JPH0553837B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent curing properties in air by coating the base surface of a molded article such as a resin,
For coatings with excellent coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the surface of the molded body. The present invention relates to a curable resin composition. In general, molded objects such as thermoplastic resins and thermosetting resins are not only lighter and have better impact resistance than metal products and glass products, but also are inexpensive and easy to mold. Due to its advantages, it is widely used to replace these materials in automobiles, motorcycles, household appliances, household goods, and many other fields. However, molded substrates made of these resins have a lower surface hardness than metals, glass, etc., and are vulnerable to scratching and friction, so they have the drawback of being easily scratched on the surface. For example, the use of these molded bodies is difficult due to drawbacks in their surface properties, such as susceptibility to surface damage due to contact, collision, scratching, etc., during the installation or transportation of molded parts, or during use of the product. severely limited. Many proposals have been made as methods for improving the above-mentioned defects on the surface of molded body substrates such as resins. Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film-forming elements, specific examples of resins or resin-forming components include silicone monomers or compositions of these components with various polymers, and resin compositions consisting of methylolmelamine and other curing components. , polyfunctional acrylic carboxylic acid ester derivatives, and compositions of these and other polymeric components have been proposed. Even if a film layer consisting of these film-forming elements is formed on the surface of a base material of a resin molded product such as polyolefin, the adhesion between the film layer and the base layer of the resin molded product is generally not good. The disadvantage is that the coating layer is easily peeled off. Furthermore, methods are known in which various treatments are applied to the surface of the resin molded body base layer in order to improve these defects. For example, surface treatments using corona discharge and primers have been proposed. However, even if surface treatment is performed, it is often difficult to sufficiently improve the adhesion between the base layer of a resin molded product such as polyolefin and the coating layer made of the crosslinked curable resin so as to be practical. Moreover, among the film-forming elements, silicone-based film-forming elements are expensive and have a disadvantage of being inferior in economic efficiency. Among the film-forming elements, various types of compounds have been proposed as polyfunctional acrylic carboxylic acid ester derivatives. for example,
Various types of compounds can be used as film-forming elements, such as poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, and poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds. is proposed. Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as a film-forming element to form a film on the substrate surface of a resin molded article, the curing speed of these films in air during curing will be low. poor curing properties or poor coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. However, many of these properties are often inferior, and it has not been possible to fully satisfy the requirements for industrial scale use. In addition, attempts have been made to improve these drawbacks by using a combination of two or more compounds among these film-forming elements, but none of them have been able to improve these drawbacks to some extent. However, there were other new difficulties when coating the surface of a base material of a resin molded product such as polyolefin. The present inventors have worked diligently to develop a coating composition that has excellent curing properties during curing and has excellent coating properties by coating the substrate surface of a molded object such as a thermoplastic resin or thermosetting resin. As a result of investigation, we found that poly(meth)acrylate of polyester polyol (a), specific amount of specific arylene bis[polyoxyalkylene(meth)acrylate (b),
Specified amount of 1-(4-isopropylphenyl)-2-
It has been discovered that the above object can be achieved by using a composition containing a hydroxy-2-methyl-1-propanone photopolymerization initiator and a specific amount of a finely powdered silica filler having a specific particle size and refractive index, and the present invention invention has been achieved. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a molded body substrate such as a resin to form an outer coat layer, the curing characteristics such as the curing speed in air during curing are improved. The resulting coating has many properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. It has the characteristics of being excellent. To summarize the present invention, the present invention comprises: (a) a poly(meth)acrylate of a polyester polyol having at least two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule and having no urethane bond; (b) Poly(meth) of the polyester polyol
The following general formula [] is in a range of more than 0 and 1000 parts by weight per 100 parts by weight of acrylate (a) However, R ¹ : H or methyl group n: 1 to 20 R ² : -CH ₂ -CH ₂ -,

【formula】

【formula】 Ar：

【formula】

[Formula] X: -O-, -S-, -SO ₂ -, -CH ₂ -,

【formula】

[Formula] R ³ , R ⁴ : arylene bis [(poly)oxyalkylene (meth)acrylate] represented by H or a lower alkyl group, and (c) poly(meth) of the polyester polyol
0.01 to 20 parts by weight of 1-
(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone photopolymerization initiator, and (d) poly(meth)acrylate of polyester polyol (a) and represented by the general formula [] Average particle size ranging from 0.5 to 200 parts by weight per 100 parts by weight of (meth)acrylate (b)
A curable resin composition for coating, characterized in that it contains finely powdered silica with a diameter of 1 mμ to 1μ and a refractive index of 1.40 to 1.60. enyl)−
The use of a 2-hydroxy-2-methyl-1-propanone photoinitiator and, among various fillers, an average particle size of 1 mμ to 1μ and a refractive index of 1.4.
