JPS5986666A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. excellent in curability, capable of yielding good films, by incorporating urethane-based poly(meth)acrylates, polyoxyalkylene di(meth)acrylates, and polymn. initiators. CONSTITUTION:Urethane-based poly(meth)acrylate compds. having two or more (meth)acryloyloxy groups (A) [e.g., reaction products of diisocyanate compds. with (meth)acrylate esters having hydroxyl groups], 0-1,000pts.wt., based on 100pts.wt. component A, polyoxyalkylene di(meth)acryates (B), and 0.01-20pts. wt., based on 100pts.wt. total of components A and B, polymn. initiators [e.g., benzoin (for UV cure) or azobisisobutyronitrile (for thermosetting)] are incorporated.

Description

Detailed Description of the Invention The present invention provides excellent curing properties in air by coating the base surface of a resin molded article, and improves the surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, and The present invention relates to a curable resin composition for coating that has excellent film properties such as heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the surface of a molded body.

In general, resin molded products such as plastic resins and thermosetting resins are lighter and more impact resistant than metal products, glass products, etc., and are inexpensive and easy to mold. It has various advantages and is widely used in place of these materials in automobiles, motorcycles, household appliances, daily necessities, and many other fields.

However, these resin molded substrates have a lower surface hardness than metals, glass, etc., and are vulnerable to scratching and friction, so they have the drawback of easily forming spots on the surface. For example, these molded products cannot be used because they have shortcomings in surface properties that make them susceptible to damage due to contact, collision, scratching, etc. during installation or transportation of parts of the molded product, or during use of the product. severely limited.

Many proposals have been made as methods for improving the above-mentioned defects of the surface of the resin molded body substrate.

This is a method in which the surfaces of the molded bodies of tX and X7 are coated with an outer coating layer made of a crosslinked curable resin.

Among these film-forming elements, specifically, resins or resin-forming components include compositions of silicone monomers and these components and various polymers, and resins consisting of notyrolmelamine and other curing components. compositions, polyfunctional acrylic carboxylic acid ester derivatives, and compositions of this and other polymeric components have been proposed. Even if four layers of these film-forming elements are formed on the surface of a resin molded body such as polyolefin, the adhesion between the film and the basic layer of the resin molded body is generally not good. There is a drawback that the coating layer easily peels off from the laminate molded product.Furthermore, in order to improve these drawbacks, methods are known in which various treatments are applied to the surface of the basic layer of the resin molded product.For example, corona radiation Surface treatment with @+C, surface treatment with primer, etc. have been proposed.However, even with narrow surface treatment, it is difficult to put into practical use the base layer of a resin molded product such as polyolefin and the coating layer that is formed from the crosslinked hardening type 6S resin. In many cases, it is difficult to improve adhesion sufficiently to withstand the above-mentioned film-forming elements.Furthermore, among the film-forming elements mentioned above, silicone-based film-forming elements have the disadvantage that they are expensive and have poor economic efficiency.

Among the film-forming elements, various types of compounds have been proposed as polyfunctional acrylic carboxylic acid ester derivatives. Various types of compounds are used as film-forming elements, for example, poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, poly(meth)acrylates of aromatic (phenolic) polyhydroxylic compounds, etc. It is proposed to do so. Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as a film-forming element and a film is formed on the basic surface of the resin molding, these films will not harden in air during curing. Poor curing properties such as speed, surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, ml water resistance,
Film properties such as solvent resistance, weather resistance, and adhesion to substrates, or many of these properties, are often inferior, and the requirements for industrial-scale use cannot be fully met. . In addition, attempts have been made to improve these drawbacks by using a combination of two or more compounds of these film-forming elements, but none of them can improve these drawbacks to some extent. However, there were other new difficulties when coating the substrate surface of a resin molded product such as polyolefin.

The present inventors have developed a coating material that has excellent curing properties during curing and excellent coating properties by disposing it on the base surface of a molded resin such as a thermoplastic resin or thermosetting resin. Keihei conducted a study on the composition of urethane-based poly(
It has been discovered that the above object can be achieved by using a composition containing meth)acrylate (a), a specific amount of polyoxydialkylene di(meth)acrylate FBL, and a specific amount of polymerization initiator FCL, and the present invention has been achieved based on this finding. . According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a resin molded body substrate to form an outer sheath stern, it has excellent curing properties such as oxidation rate in air during curing, The surface hardness, scratch resistance, abrasion resistance, flexibility,
It has overall excellent properties in many coating properties such as surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates.

