JPH06279705A - Ultraviolet-curing coating material for hard coat - Google Patents

Abstract

PURPOSE:To provide and additive which is incorporated into an UV-curing coating material used for hard coat for polycarbonate to improve the adhesion after hard coating and a method of using the same. CONSTITUTION:The coating material is obtained by mixing a UV-curing acrylic coating material with at most 50wt.% end-modified polycarbonate oligomer which is derived from a dihydric phenol compound and terminated by a monohydric phenol having a reactive olefin group and which has an average molecular weight of below 10.000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable coating material for hard coat, and more particularly, the present invention provides an ultraviolet-curable coating material for hard coat which has excellent adhesion to polycarbonate.

[0002]

2. Description of the Related Art Conventionally, since the surface of a polycarbonate molded product is easily scratched, a hard coating is applied to the surface of the molded product for the purpose of imparting abrasion resistance and scratch resistance. Generally, hard coats are applied by applying a curable paint to the surface of a polycarbonate molded product, and curing treatment is performed, but recently, hard coats using an ultraviolet curable paint have been increasing from the viewpoint of ease of handling and safety. .

The ultraviolet curable coating composition is mainly composed of acrylic acid ester and is irradiated with ultraviolet rays to polymerize on the surface to form a strong film. However, the ultraviolet curable coating material is only physically adhered to the polycarbonate surface, and in many cases, sufficient adhesive force cannot be obtained such as when the solubility parameters are different, and improvement has been demanded.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks found in conventional hard coats, and provides an ultraviolet-curable coating material for hard coats which is particularly excellent in adhesion to a polycarbonate molded article. It is a thing.

[0005]

As a result of intensive studies to solve the conventional problems, the inventors of the present invention have found that a polycarbonate oligomer having a reactive olefin at the terminal (hereinafter, simply referred to as a terminal-modified polycarbonate) in an ultraviolet curable coating material. It has been found that the mixture of the oligomer) exerts excellent adhesion to the polycarbonate molded product, and the present invention has been completed based on this finding.

That is, the present invention provides an acrylate-based UV-curable coating composition having a viscosity average molecular weight of 10,000 having a terminal group derived from a monohydric phenol having a reactive olefin.
End modified polycarbonate oligomer of less than 50% by weight
The present invention relates to an ultraviolet curable coating material for hard coat, which is obtained by mixing the following.

The terminal-modified polycarbonate oligomer used in the present invention is obtained in the same manner as in the conventional method for producing a polycarbonate resin, except that a monohydric phenol having a reactive olefin is used as a molecular weight modifier or an end terminator. .

That is, in the interfacial polymerization method, after reacting the dihydric phenol compound with phosgene in the presence of a reaction-inert organic solvent and an aqueous alkali solution, a terminal terminating agent and a tertiary amine or quaternary ammonium are used. A method of polymerizing by adding a polymerization catalyst such as a salt, the pyridine method is a method in which a dihydric phenol compound and an endcapping agent are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown to directly obtain a polycarbonate resin. is there. In the interfacial polymerization method, a method of adding a terminal terminator during the reaction between the dihydric phenol compound and phosgene may be used.

The molecular weight modifier or the terminal terminator used in the terminal-modified polycarbonate oligomer of the present invention is a monohydric phenol having a reactive olefin.

Specifically, 4'-hydroxychalcone,
3'-hydroxychalcone, 2'-hydroxychalcone, 4-
Ethoxy-2'-hydroxychalcone, 4-ethoxy-3'-
Hydroxychalcone, 4-ethoxy-4'-hydroxychalcone, 4-diethylamino-4'-hydroxychalcone, 4
-Methoxy-4'-hydroxychalcone, 4-nitro-4'-hydroxychalcone, 4-dimethylamino-4'-hydroxychalcone, 4-methyl-4'-hydroxychalcone and other chalcone derivatives, p-hydroxystyrene, p -Styrene derivatives such as isopropenylphenol, O-allylphenol, allylphenol derivatives such as eugenol, cinnamylidene-3-hydroxyacetophenone,
Cinnamylidene 4-hydroxyacetophenone, 4-
Hydroxycinnamylidene acetophenone, 2-β-methylcinnamylideneethyl-4-hydroxyphenylketone, 2-cinnamylideneethyl-3-hydroxyphenylketone, 2-4-hydroxyphenylcinnamylidene ethylphenylketone and other cinnamylidenes Derivatives are exemplified. These monohydric phenols are used alone or in combination of two or more.