The most characteristic combination is the use of fine silica powder of 1.6 to 1.6. A coating composition containing a poly(meth)acrylate of a polyester polymer as the component (a) and arylene bis[(poly)oxyalkylene(meth)acrylate] as the component (b) is blended with other ordinary polymerization initiators. Because it is coated onto a substrate to a thickness of, for example, only a few microns to a dozen microns, and the exposed area per unit weight of the coating material is extremely large, the polymerization inhibiting effect of atmospheric oxygen is quite large, and it takes a long time to cure. Polymerization within an economically reasonable short period of time is insufficient to cure the resulting coating; as a result, the surface hardness, scratch resistance, abrasion resistance, and flexibility of the coating are insufficient. surface gloss,
However, they still suffer from insufficient heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate surface. In contrast, in the present invention, 1-(4-
isopropylphenyl)-2-hydroxy-2-
Methyl-1-propanone photopolymerization initiator has a higher photopolymerization rate than other photopolymerization initiators such as a phenone polymerization initiator, which is a typical photopolymerization initiator, and can be used in combination with methyl-1-propanone photopolymerization initiator. The silica-based filler used in this invention has a particle size of 1 μm to 1 μm and a refractive index of 1.4 to 1.6, and has a significantly greater effect on imparting thixotropy to uncured resin than other inorganic fillers. It works by keeping the coating material in a pseudo-hardened state and blocking oxygen. In the coating composition of the present invention, these two effects are organically related and integrated, and even when the coating is extremely thin, the polymerization inhibiting (not inhibiting) effect of atmospheric oxygen is suppressed, and compared to Within a relatively short period of time, the composition is highly and effectively polymerized and cured, and the aforementioned improvements in the physical properties of the coating film are achieved. The poly(meth)acrylate of polyester polyol (a) blended into the curable resin composition for coating of the present invention has at least two or more acryloyl ochral groups or methacryloyl oxyl groups in one molecule, and It is a poly(meth)acrylate of polyester polyol that does not have urethane bonds. Here, the polyester polyol constituting the poly(meth)acrylate of the polyester polyol is formed by polycondensing a polycarboxylic acid and a polyol. It is a polyester polyol having hydroxyl groups. Examples of the polycarboxylic acid component units constituting the polyester polyol include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, brassylic acid, Aliphatic polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, butanetricarboxylic acid, butanetetracarboxylic acid, hymic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride,
Examples include alicyclic polycarboxylic acids such as hexahydrophthalic anhydride, aromatic polycarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Examples of the polyol component units constituting the polyester polyol include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, Dibutylene glycol, tributylene glycol, dihexylene glycol, diglycerin, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol,
Aliphatic polyols such as polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,
Alicyclic polyols such as 2-bis(4-hydroxycyclohexyl)ethane and bis(4-hydroxycyclohexyl)methane, xylylene glycol, 2,2-bis(4-hydroxyphenyl)-propane, 2,2-bis( Examples include aromatic polyols such as 4-hydroxyphenyl)ethane and bis(4-hydroxyphenyl)methane. Among the polyester polyol components formed from these polycarboxylic acid component units and polyol component units, a polyester polyol component composed of aliphatic, alicyclic, or a mixture thereof is preferable.
Particularly preferred is an aliphatic polyester polyol component. By reacting the polyester polyol with acrylic acid or methacrylic acid in the presence of a catalyst, if necessary, a poly(meth)acrylate of the polyester polyol can be obtained. The number average molecular weight of the poly(meth)acrylate of the polyester polyol is usually 300 to 7000, preferably 300 to 7000.