To summarize the present invention, the present invention comprises: (a) a urethane-based poly(meth)acrylate having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule; (bl) the urethane-based poly(meth)acrylate; (a
) 1 i'+ 11J l beyond 0 for ON setting part
polyoxydialkylene di(meth)acrylate in the range of 10 parts by weight, and +cl; the total of the urethane-based poly(meth)acrylate compound Kl and the poly(meth)acrylate 1/-(bl) of the alkane polyol; 1o 1. ) A resin coating composition characterized in that it contains a total of 0.01 to 20 parts by weight of a polymerization initiator based on the vertical part (t).

The urethane-based poly(meth)azilylate compound ta+ blended into the private curable resin composition of the present invention has one or more urethane bonds in one molecule and two or more acryloyloxyl groups or methacryloyl groups. It is a (meth)acrylate-based polyfunctional compound having an oxyl group. Specifically, urethane-based poly(meth)acrylate compounds obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group with a diisocyanate compound, and urethane-based poly(meth)acrylates made of polyurethane polyol poly(meth)acrylates. ) acrylate compounds, urethane-based poly(meth)acrylate compounds consisting of poly(meth)acrylates of polyester-based polyurethane polyols, and the like. The polyol component units constituting these ◇′) urethane poly(meth)acrylate compounds include aliphatic polyols, alicyclic polyols, aromatic polyols, polyoxyalkylene glycols, polyoxyalkane polyols, arylene bis[polyoxy Examples include alkane copolyols, polyester polyols, polyurethane polyols, polyester polyurethane polyols, polyurea polyols, and more specifically enalene glycol, propylene glycol, butylene glycol,
Hexylene glycol, octylene glycol, chrycerin, trimethylolpropane, pentaerythritol, diethylene glycol, triethylene nolicol, nfuropylene glycol, diethylene glycol, diethylene glycol, noglycene, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol, polyoxy Ethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane,
2.2-bis(4-hydroxyphenyl)propane2.
2-bis(4-hydroxyphenyl)ethane, bis(4
- (meth)acrylates of polyglycidyl ethers of the various polyhydric alcohols; Various polyhydric alcohol component units and cono-phosphoric acid, glutaric acid,
Polyhydric carboxylic acid component units such as adipic acid, superric acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, etc. Examples include polyester polyols formed from the various polyol component units described above and polyurethane polyols formed from the various diisocyanate component units described below. Furthermore, the diincyanate component units constituting these urethane-based poly(meth)acrylate compounds may be any of aliphatic diisocyanates, aliphatic diisocyanates, and aromatic diisocyanates. Of course, biscarbonate compounds of dinitrile corresponding to these diisocyanate component units or (1) biscarbamate compounds corresponding to these diisocyanate component units may also be used. Specifically,
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, methylcyclohexane-2,4-diisocyanate, 6-yne Dianatomethyl-6.5゜5-trimethylcyclohexyl isocyanate, 4,4'-dicyclohexylmethane diisocyanate, inpropylidene bis(4-cyclohexyl isocyanate), phenylene diisocyanate, tolylene diisocyanate , diphenylmethane diisocyanate, bistolylene diisocyanate, and the like. A poly(meth)acrylate of a polyurethane polyol is obtained by reacting the polyurethane polyol with acrylic acid or methacrylic acid according to a conventional method in the presence of a catalyst depending on the packaging. A poly(meth)acrylate of a polyester polyurethane polyol can be obtained by reacting it with methacrylic acid.

