g, phenethyl alcohol 29.3g
g and 1 g of silicone surfactant were added and mixed.

Add 11% of aluminum acetylacetonate to this mixture.
7 g was added and mixed with Azusa to form a paint. Glue Application and Evaluation A performance test of the coating film was conducted in accordance with Example 1 using the coating material described above.

The results are shown in Table 1. Table 1 Example 2 '1} Preparation of paint The silane hydrolyzed composition 41 of Example 1 was heated with "Epicote 827" (product of Shell Chemical Co., Ltd., epoxy equivalent: about 185, bisphenol A type epoxy resin) for 14 hours. Diacetone alcohol 20%, benzyl alcohol 100%
g, 305 g of methanol, and a silicone surfactant were added and mixed, and further, methanol silica sol 132 was added and mixed.

4 pieces of aluminum acetylacetonate were added to this liquid mixture, and the mixture was mixed to obtain a paint. (2) Coating and Evaluation Coating was carried out in accordance with Example 1 using the paint described above.

Further, evaluation was carried out according to Example 1 except for chemical resistance. The results are shown in Table 2. {Mura Chemical Resistance Tezto-stained lenses were immersed in a mixed solution of ethanol/water (70/30 weight ratio) at 21 to 220 for 2 hours, and then evaluated by the change in transmittance. △T = Transmittance before immersion - Transmittance after immersion △C = Transmittance after immersion) - Transmittance before immersion)
I.

〇〆og (transmittance before immersion groove) The change in transmittance was expressed by △T and △C above.

Comparative example 3tl - Adjustment of paint 442.1g of H-GMS of Example 1 was added with "Epicote" 1
55.4 g of diacetone alcohol, 223.8 g, and benzyl alcohol, 111.6 g were mixed to obtain a homogeneous solution.

To this solution, methanol silica sol 142 base, 597.5 g of methanol, and 3.8 g of silicone surfactant were added and mixed well. 42.7 g of aluminum acetylacetonate was added to this mixed solution and mixed to obtain a paint. ■
Application and Evaluation A performance test of the coating film was conducted in accordance with Example 2 using the above-mentioned coating material.

The results are shown in Table 2. Table 2 Example 3 {11 H-OMS394 of Paint Adjustment Example 1. H-BC of Comparative Example 2
E205. The rest was mixed.

The following solution, which was separately prepared in advance, was added to and mixed with this mixed solution. The additive solution was "Epicoat 827" 24.
8g, "Shodyne 508'' (product of Showa Denko K.K., epoxy equivalent: approx. 190, phthalate glycidyl ester epoxy resin) 64. Thigh, benzyl alcohol 385
g, acetylacetone 96. and 4.8 g of a silicone surfactant were mixed. Further, 1,962 g of methanol silica sol was added and mixed to the solution consisting of the silane hydrolyzed composition, epoxy resin, etc., and then 73 g of aluminum acetylacetonate was added and mixed. Heat was added, and the mixture was expanded and used as paint.

■ Application and evaluation Using the paint described in the previous section, a lens molded product of 75 Yanagi diameter and 1.8 Yanagi thickness injection molded with polymethyl methacrylate (Mitsubishi Rayon Co., Ltd. product, "Acrivet" VH) was coated with immersion therapy at a pulling rate of 10c. The coating was applied under the conditions of 1/min, and heated and cured for 2 hours in a 970 hot air dryer.

Performance evaluation was conducted in accordance with Example 1 except for chemical resistance.

The results are shown in Table 3. Chemical resistance test A commercially available PVC adhesive sealant was attached to a dye lens, and the dye transfer to the adhesive tape was observed after being left at 8000°C for 2 hours and 40q○ for 2 weeks, respectively. Comparative Example 4m Preparation of Paint A solution 58.89% of the epoxy resin prepared in advance as described in Example 3 was mixed and dissolved in the H-GMS58.3 key of Example 1.

To this mixed solution, 21 cycles of methanol silica sol were added and mixed, and then aluminum acetylacetonate 8.17
g was added, and the mixture was mixed to make a paint. '2} Coating and Evaluation A performance test of the coating film was conducted according to Example 3 using the above-mentioned coating material.

The results are shown in Table 3. Table 3 Comparative Example 5 The same procedures as in Example 1 were carried out except that methanol silica sol, which is one of the components C of the present invention, was not added.

As a result, the obtained coating had a steel wool attraction hardness of B to C and a putt abousion test of 15.3.
The dye property was 83.0.

This shows that silica sol is an essential component to obtain a coating with good hardness. Comparative Example 2 In Example 1, an experiment was conducted in which aluminum triisopropoxide was used instead of aluminum acetylacetonate, which is one of the D components of the present invention.

As a result, many fine particles 4 and foreign matter were generated in the coating, and an optical material having satisfactory quality could not be obtained.

Claims (1)

[Scope of Claims] 1. A coating composition characterized by containing the following components A, B, C and D. A: A hydrolyzate of a silane compound having in its molecule at least one glycidyl group or methylglycidyl group and two or more alkoxyl groups bonded to a silicon atom. B Hydrolyzate of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane. C Fine particulate silica with an average particle diameter of about 1 to 10 mμ. D An aluminum chelate compound represented by the general formula A1・X_n・Y_3_-_n. (Here, X is a lower alkoxyl group, Y is M'COCH_
Ligands (M^1) resulting from compounds selected from the group consisting of 2COM^2 and M^3COCH_2COOM^4
, M^2, M^3 and M^4 are lower alkyl groups), n
is 0, 1 or 2. )