5000 range. The (meth)acrylate (b) of the general formula [] that is blended into the curable resin composition for coating of the present invention is:
It is an acrylic ester or methacrylic ester of a glycol compound in which the phenolic hydroxyl group of a divalent phenol and two molecules of mono- or polyoxyalkylene glycol are bonded by forming an ether bond. Specifically, the divalent phenols constituting the (meth)acrylate (b) include hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, 4,4'-dihydroxydiphenyl ether, , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 1,1-bis(3,5-dimethyl-4 -Hydroxyphenyl)ethane, 2,2-bis(3,5-dimethyl-
Examples include 4-hydroxyphenyl)propane. Specifically, the oxyalkylene group constituting the (meth)acrylate ( _b ) includes oxyethylene group [-O- _CH2CH2- ], oxypropylene group [-
O-CH ₂ -CH(CH ₃ )-], oxybutylene group [-
O-CH ₂ CH (C ₂ H ₅ )-], and a mixture of two or more of these components may be used. The average number of oxyalkylene groups contained in the (meth)acrylate (b) is usually in the range of 1 to 20. Further, its number average molecular weight is usually in the range of 300 to 3,000, preferably 300 to 2,000. Specifically, the arylene bis[(poly)oxyalkylene (meth)acrylate] is p-
Phenylene bis [(poly)oxyethylene (meth)
acrylate], m-phenylene bis [(poly)oxyethylene (meth)acrylate], o-phenylene bis [(poly)oxyethylene (meth)acrylate], bisphenol A bis[(poly)oxyethylene (meth)acrylate], Bisphenol F bis[(poly)oxyethylene(meth)
acrylate], p-phenylene bis [(poly)oxypropylene (meth)acrylate], m-phenylene bis [(poly)oxypropylene (meth)
acrylate], bisphenol A bis[(poly)oxypropylene (meth)acrylate],
Bisphenol F bis[(poly)oxypropylene (meth)acrylate] and the like can be exemplified. The blending ratio of the arylene bis[(poly)oxyalkylene (meth)acrylate] (b) is greater than 0 and 1000 parts by weight per 100 parts by weight of the poly(meth)acrylate of the polyester polyol (a). It is necessary that the amount be within a range of 5 to 700 parts by weight, especially 5 to 700 parts by weight.
Preferably it is in the range of 20 to 500 parts by weight.
The poly(meth)acrylate of the polyester polyol of the arylene bis[(poly)oxyalkylene(meth)acrylate] (b) (a)
If the blending ratio exceeds 1000 parts by weight to 100 parts by weight, the surface hardness, abrasion resistance, etc. of the outer coating will decrease. The film forming element component (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 further include other polymerizable monomer components. In addition, copolymerization is also possible. Other polymerization components include, for example, by-products or production intermediates during the production of the poly(meth)acrylate of the polyester polyol (a), such as the mono(meth)acrylate of the polyester polyol, the arylene bis [(Poly)oxyalkylene (meth)acrylate] In addition to by-products or production intermediates during the production of (b), such as mono(meth)acrylate of arylene bis[polyoxyalkylene] glycol, (meth)acrylic acid , (meta)
Examples include (meth)acrylic acid esters such as methyl acrylate and 2-hydroxyethyl (meth)acrylate. In order to apply the curable resin composition for coating of the present invention to the substrate surface of a molded body and crosslink and cure the composition to form a film, a photopolymerization initiator (c) is blended into this composition. It is necessary. As the photopolymerization initiator (c), 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1
- Use propanone. As a curing method, a photopolymerization curing method using ultraviolet rays or the like is employed. The blending ratio of the photopolymerization initiator (c) is 100 parts by weight in total of the poly(meth)acrylate of the polyester polyol (a) and the arylene bis[(poly)oxyalkylene(meth)acrylate] (b). It is necessary to range from 0.01 to 20 parts by weight, and more preferably from 0.1 to 10 parts by weight. The blending ratio of the polymerization initiator is the poly(meth)acrylate of the polyester polyol (a)
If the amount is less than 0.01 part by weight based on a total of 100 parts by weight of arylene bis[(poly)oxyalkylene (meth)acrylate] (b), the polymerizability of the composition decreases, making it impossible to obtain a hard film, and When the amount exceeds 20 parts by weight, the coating obtained from the composition becomes colored. In the curable resin composition for coating of the present invention, a fourth essential component is added in order to improve the surface hardness, scratch resistance and abrasion resistance of the cured film obtained therefrom, and also to improve the thixotropic performance during application. , a specific silica fine powder filler is blended. The properties of the silica fine powder filler blended in the present invention include an average particle size in the range of 1 mμ to 10 μ, preferably 1.5 mμ to 1 μ, and a refractive index in the range of 1.40 to 1.60, preferably 1.42 to 1.58. fine powder is used. If the average particle size is larger than 1 μm, uniform dispersibility in the resin composition will be poor, and thixotropic performance and film transparency during coating curing will be impaired. On the other hand, particles with an average particle size smaller than 1 mμ are not economical. If the refractive index is outside the above range, the transparency of the coating will be impaired due to its relationship with the refractive index of the coating resin composition itself. In addition, the surface of this fine powdered silica filler is coated with alkyl carboxylate or silane coupler, Cl ₂ Si
Those whose surfaces have been treated with (CH ₃ ) ₂ , alcohol, etc. can also be used in the same way. Further, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the silica filler is suspended in water or alcohol can also be used. The blending ratio of the fine powder silica filler is the sum of the poly(meth)acrylate of the polyester polyol (a) and the arylene bis[(poly)oxyalkylene(meth)acrylate] (b).