Among the urethane-based poly(meth)acrylate compounds, the urethane-based poly(meth)acrylate compound obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group with a diisocyanate compound has a hydroxyl group that can be removed. Polyhydroxyl group-containing compound and (meth)acrylic acid ester component unit
Examples include reactants with acrylic acid, reactants with epoxy compounds and (meth)acrylic acid, and specific examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacrylate. 2-hydroxypropyl acid, acrylate of glycidyl acrylate, methacrylate of glycidyl acrylate, acrylate of lysine methacrylate, methacrylate of lysine methacrylate, glycerin monoacrylate, glycerin monomethacrylate, glycerin -1
, 3-diacrylate, glycerin-1,3-dimethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, pentaerythritol Tall Monomethacrylate, Pentaerythritol Diacrylate, Pentaerythritol Dimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Dipentaerythritol Monoacrylate, Dipentaerythritol Monomethacrylate, Dipentaerythritol Diacrylate, Dipentaerythritol Dimethacrylate, Di Pentaerythritol triacrylate, dipentaerythritol trimethacrylate,
Dipentaerythritol triacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, bis(acryloyl quinethyl) hydroxyethyl isocyanurate, bis(methacryloyloxyethyl) hydroxyethyl isocyanurate, propylene glycol di Diacrylate of glycidyl ether, dimethacrylate of propylene glycol diglycidyl ether, glycerin-1,3-
Diazilycidyl ether of diglycidyl ether, dimethacrylate of glycerin-1,6-diglycidyl ether, triacrylate of glycerin triglycidyl ether, tri-7 methacrylate of glycerin triglycidyl ether, pentaerythritol diglycidyl ether Diacrylates, diacrylates of pentaerythritol diglycidyl ether triacrylates of tristhritol triglycidyl ether, trimethacrylates of pentaerythritol triglycidyl ether, diacrylates of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether compound, dimethacrylate of 2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, diacrylate of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, 2,2-bis(4- Examples include dimethacrylates of (hydroxyphenyl)propane diglycidyl ether, and examples of the diisocyanate component units include the compounds listed above. Among the urethane-based poly(meth)acrylate compounds (BL), urethane-based poly(meth)acrylate compounds containing an aliphatic alkylene diisocyanate component unit and an alicyclic diisocyanate component unit as diiso7anate component units are used. ) It is preferable to use an acrylate compound because it improves the hue, weather resistance, flexibility, etc. of the cured film.

The polyoxyalkylene (meth)acrylate fbl that is incorporated into the curable resin phase parabolite for coating of the present invention is an acrylic ester or a tutaacrylic ester of polyoxyalkylene glycol.

The oxydialkylone group constituting the polyoxydialkylene di(meth)acrylate has the general formula [I] [wherein R1, R2, R5 and R4 are each a hydrogen atom or a carbon atom number of 1 to 12]. Indicates an alkyl group. ], and the degree of polymerization of the oxyalkylene group is usually in the range of 1 to 40, preferably 1d1 to 20. The number average molecular it (Mn) of the polyoxydialkylene di(meth)acrylate is usually 200 to 30
00. Preferably it is in the range of 200 to 1000.

Specifically, the polyoxydialkylene di(meth)acrylate is 1, polyoxydiethylene diacrylate-1,
Examples include polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxyethylene dimethacrylate, polyoxyethylene polyoxypropylene diacrylate, polyoxyethylene polyoxypropylene dimethacrylate, and the like. Among the polyoxydialkylene di(meth)acrylates, polyoxyethylene di(meth)acrylate or polyoxypropylene di(meth)acrylate is preferred. The polyoxy7 alkylene di(meth)acrylate) (
The blending ratio of bl is more than 0 to 1 with respect to 100 parts by weight of the urethane-based poly(meth)acrylate fal.
000 parts by weight, and preferably 5 to 600 parts by weight, particularly 5 to 200 parts by weight. If the blending ratio of the polyoxydialkylene di(meth)acrylate (bl to the polyoxydialkylene di(meth)acrylate + al l 00 heavy parts is more than 10 parts by weight, the curability of the composition in air will decrease. As the surface hardness decreases, the surface hardness, abrasion resistance, etc. of the outer coating also decrease.

The film-forming element component (1 (polymerizable monomer component)) blended into the curable resin composition for coating of the present invention may consist of only the above-mentioned two essential components, but may also include other polymerizable monomers. It is also possible to copolymerize by adding other components.As other polymerizable monomer components, the urethane poly(meth)
In the production of acrylate compounds or the polyoxyalkylene di(meth)acrylates, there are still production intermediates, such as urethane mono(meth)acrylate compounds, polyoxyalkylene glycols (7).
In addition to mono(meth)acrylate, (meth)acrylic acid, methyl (meth)acrylate, (meth)acrylic acid-
Examples include (meth)acrylic esters such as 2-hydroxyethyl.

The curable resin composition for coating of the present invention is
- to form a film by crosslinking and curing the composition (it is necessary to add a polymerization initiator to this composition; the curing method is a curing method using ultraviolet rays). , curing methods using heat rays are usually employed. In the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator. Specifically, the photosensitizer includes benzoin, benzoin methyl ether, benzoin ethyl ether. ,
benzoin or its ethers such as benzoin isopropyl ether and benzoin isobutyl ether; benzophenone compounds such as benzophenone, p-chlorobenzophenone and p-methoxybenzophenone; benzyl compounds Th such as benzyl dimethyl ketal and benzyl diethyl ketal; 1 (4W 7 Furobylphenyl)-2-hydroxy-2-methyl-1-
Hydroxyalkylphenyl ketones such as propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, and 1-(4-4, art -butylphenyl)=2-hydroxy-2-methyl-1-propanone. An example of the system compound 18-mono may be mentioned. In the case of curing by heat, a radical initiator is blended, and specific examples of the radical initiator include (C is an azo compound such as azobinisobutyronitrile, pennyyl peroxide, lauryl peroxide, di-tert-butyl peroxide, Examples include peroxides such as dicumyl peroxide and cumene hydroperoxide.Furthermore, both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and ultraviolet rays It is also possible to adopt a method in which curing and thermosetting proceed simultaneously (7. It is also possible to adopt a method in which thermosetting proceeds after ultraviolet curing has progressed and filtered.