The molecular weight regulator or the terminal terminator is used in an amount of 200 to 11 mol, preferably 100 to 20 mol, per 100 mol of the dihydric phenol compound.

Specific examples of the dihydric phenol compound used for producing the terminal-modified polycarbonate oligomer of the present invention include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl) ether. Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BP
Z), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-) 3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α, ω-bis [3 Examples include-(O-hydroxyphenyl) propyl] polydimethylsiloxane bisphenol and the like.

Of these, bis (4-hydroxyphenyl) ether, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, 2,2-bis (4-hydroxy-3-). Methylphenyl) propane and 1,1-bis (4-hydroxyphenyl) -1-phenylethane are preferred. These bisphenol compounds can be used alone or in combination of two or more kinds.

The reaction-inert solvent used for producing the terminal-modified polycarbonate oligomer of the present invention includes:
Chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene; benzene, toluene, Aromatic hydrocarbons such as xylene and ethylbenzene; ether compounds such as diethyl ether can be mentioned, and two or more kinds of these organic solvents can be mixed and used.

If desired, ethers other than the above,
Solvents having an affinity for water, such as ketones, esters, nitriles, etc., may be used within limits that the mixed solvent system is not completely compatible with water.

As the polymerization catalyst, trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,
Tertiary amines such as N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like.

The terminal-modified polycarbonate oligomer in the present invention further comprises a branched-chain polycarbonate oligomer in which a branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, based on the above dihydric phenol compound. It is possible to

As a branching agent, phloroglucin, 2,6
-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzole, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′,
Polyhydroxy compounds such as α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,3-bis (4-hydroxyphenyl) oxindole (= isatin bisphenol) Is exemplified.

The terminal-modified polycarbonate oligomer used in the present invention has a viscosity average molecular weight of less than 10,000, preferably 1,000 to 8,000.

As a method of adding the terminal-modified polycarbonate oligomer to the UV-curable coating, if the oligomer is easily dissolved in the UV-curable coating to be added, it may be mixed as it is, but it is not dissolved or is easily dissolved. If not, the oligomer can be dissolved in a solvent and added to the paint.

The solvent used when the terminal-modified polycarbonate oligomer is dissolved in a solvent and added is
Toluene, dimethylformamide, cyclohexanone,
Examples include ethyl acetate, acetone, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, tetrahydrofuran and the like.

Considering that the polycarbonate molded article to which the UV-curable coating material for hard coat of the present invention is applied is generally bisphenol A type polycarbonate, monochloromethane and dichloromethane which are good solvents for bisphenol A type polycarbonate. , Chloroform, monochlorobenzene, and 1,4-dioxane may attack the surface of the polycarbonate molded article, and these solvents are not preferable.

In the present invention, the content of the terminal-modified polycarbonate oligomer is usually 50% by weight or less. However, in consideration of melt viscosity and economical efficiency, 0.
1 to 20% by weight is desirable. When the terminal-modified polycarbonate oligomer is dissolved in a solvent and mixed, it is preferably 0.1 to 20% by weight based on the total amount excluding the solvent.

Preferred examples of the UV-curable coating material in the present invention include epoxy-based, urethane acrylate-based, polyester acrylate-based, polybutadiene acrylate-based, and polyol polyacrylate-based monomer-type or oligomer-type UV-curable coatings. These UV-curable coatings may be added with an acrylic acid ester monomer or a solvent such as toluene according to the purpose.

A polycarbonate molded product having a hard coat applied to the surface of the molded product by the ultraviolet-curable coating material of the present invention is molded by extrusion molding, injection molding, compression molding, blow molding, wet molding or the like.

In the production of molded articles, if desired, antioxidants, light stabilizers, colorants, inorganic and organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants and antistatic agents. And the like may be appropriately used in combination.

[0027]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Reference Example 1 (Production of Terminal-Modified Polycarbonate Oligomer) In 5.8 liters of 8.8% (w / v) sodium hydroxide aqueous solution,
1,1-bis (4-hydroxyphenyl) cyclohexane (B
1070 g of PZ) and 1 g of hydrosulfite were added and dissolved. To this, 3.6 liters of methylene chloride was added, and 4'-hydroxychalcone was added while stirring while maintaining the liquid temperature at 15 ° C.
256 g was added, and then 520 g of phosgene was introduced for 60 minutes. After the introduction of phosgene, the reaction solution was emulsified by vigorous stirring. After emulsification, 2 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization. After the reaction was completed, the polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing solution was repeatedly washed with water until the pH became neutral, and then 4.7 liters of isopropanol was added to the polymerization product. Was allowed to settle. The precipitate was filtered and vacuum dried to obtain about 1.2 kg of a terminal olefin polycarbonate oligomer. The viscosity average molecular weight of this oligomer is
It was 0.5 × 10 ⁴ .