The amount ranges from 0.5 to 200 parts by weight, preferably from 0.5 to 100 parts by weight per 100 parts by weight. The curable resin composition for coating of the present invention has the above-mentioned essential 4
In some cases, the composition consists only of the following ingredients, but if necessary, polymerization inhibitors, dyes, solvents, ultraviolet absorbers, stabilizers such as antioxidants, fluorescent brighteners, methyl (meth)acrylate, Various additives such as (reactive) oligomers such as polyurethane acrylate and polymers such as polymethyl methacrylate can be blended. The blending ratio of these additives is appropriate. The curable resin composition for coating of the present invention is maintained in a suspended state by adding a solvent as necessary to improve its coating workability. The solvent is also used for the purpose of suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specifically, the solvents include benzene, toluene, xylene, cumene,
Hydrocarbons such as ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichloride, ethylene dichloride, perchlorene, titanium trichloride, ethane tetrachloride, Halogenated hydrocarbons such as propylene chloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanonol, ethylene glycol, propylene glycol, glycerin,
Alcohols such as ethylene glycol monomethyl ether and diethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; acetonitrile; Examples include nitriles such as pionitrile and capronitrile, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate.
The blending ratio of these organic solvents is based on the poly(meth)acrylate of the polyester polyol.
(a) and the arylene bis[(poly)oxyalkylene (meth)acrylate (b) in a total of 100 parts by weight, usually 5 to 3000 parts by weight, preferably
It ranges from 10 to 2000 parts by weight. In the composition of the present invention, a method for preparing a suspension composition from a composition containing the above-mentioned essential components and various additive components such as a solvent and a stabilizer added as necessary is to prepare the suspension composition by adding the above-mentioned raw material mixture. Examples of kneading and mixing methods include a normal roll, a Banbury mixer, a ball mill, an attritor, a whipper, an oak mixer, a desolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, a mixer, a mixing tank, etc.