7. Conversely, proceed with heat curing and then proceed with ultraviolet curing. It is also possible to adopt the method. The blending ratio of the polymerization initiator fcl is in the range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of the urethane-based poly(meth)acrylate compound +a+ and the polyoxydialkylene di(meth)acrylate 10. It is preferable that the amount of egg is 0.01 to 10 eggs. The blending ratio of the polymerization initiator is from 0.01 parts by weight to a little more than 1 part by weight per 100 parts of the urethane-based poly(meth)acrylate compound fa, l and the polyoxydialkylene di(meth)acrylate. When the amount exceeds 20 parts by weight, the polymerizability of the composition decreases and hard film breakage cannot be obtained, and when the amount exceeds 20 parts by weight, the film obtained from the composition becomes yellow colored.

The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, but may further include a polymerization inhibitor, a transparent filler, a normal phase, a dye, a solvent, UV absorbers, stabilizers such as antioxidants, fluorescent whitening agents,
Kokichi is able to blend various additives such as (reactive) oligomers such as methyl (meth)acrylate and polyester acrylate, and polymers such as polymethyl methacrylate. The blending ratio of these additives is determined as appropriate.

In the curable resin composition for coating of the present invention, a finely powdered inorganic filler may be blended as necessary within a range that maintains the transparency of the resulting cured film. The average particle size of the fine powder next autumn 411T: The average particle size of the mechanical filler is arbitrary as long as it is shaded in powder form, but it is usually between 1 mμ and 10 mμ.
μ, preferably 1 is 1.5mμ or 1μ@! , If5
It is. In addition, in order to maintain the transparency of the outer nuclear coating layer, the refractive index of the finely powdered inorganic filler is usually 1.40 to -1.6o, preferably σ.

It ranges from 1.42 to 1.5B. Specifically, such fine powder inorganic fillers include glass powder, mica, glass peas, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica, silica sand, quartz, kaolinite, montmorillonite, and site, talc, edge stone,
Examples include pottery stone and feldspar. The surface of these finely powdered inorganic fillers is coated with alkyl carboxylate 7
4*(rf,'/titanium coupler titanium coupler,
C7J2Sl(C:H3) 2, which has been surface-treated with alcohol or the like, can also be used in the same way. It is also possible to use colloidal silica sol, methanol silica sol, ethanol silica sol, tubulobanol silica sol, etc. in which the inorganic filler is left in water or alcohol. ξ Among these fine powder inorganic fillers, when combined with fine powder silica, the surface hardness, scratch resistance and abrasion resistance of the outer nuclear coating layer are significantly improved, and the transparency and Horiza Motozawa It is particularly preferable because it does not damage the The blending ratio of these finely powdered inorganic fillers is usually 0.1 U (1 part by weight) of the urethane-based poly(meth)acrylate compound) and the polyoxydialkylene di(meth)acrylate-Hbl. 5 to 201 parts by weight, preferably from 0.5 to 100 parts by weight.

In order to improve the coating workability of the curable resin composition for rhymes of the present invention, a solvent is added as necessary to maintain it in a solution state or a suspended state.

It is also used to suspend the composition in a solvent, to adjust the viscosity of the composition, or to improve the wettability of the composition to molded objects. Specifically, the solvents include benzene, toluene, xylene, cumene, ethylbenzene, hegysan, heptane, otatane, petroleum ether,
Hydrocarbons such as ligroin, cyclohexane, methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, 7'omoform, trichlene, ethylene dichloride, perchlorene, ethane dichloride, propylene dichloride, chlorobenzene, fromobenzene Nato's halogenated hydrocarbon scale, methanol, ethanol, impropatol, phthanol, pentanol,
Alcohols such as hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, diethyl ether, dipropyl ether, ctyl ethyl ether, Ethers such as dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionitrile, capronitrile, methyl oxate, ethyl formate,
Examples include esters such as methyl acetate, etinope acetate, propyl acetate, inobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate.