Reference Example 2 A terminal olefin polycarbonate oligomer was obtained in the same manner as in Reference Example 1 except that 1025 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane was used instead of BPZ. The viscosity average molecular weight of this oligomer was 0.5 × 10 ⁴ .

Reference Example 3 An end-modified polycarbonate oligomer was obtained in the same manner as in Reference Example 1 except that 153 g of p-isopropenylphenol was used instead of 4′-hydroxychalcone of Reference Example 1.
The viscosity average molecular weight of this oligomer was 0.5 × 10 ⁴ .

Reference Example 4 (Production of an end-modified polycarbonate oligomer having no reactive olefin at the end) Same as Reference Example 1 except that 171 g of p-tert-butylphenol was used instead of 4′-hydroxychalcone of Reference Example 1. To obtain a terminal-modified polycarbonate oligomer. The viscosity average molecular weight of this polycarbonate oligomer was 0.5 × 10 ⁴ .

Example 1 Of the terminal-modified polycarbonate oligomer obtained in Reference Example 1,
500 ml of 35 w / v% toluene solution was applied to a urethane acrylic UV-curable coating (Arakawa Chemical Industry Co., Ltd. B
S575) was added to 3 liters and mixed by stirring to prepare an ultraviolet-curable coating material for hard coat. A test piece using a commercially available polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd. Iupilon S-2000 (viscosity average molecular weight 2.4 x 10 ⁴ )), a disk with an outer diameter of 120 mm and a thickness of 1.2 mm. Apply the paint to a thickness of about 30 μm and apply a dose of 340 mJ with an 80 W / cm mercury lamp.
It was irradiated for 30 seconds to be cured, and a hard coat was applied to the disk surface.
The adhesion of the hard coat was evaluated by a cross-cut test by peeling cellophane tape. The results of the evaluation test are shown in Table 1.

Example 2 The procedure of Example 1 was repeated except that the terminal-modified polycarbonate oligomer obtained in Reference Example 2 was used, and the adhesion of the hard coat was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results
Shown in.

Example 3 The procedure of Example 1 was repeated except that the terminal-modified polycarbonate oligomer obtained in Reference Example 3 was used, and the adhesion of the hard coat was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results
Shown in.

Comparative Example 1 Example 1 was repeated except that the end-modified polycarbonate oligomer solution was not added. The hard coat adhesion was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated, except that the end-modified polycarbonate oligomer obtained in Reference Example 4 was used. The hard coat adhesion was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Table 1 shows the measurement results of Examples and Comparative Examples.

[0038]

[Table 1] Cross-cut test: cross-cut cellophane tape peeling, residual squares / 100 viscosity average molecular weight: 20 ° C., the intrinsic viscosity was determined with a methylene chloride solution, and calculated from the following conversion formula. [Η] = 1.
23 x 10 ^-4 M ^0.83

[0039]

EFFECTS OF THE INVENTION The UV-curable coating material for a hard coat obtained by mixing the terminal-modified polycarbonate oligomer having terminal reactivity with the UV-curable coating material of the present invention has improved adhesion to the polycarbonate substrate after the hard coating. Can be made.

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Claims (3)

[Claims] 1. A hard coat obtained by mixing 50% by weight or less of an end-modified polycarbonate oligomer having a viscosity average molecular weight of less than 10,000 and having an end group derived from a monohydric phenol having a reactive olefin, with an acrylate-based UV-curable coating material. UV-curable paint 2. The ultraviolet-curable coating material for hard coat according to claim 1, wherein the content of the terminal-modified polycarbonate oligomer is 0.5 to 20% by weight. 3. The ultraviolet curable coating composition for a hard coat according to claim 1, wherein the terminal-modified polycarbonate oligomer has a viscosity average molecular weight of 2,000 to 8,000, and the content of the terminal-modified polycarbonate oligomer is 0.5 to 20% by weight.