Uniformly dispersed compositions are obtained by these methods. The suspension composition may be applied to the surface of the substrate of the molded body using conventionally known methods such as brush coating, spraying, dipping, barcoding, roll coater, spin coater, and gel coater. can be adopted. 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. In addition, as a method for curing the above-mentioned coating film to form a film, a method of polymerizing and crosslinking curing with light, especially ultraviolet rays, is used, and photocuring is usually carried out at a temperature of -10 to 150°C, preferably 5 to 130°C. Light irradiation is carried out, and the time is usually 1 sec to 1 hr,
Preferably it is 1 sec to 10 min. The curable resin composition for coating of the present invention can be coated on the surface of any molded body made of thermoplastic resin, thermosetting resin, metal, or the like. 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, for example, polyolefins such as a homopolymer of α-olefin or a copolymer mainly composed of α-olefin, polyacrylic acid ester resin, polycarbonate resin, polyester resin,
Examples include 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-decene; or a copolymer consisting of a mixture of two or more of the above-mentioned α-olefins, and a lower aliphatic vinyl carboxylate such as vinyl acetate or vinyl propionate;
Contains a small amount (for example, 30 mol% or less) of other components such as acrylic acid carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid, and salts of acrylic carboxylic acids. Examples include copolymers. Among these polyolefins,
Polyolefins having crystallinity are commonly used. Specific examples of the polyacrylic carboxylic acid ester resin include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. can. Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A 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, nylon
10, nylon 12, etc. In addition to the above resins, polyacetals include polystyrene, acrylonitrile-styrene copolymer, acrolinitrile-butadiene-styrene copolymer,
polysulfone resin, polyphenylene oxide,
Examples include modified polyphenylene oxide, polyphenylene sulfide resin, and polyether sulfone resin. Specifically, the thermosetting resin constituting the base layer includes unsaturated polyester resin, epoxy resin,
Examples include melamine resin, diallyl phthalate resin, and polyallyl glycol carbonate resin. Furthermore, specific examples of the metal constituting the base layer include aluminum, iron, stainless steel, and the like. When coating the substrate surface of a molded article such as a resin with the curable resin composition for coating of the present invention, the substrate surface of the molded article is washed with various solvents, an alkaline aqueous solution, and a surfactant. Various surface treatments such as ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. can be applied. Furthermore, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the substrate surface of the molded article, an intermediate adhesive layer made of a primer may be placed between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. When the base layer is polyolefin, the primer may be α,β-unsaturated carboxylic acid, its acid anhydride, its ester, etc.
Modified polyolefins grafted with β-unsaturated carboxylic acid or derivative components thereof are commonly used. In this way, the composition of the present invention is coated on the surface of the base layer of the molded article, which has been subjected to surface treatment or primer treatment as necessary, by the method described above, and then subjected to a curing treatment. 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, examples include 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 panels. Shower domes can be used for coffee, water tanks, lighting equipment covers, stereo device covers such as players, various meter dials and covers, car headlight or tail lamp covers, level sensors, shatterproof films for glass, and mold release. Films, insulating films, agricultural films and other films, optically reproducing video disks, viewing windows for various devices such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motor boats, etc., and automobiles. glass (windshields, rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, etc., tableware, mirrors, various containers such as oil bottles and cosmetic bottles, relay cases, fuse boxes, and motorcycles. side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelves, Wall sheets, wallpaper, furniture, lightweight wallboards, tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain rods, rain gutters, insulation materials, waterproof coating materials,
Curtains, window frames, automobile foil, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames,
Examples include fans, instrument panels, bumpers, and brakes. In addition to the above, we also offer home appliances, automobile parts, motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, electronic parts,
It can also be used in packaging materials, sports equipment, medical equipment, and electronic power-related parts. Next, the present invention will be specifically explained using examples. In addition, in the main text of the specification or the examples, evaluation was performed by the following method. (1) Refractive index Add 2wt% of a sufficiently dried inorganic substance to a liquid with a known refractive index, and after sufficiently dispersing it, visually check the transparency. The refractive index should be the same as that of the most transparent liquid. (2) Surface gloss (gloss) This was performed according to the 60 degree specular gloss in JIS K5400-1979. (3) Light transmittance Conducted according to JIS K6714. (4) Adhesion The test was conducted according to the cross-cut test in JIS K5400-1979. Judgment is based on how many of the 100 pieces are glued together. (5) Sand abrasion 800g of silicon carbide abrasive material is dropped onto the coating according to the method of JIS T8147-1975. Abrasion resistance is expressed by the difference in surface gloss before and after the test.
The smaller the number, the better the wear resistance. (6) Taber wear According to the method of ATSM D-1044, wear ring CS
−10, rotate the film 1000 times with a load of 500 g. Wear resistance is expressed 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 K5651. (8) Flexibility A strip test piece with a width of 5 mm and a length of 10 cm is 2 cm in diameter.
It is folded along the outer circumference of a cylinder and represents the angle at which the coating cracks or peels off from the substrate. The larger the value, the better the flexibility. (9) Water resistance After immersing the test piece in pure water at 40°C for 240 hours, the appearance and adhesion of the outer coating layer were evaluated. (10) Heat resistance After holding the test piece in a gear aging tester at 80°C for 400 hours, the appearance and adhesion of the outer coating layer were evaluated. (11) Volatile oil resistance The appearance and adhesion of the outer coating layer after immersing the test piece in petroleum benzine for 24 hours at room temperature was evaluated. (12) Gasoline resistance The appearance and adhesion of the outer coating layer were evaluated after the test piece was immersed in regular gasoline for 24 hours at room temperature. (13) Sheet cycle resistance The test piece was kept in an air oven at 80℃ for 2 hours, then left at room temperature for 1 hour, then kept in a cold room at -30℃ for 2 hours, and then kept at room temperature for 1 hour. put. 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 Place the test piece in a sunshine weatherometer.