The blending ratio of these organic solvents is as follows:
A total of 100 meth)acrylate compound 1a+ and the polyoxydialkylene di(meth)acrylate tbl
The amount is usually 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight.

In the composition of the present invention, the above-mentioned essential components and various additive components such as inorganic or organic fillers, solvents, stabilizers, etc. added as necessary can be mixed into a solution-like composition or a suspension-like composition. 10 is a method of preparing a product by blending the above-mentioned raw material mixture and using a regular roll or Banbury mixer.
, ball mill, attritor, winover, oak mixer, dissolver, homogenizer, colloid mill,
Examples include kneading and mixing methods using a sand mill, a vibration mill, a mixer, a mixing tank, etc., and a uniformly dissolved or dispersed composition can be obtained by these methods. Methods for applying the solution composition and suspension composition to the substrate surface of the all-resin molded article include brush coating method, spray method, dipping method, bar code method, roll coater method, spin coater method, and gel coater method. Conventionally known methods such as the following can be employed. Examples of methods for drying the coating film include natural drying, forced drying using a carrier gas, and heating drying using an infrared oven, far-infrared oven, and hot air oven. Examples of methods for curing the above-mentioned coating film to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, a method of polymerizing and crosslinking hardening with heat, and the like. Among these polymerization crosslinking and curing methods, in the photocuring method, light irradiation is usually carried out at a temperature of -10 to 150°C, preferably 5 to 160°C, and the time is usually 1 sec to 1 hr, preferably 1 sec to 10 sec. I sing a song.

Further, in the thermosetting method, the temperature during curing is usually -10 to 150°C, preferably 7 to 1.130°C, and the time required for curing is usually 0.05 to 1.130°C. □hr is preferably 0.1 to 1, f311 rmis.

The curable resin composition for coating of the present invention has thermoplasticity of -25-
-F- The base surface of any molded article made of resin or thermosetting resin can be coated. The shape of the molded product may be a film, a sheet, a plate, a molded product having a curved surface or an uneven surface, or any other shape.

Specifically, the thermoplastic resin constituting the base layer includes polyolefins such as homopolymers of α-olefins or copolymers mainly composed of α-olefins;
Polyacrylic ester resin, polycarbonate resin,
Examples include polynisder resin and polyamide resin. Among these thermoplastic resins, the base resin layer constituting the laminate molded product is preferably polyolefins, polyacrylic ester resins, or polycarbonate resins. Specifically, the polyolefins include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-thecene; A copolymer consisting of a mixture of two or more olefins, or a copolymer containing the above-mentioned A copolymer containing a small amount (for example, 30 molar proportion or less) of other components such as metal salts of , acrylic carboxylic acid esters such as methyl methacrylate, gold salts of methacrylic acid, and salts of acrylic carboxylic acids. I can give an example. Among these polyolefins, polyolefins having crystallinity are usually used.

Specific examples of the polyacrylic carboxylic acid ester resins include homopolymers and copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. can do. Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A and polycarbonate. Specific examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, bisphenol A/isophthalic acid/terephthalic acid copolycondensate, and oxybenzoic acid polycondensate. Specifically, the polyamide resin includes nylon 6, nylon 6.6, and nylon 10.
, Nylon 12 can be opened. In addition to the above resins, polyacetal, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide,
Examples include polyphenylene sulfide resin and polyether sulfone resin.

a thermosetting resin constituting the base layer; 1. Specifically,
Examples include unsaturated polyester resins, epoxy resins, melamine resins, diallyl phthalate resins, and polyallyl glycol carbonate resins.

When coating the base surface of a resin molded body with the wandering curable resin composition of the present invention, the base surface of the molded body may be washed with various solvents, washed with an alkaline aqueous solution, or treated with a propensity-activating agent. Cleaning, ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment,
Arc discharge treatment, glow walk treatment, plasma discharge treatment,
Various surface treatments such as chemical conversion treatment can be performed.

Further, when laminating the outer coating layer made of the curing type resin acid for vN of the present invention on the base surface of the molded article, an intermediate adhesive layer made of a brimer is provided between the base layer and the outer coating layer. It is also possible to improve the adhesion between the two layers by forming a 31-laminate with the two layers in place. When the base layer is a polyolefin, a modified polyolefin grafted with an α/β-unsaturated carboxylic acid or its derivative component is usually used as the brimer, and if necessary, surface treatment is applied as described above. The composition of the present invention is applied to the base layer plate surface of the resin molded body that has been subjected to the brimer treatment by the method described above, and then a curing treatment is performed.

A resin molded article on which a coating made of the curable resin composition for coating of the present invention is laminated can be used for various purposes. Specifically, we manufacture daylight panels, sky domes, solar water heater panels, glove box panels, watch glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee maker shower domes. and coffee containers, water tanks, covers for lighting equipment, covers for stereo devices such as players, dials and covers for various meters, covers for car headlamps and tail lamps, level sensors, glass shatter prevention films and release films, Various films such as insulating fill-no, agricultural film, optically regenerated video discs, observation windows for various equipment such as clothes dryers, electric washing machines, dryers, oil tanks, etc., first-generation glass protection for motorcycles, jeeps, motor boats, etc., and automobiles. glass (front glass, rear window, opera window, triangular window, sunroof), window glass for greenhouses, houses, aquariums, etc., tableware, mirrors, various containers such as oil bottles and cosmetic bottles, relay cases, fuse boxes, etc. , motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulation films, floor tiles, floor sheets,
Doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, furniture, lightweight wall boards, tableware, chairs, bathtubs, toilet bowls, refrigerators, cabinets, wall panels, water supply and drainage pipes,
Wiring pipes, ducts, curtain rods, rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, rain doors, shutters , waterproof pans, pipes, wiring materials, gear cams, knobs,! 'tl Valve frames, fans, instrument panels, bumpers, brakes, etc. can be opened.

In addition to the above, it is also used in home appliances, automobile parts, motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and nuclear power-related parts. can do.

Next, the present invention will be specifically explained using Example 1 (Y-).

Furthermore, tli state: Unwritten -! In Example F, the evaluation was carried out in the following manner.

(1) Refractive index A sufficiently dried inorganic substance is placed in a liquid with a known refractive index for 2w.
After adding t4 and thoroughly dispersing it, visually check the transparency. The refractive index is the same as that of the most transparent liquid.

(2) Surface gloss (ri'loss) Measured according to 60 degree specular gloss r in JIS K 54 (10-1979).

(3) Light transmittance It was conducted according to JIS K 6714.

(4) Adhesion The test was carried out according to the square test in JIS K 5400-1979. The judgment is based on how many of the 100 gobans were glued together.

(5) Sandfall abrasion 8 according to the method of JIS T 8147-1975
Drop 00g of silicon carbide abrasive material onto the coating. Abrasion resistance can be determined by the difference in surface gloss (cross) before and after the test.

The smaller the number, the better the wear resistance.

(6) Taper wear According to the method of ASTM D-11144, wear ring C
810, the coating was run 1000 times with a load of 500 g. Wear resistance can be measured by the amount of wear on the coating after the test. The smaller the amount of wear, the better the wear resistance.

(7) Pencil hardness Measured according to JIS K 5651.

(8) A strip-shaped test piece with a visibility width of 5 mm and a length of 10 CrrL has a diameter of 2α.
Fold it along the outer circumference of the cylinder to see if the coating cracks or
It is expressed as the angle at which it peels off from the substrate. The larger the value, the better the flexibility.0 (9) Water resistance A test piece was immersed in pure water at 40°C for 240 hours, and the appearance and adhesion of the open coating layer were evaluated.

After holding the test piece in a gear set aging tester at 81)° C. for 400 hours, the appearance and adhesion of the outer coating layer were evaluated.

(11) Volatile oil resistance test piece was immersed in petroleum benzine for 24 hours at room temperature, and then the appearance and adhesion of the outer coating layer were evaluated.

(No. 12 gasoline resistance test piece was immersed in regular gasoline at room temperature for 24 hours, and the appearance and adhesion of the outer coating layer were evaluated.

(13) The heat cycle resistance test piece was kept in an air oven at 80°C for 2 hours, then left at room temperature for 1 hour, and then placed in a cold room at -30°C for 2 hours.
Hold for an hour and then leave at room temperature for 1 hour. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated.

(14) Weather resistance test pieces were held in a sunshine weatherometer for 400 hours to evaluate the appearance and adhesion of the outer coating layer.

In addition, a synthesis example of urethane-based polyacrylate is shown in the following reference example.

Reference Example 1 Diacrylate of propylene glycol diglycidyl ether (Kyoeisha Yushi Kagaku KK!!!+, trade name Epoxy Ester 70PA) 100g (0.3 mol)
20g (13,12M) of xamethylene diisocyanate was placed in a 500rn14 Turow flask under nitrogen atmosphere.
was added and stirred for 15 hours at room temperature to synthesize a urethane polyacrylate (PGAHI) consisting of a diacrylate of propylene glycol diglycidyl ether and a hexamethylene diisocyanate component unit.