After holding for 400 hours, the appearance and adhesion of the outer coating layer were evaluated. In addition, the following reference examples show synthesis examples of poly(meth)acrylates of polyester polyols. Reference example 1 Pentaerythritol 136g, succinic acid 59g,
3 g of paratoluenesulfonic acid and 100 g of toluene were charged, and an esterification reaction was carried out at 150°C for 2 hours in a nitrogen atmosphere. After cooling, 220 g of acrylic acid, 3 g of hydroquinone, and 200 g of toluene were added, and an esterification reaction was carried out at 120°C for 4 hours. After washing the reaction solution with weak alkaline water and water, 0.05 g of hydroquinone was added and low-boiling substances were distilled off to obtain a polyacrylate of polyester polyol having an average molecular weight of 700. It was confirmed by NMR that the average number of double bonds in one molecule of this polyacrylate of polyester polyol was 4.2. Reference example 2 Trimethylolpropane 138g, adipic acid 73g
g, paratoluenesulfonic acid 3g, acrylic acid
A polyacrylate of a polyester polyol having an average molecular weight of 620 and an average number of double bonds per molecule of 3.6 was obtained from 220 g of polyester, 3 g of hydroquinone, and 400 g of toluene in the same manner as in Reference Example 1. Reference example 3 Pentaerythritol 136g, itaconic acid 65.5g
g, acrylic acid 140g, methacrylic acid 100g, toluene 800g, 98% sulfuric acid 6ml and phenothiazine
Prepare 0.2g and heat at 100 to 110℃ for 8 hours in nitrogen atmosphere.
An esterification reaction was performed. After washing the reaction solution with weak alkaline water and water, 0.05 g of hydroquinone was added and low-boiling substances were distilled off to obtain a poly(meth)acrylate of a polyester polyol with an average molecular weight of 750 and a number of acryloyloxyl groups in one molecule of 5.3. Ta. Reference example 4 Pentaerythritol 136g, diethylene glycol 106g, succinic acid 177g, acrylic acid 240g
The average molecular weight was determined by the method described in Reference Example 3 except that
1200, a polyacrylate of polyester polyol having an average number of double bonds in one molecule of 5.5 was obtained. Example 1 30 g of polyacrylate of the polyester polyol described in Reference Example 1, 70 g of 2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane, 1-(4-isopropylphenyl)-
2-hydroxy-2-methyl-1-propanone 5
g and 100 g of 1,1,1-trichloroethane were added to the mixture with stirring until the average particle diameter
Finely powdered silica (manufactured by Nippon Aerosil Co., Ltd., trade name R-972) having a particle size of 20 mμ and a refractive index of 1.45 was gradually added (amount used: 5 g) and thoroughly stirred until uniform dispersion was obtained. After that, the mixture was transferred to an attritor (manufactured by Mitsui Miike Manufacturing Co., Ltd.) filled with steatite balls, and the agitator was turned on while cooling the tank with water.
Rotate at 150 rpm and mix for 3 hours. Thereafter, 120 g of toluene was added, and after further mixing for 10 minutes, the mixture was taken out from the attritor to prepare a coating composition [A]. On the other hand, polypropylene (Mitsui Petrochemical Industries)
An injection square plate (thickness: 3 mm) made from 1,1,1-trichloroethane vapor (manufactured by Mitsui Petrochemical Polypropylene SJ-313) was exposed to 1,1,1-trichloroethane vapor for 1 minute, then dried at room temperature for 1 minute, and then exposed to anhydrous maleic acid. Acid denaturation
The injection square plate was immersed in a 15 g/toluene solution [B] of PER (propylene content 67 mol%, maleic anhydride content 6 w%) for 20 seconds and slowly pulled up. After drying at room temperature for 5 minutes, heat drying was performed at 80° C. for 30 minutes. Next, the primer-treated polypropylene square plate was immersed in the coating composition [A] for 30 seconds, slowly pulled up, and then dried at room temperature for 1 minute and then at 60° C. for 5 minutes. This test piece was heated using a 1.5kW high-pressure mercury lamp (120W/cm).