Reference example 2 Dipentaerythritol pentaacrylate 50g (0
A mixture of 30 g (0,064 mol) of dipentaerythritol tetraacrylate and 20 g of dipentaerythritol hexaacrylate and 120 g of methyl isobutyl ketone were placed in a 500M14 flask, and 6-cyanatomethyl-3. 5.5-trimethylcyclohexyl isocyaner)
Add 17.6g (0.08mol) and leave at room temperature for 15h.
r Stirring] 2. Dipentaerythritol polyacrylate;
・Component unit and 6-isocyanatomethyl, 5.5.5
-) Synthesis of a methyl isobutyl ketone solution of urethane polyacrylate (DPAIP) consisting of rimethercyclohexyl isocyanate component units 1. is.

Reference Example 6 74 g (0.2 M) of bis(acryloyloxyethyl) hydroxyethyl isocyanurate and 100 g of methyl isobutyl ketone were placed in a 5.00 yt 14 tube flask, and 6-cyanatomethyl-3.
5.5-trimethylcyclohexyl isocyanate 22
g (0,1,M) and stirred for 15 hours at room temperature to combine bis(acryloyloxyethyl)hydroquine ethyl isocyanurate component unit and 3-isocyanatomethyl-3
, 5,5-) urethane poly-11 acrylate (BAI
A methyl isobutyl ketone solution of IP) was synthesized.

Example 1 Urethane polyacrylate (P(,
AHI) 135 g, diethylene glycol diacrylate) 15 g, benzoin isopropyl ether 5
g and methyl isobutyl ketone 120g'J&500
d) The mixture was charged into a 4-cell tube and stirred for 1 hour at room temperature to prepare a transparent coating composition [A].

On the other hand, an injection square plate (thickness 6 mm) made from polypropylene (manufactured by Mitsui Petrochemical Industries KK, trade name Mitsui Petrochemical Polypro 5J-315) was exposed to the vapor of 1.1.1-) lychloroethane for 1 minute. After that, it was dried for 1 minute at room temperature, and then an injection square plate of maleic anhydride-modified PEL-1 (containing propylene of 167 mol, maleic anhydride m content of 6 V, rtl) was placed in 15 g/l of toluene mW [B] for 20 minutes. Dip it for a second and slowly pull it out at 37-. After drying at room temperature for 5 minutes, heat drying was performed at 80° C. for 30 minutes. Next, the following coating composition [A]
The primer-treated polypropylene square plate was immersed in the solution for 60 seconds, slowly pulled up, and then heated at room temperature for 1 minute.
Next, drying was performed at 60° C. for 5 minutes. This test piece was 1.
Under 5K, W high pressure mercury lamp (120W/cIIl), 1
Ultraviolet # at a distance of 5cm? It was irradiated for 30 seconds to completely cure the outer covering M layer. The film performance is shown in Table 1.

Example 2 In Example 1, the coating composition described in Example 1 [
A) Instead of using 176 g of the urethane-based polyacrylate (DPAIA) solution described in Reference Example 2,
After using a coating composition consisting of 15 g of nonaethylene glycol diacrylate, 5 g of benzoin isopropyl ether, and 29 g of methyl isobutyl ketone, a test piece was prepared in which the surface of polypropylene was coated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 In Example 2, instead of using the urethane-based polyacrylate solution and nonaethylene glycol cyacrylate described in Reference Example 2, the urethane-based polyacrylate (BAIIP) and tripropylene glycol described in Reference Example 6 were used. A test piece was prepared by coating the surface of polypropylene using the amount of diacrylate shown in Table 1 and using the method described in Example 2. The results are shown in Table 1.

Examples 4-6 In Example 1, the coating composition described in Example 1 [
Instead of using A], a coating composition prepared by using the urethane poly(meth)acrylate, polyoxyalkylene diacrylate, polymerization initiator, and solvent listed in Table 1 in the amounts listed in Table 1 was used. A test piece was prepared by coating the surface of polypropylene in the same manner as in Example 1. The end of the year is shown in Thorn 1.

Examples 7 to 8 The tri/tan-based poly(meth)acrylate, polyoxyalkylene diacrylate, -polymerization initiator and i, '+, i-trichloroethane listed in Table 1 were listed.
The amount described in 11 was weighed out, and to this mixture, finely powdered silica (manufactured by Nippon Aerosil KK, trade name) i, -972> having an average particle diameter of 20 mμ and a refractive index of 1.45 was gradually added (feed). (Dosages are listed in Table 1) and stirred thoroughly until uniform dispersion was obtained. The mixture was transferred to an attritor (manufactured by Mitsui Miike Seisakusho KK) filled with steatite balls, and the agitator was heated while cooling the tank with water.
was rotated at 150 rpm and mixed for 6 hours. Thereafter, the amount of n-butanol listed in Table 1 was added, and an additional 10
After mixing for a minute, remove the mixture from the attritor and
This was designated as coating composition [A]. Example 1 in Example 1
A test piece having a polypropylene surface coated was prepared by the method described in Example 1, except that the coating composition described in Example 1 was used instead of the coating composition described in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 2 The urethane polyacrylate, photosensitizer, and solvent listed in Table 1 were weighed out in the amounts listed in Table 1FC, and heated at room temperature for 1 hour.
A test piece was prepared by coating the surface of polypropylene by the method described in Example 1, except that the coating composition [A] prepared by stirring and mixing was used.

The results are shown in Table 1.

Comparative Example 6 Table 1 shows the performance of polypropylene alone (manufactured by Mikata Petrochemical Industries KK, 5J-313) that was not coated with the coating composition of the present invention.

The abbreviations used in Table 1 below represent the following compounds.

(n D E G D A... Diethylene glycol diacrylate (21T P G D A... Triflopylene gelicol diacrylate + 31 N E G D A... Tuna ethylene glycol diacrylate 41- +4) BIE・・・・・・・・・Benzoin isopropyl ether (51IHP・・・・・・・・・1-(4-′(sobrobylphenyl)-2-hydroxy- 2-Methyl-1-propanone (6) R=H・・・・・・・・・GMAHIR=CHS
...... G D M HI-42 = Example 9 Poly-4-methyl-1-pentene (Mikata Petrochemical Industry K
An injection molded sheet made by K, product name: 'J'px MXDl'14) with a thickness of 6 dragons was molded with maleic anhydride modified E'PR (
Brimer treatment was performed by immersing the sample in a 1.1.1-) dichloroethane solution containing anhydrous 71/Ia 112-containing 44; 7.7 wt%) at a concentration of 15 g/β for 10 seconds. 5 at room temperature
After opening for 10 minutes, the sample was immersed in the composition described in Example 8, e4, for 10 seconds. After drying at room temperature for 1 minute and then at 60°C for 5 minutes, photopolymerization was performed using the method described in Example 8 to obtain poly-4-
A test piece was prepared by coating the surface of methyl-1-pentene. The results are shown in Table 2.

Examples I D to 11 In Example 9, instead of using poly-4-methyl-1-pentene as the base polymer, a 6p old Q) polymeric compound as described in Table 2 was used, and In addition to pretreatment, a test piece was prepared in which the surface of the polymer was crushed using the method described in Example 1.The results are shown in Figure 2.

Comparative Examples 4 to 6 PoIJ-4- which is not covered with the composition for being stepped on according to the present invention
Methyl-1-pentene (manufactured by Mikata Petrochemical Industries KK, T
PX MXOO4) Polycarbonate (Quantitative Kasei KK
Table 2 shows the performance of Panlite L-1250) and polymethyl methacrylate (Mitsubishi Rayon KK 11, Acrylai L).

/ / Example 12, Comparative Example 7 In Example 1, the coating composition described in Example 1 [
Instead of using the coating composition [A] described in Example 8, and instead of using polypropylene as the molded body substrate, a 2-thickness unsaturated polyester resin (
A test piece having a surface coated with unsaturated polyester resin was prepared by the method described in Example 1 except that Rivolac MC8-302 (manufactured by Showa Kobunshi KK) was used. The film thickness of this test piece is 8μ, the surface gloss (cross) is 84, and the adhesion is 100.
/100, and the pencil hardness was 4H (Example 12).

On the other hand, the unsaturated polyester resin not coated with the coating composition of the present invention had a surface gloss (cross) of 63 and a pencil hardness of 6H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi 48- 544-

Claims (1)

[Claims] fll fal A urethane-based poly(meth)acrylate compound having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule, (bl The urethane-based poly(meth)acrylate compound + al l 00 parts by weight 1000 over 0 for
Polyoxydialkylene di(meth) in parts by weight range
acrylate, a polymerization initiator in the range of 0.01 to 20 parts by weight per 100 parts by weight of the urethane-based poly(meth)acrylate compound (al and the polyoxydialkylene di(meth)acrylate). (2) The urethane-based poly(meth)acrylate compound f
al and the polyoxydialkylene di(meth)-1-+
s 0.5 to 2 per 100 parts by weight of acrylate
The curable resin composition for coating according to claim 11, which contains a finely powdered inorganic filler in an amount of 0.00 parts by weight.