Below, the outer coating layer was cured by irradiating it with ultraviolet light for 30 seconds at a distance of 15 cm. Table 1 shows the performance of this coating. Example 2 In Example 1, the polyacrylate of the polyester polyol described in Reference Example 2 was used as the coating composition [A] instead of the polyacrylate of the polyester polyol used in Example 1 (Reference Example 1). 2,2-bis(4-acryloyloxyethoxyethoxyphenyl) instead of 2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane in Example 1.
A coating composition [A] was prepared in exactly the same manner as in Example 1, except that 30 g of propane was used, and an outer coating layer was cured using this in the same manner as in Example 1. Table 1 shows the performance of this coating. Example 3 In Example 1, 70g of the polyacrylate of the polyester polyol described in Reference Example 4 was used in place of the polyacrylate of the polyester polyol used in Example 1.
2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane in place of 2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane
A coating composition [A] was prepared in the same manner as in Example 1, except that 30 g of bis(4-acryloyloxypropoxyphenyl)propane was used, and an outer coating layer was formed using this in the same manner as in Example 1. Cured and formed. The coating performance is shown in Table 1. Comparative Examples 1 and 2 In Example 1, 5 g of each photopolymerization initiator listed in Table 1 was used instead of the photopolymerization initiator 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone. A coating composition was prepared in the same manner as in Example 1 except for the blending, and an outer coating layer was formed using this in the same manner as in Example 1. The coating performance is shown in Table 1. Comparative Example 3 An outer coating layer was formed in the same manner as in Example 1, except that the fine powder silica filler was not blended in Example 1, and 150 g of toluene was used as a solvent to prepare the coating composition [A]. Performance was evaluated. The results are shown in Table 1. Comparative Example 4 In Comparative Example 3, 70 g of the polyacrylate of Reference Example 3, 30 g of 2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane, and light were used in place of the polyacrylate of the polyester polyol of Reference Example 1. An outer coating layer was formed in the same manner as in Comparative Example 3 except that 5 g of benzophenone was used as a polymerization initiator, and the performance was evaluated. The results are shown in Table 1. Comparative Example 5 In Example 1, fine powder silica filler R-
972 (trade name) instead of using 5g, the average particle size
An outer coating layer was formed in the same manner as in Example 1, except that 5 g of Thyroid 244 (trade name) silica filler of 1600 mμ was used. Table 1 shows the performance evaluation results of the outer coating. The abbreviations used in Table 1 below represent the following compounds, respectively. BAEP…2,2-bis(4-acryloyloxyethoxyphenyl)propane BADEP…2,2-bis(4-acryloyloxyethoxyethoxyphenyl)propane BAPP…2,2-bis(4-acryloyloxypropoxyphenyl)propane BIE…benzoin isopropyl ether BPH…benzophenone 1HP…1-(4-isopropylphenyl)-2-
Hydroxy-2-methyl-1-propanone

【table】

【table】

Claims (1)

[Scope of Claims] 1 (a) A poly(meth)acrylate of a polyester polyol having at least two acryloyloxy or methacryloyloxy groups in one molecule and having no urethane bond, (b) Polyester polyol poly(meth)
The following general formula [] is in a range of more than 0 and 1000 parts by weight per 100 parts by weight of acrylate (a) However, R ¹ : H or methyl group n: 1 to 20 R ² : -CH ₂ -CH ₂ -, [Formula] [Formula] Ar: [Formula] [Formula] X: -O-, -S-, - SO ₂ −, −CH ₂ −,
[Formula] [Formula] R ³ , R ⁴ : arylene bis [(poly)oxyalkylene (meth)acrylate] represented by H or a lower alkyl group, and (c) poly(meth) of the polyester polyol
0.01 to 20 parts by weight of 1-
(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone photopolymerization initiator, and (d) poly(meth)acrylate of polyester polyol (a) and represented by the general formula [] Average particle size ranging from 0.5 to 200 parts by weight per 100 parts by weight of (meth)acrylate (b)
A curable resin composition for coating, characterized in that it contains finely powdered silica having a thickness of 1 mμ to 10μ and a refractive index of 1.40 to 1.60.