JPS5984926A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:The titled composition, containing a poly(meth)acrylate compound of a polyepoxy compound and a polyurethane poly(meth)acrylate and a polymerization initiator respectively in specific amounts, and having improved curing and film characteristics. CONSTITUTION:A curable resin composition for coating prepared by kneading and mixing (A) a poly(meth)acrylate of a polyepoxy compound, e.g. a polyglycidyl ether of ethylene glycol, etc. having two or more epoxy groups in one molecule, consisting of the polyepoxy compound and (meth)acrylic acid, with (B) a urethane poly(meth)acrylate compound having two or more (meth)acryloyloxy groups in one molecule, (C) a polymerization initiator, e.g. benzoin, together with various additives if necessary added thereto. The amounts of the components are as follows: >0-1,000pts.wt. based on 100pts.wt. component (A) component (B), and 0.01-20pts.wt., based on 100pts.wt. total amounts of the componens (A) and (B), component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides (JI for coating the substrate surface of a 11I fat molded body): - Excellent ease of use in the air, surface hardness of the coating, 1 (!11 Abrasion resistance, abrasion resistance, flexibility, surface gloss, [αIj heat resistance, water resistance, solvent resistance, surface roughness and molded product, 14 (adhesion to body surface) Concerning a post-curing type (1-fat Al composition) with excellent film properties.

In general, thermosetting resin moldings (1, gold maple products, crow products, etc.) are made of resin molded products (1, gold maple products, crow products, etc.), and are lightweight and impact resistant. There are various types of scales that are not only good scales, but also cheap and easy to mold.
1 with A11 points Automobile, auto pie, %'?
Li soil is widely used in place of these materials in products, daily wear (cargoes), and many other fields. If the surface hardness is low and you scratch it, it will look like #f1M 7
However, it has the disadvantage that the surface is easily scratched because it is weak.

For example, the surface of the molded body is susceptible to injury due to spillage, cuffs, and pulls during installation or transportation of molded parts, or during product use (Table 1)! -1) The use of these molded bodies is severely limited due to their poor performance.

Many proposals have been made to address the above-mentioned drawbacks of the surface of the resin molded substrate.

The method e.'1 is a method in which the surface of these molded bodies is coated with 41 layers of outer covering made of Kyurin-Kuraya resin.

Out of these 1 units, 411 + ↑
Specifically, examples of the composition-forming component include silicone monomers or compositions of these components with various polymers, resin compositions consisting of methylolmelamine and other curing components, and polyfunctional resin compositions. A t1 arsenic acrylic carboxylic acid ester spindle or a composition of this with a 1:i2 polymerization component has been proposed. Even if a tympanic membrane layer consisting of these film-forming elements is formed on the base surface of a resin molded product such as polyolefin, the adhesion between the ruptured membrane layer and the base layer of the Tree III molded product is generally not good. There is a drawback that the ruptured membrane layer is easily peeled off from the body. Furthermore, in order to improve these drawbacks, the surface VCf+ of the resin molded body base layer
There are also known methods for carrying out the processing described in iii. For example, surface treatment using corona discharge and surface treatment using brimer have been proposed. However, even with surface treatment, it is not possible to sufficiently improve the adhesion between the base layer of the resin molded product made of polyolefin or the like and the coating layer made of the cross-curing resin for practical purposes. It is often difficult. It's a place.
Among the film-forming elements, silicone-based film-forming elements are expensive and have poor redness.

Among the film-forming elements mentioned above, 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) polyhydroxyl compounds, etc. It is proposed to do so. Even if these polyfunctional acrylic yarn carboxylic acid ester derivatives are used alone as film-forming elements and are formed as a Fr1k film on the base surface of a resin molded product, these films will not be as stable as the curing speed in live air during curing. Poor curing properties, hardness, scratch resistance, surface scratchability, abrasion, flexibility, surface roughness, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates. The coating properties, or many of these properties, are often inferior, and it has not been possible to fully satisfy the requirements for industrial-scale use. Although attempts have been made to improve these drawbacks by using a combination of two or more of these film-forming elements, none of them have been able to improve these drawbacks to some extent. However, there were other new difficulties when coating the substrate surface of a resin molded article such as polyolefin.

The present inventors have discovered that by coating the base surface of a molded resin such as a thermoplastic resin or a thermosetting resin, it has excellent curing properties during curing, and that the resulting film has excellent hardening properties. As a result of intensive studies on the composition for use in the production of polyurethane, we found that a poly(meth)acrylate of polyevoquine compound (a), a specific amount of polyurethane poly(meth)acrylate (1)), and a specific amount of a polymerization initiator (C) were used. It has been found that the above object can be achieved by administering a composition containing the present invention, and the present invention has been completed. 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 coating layer, the curing speed in air during curing is The resulting coating has excellent surface hardness, scratch resistance,
Many coating properties such as abrasion resistance, flexibility, surface gloss, amphiphilicity, water resistance, solvent resistance, weather resistance, and adhesion to substrates are generally well-characterized. ing.

To summarize the present invention, the present invention relates to (a) a poly(meth)acrylate of a polyevoquine compound having at least two or more epoxy %2 in one molecule, (b) a poly(meth)acrylate of a 7J polyester/compound (meth)acrylate compound (a>
I ooct heavy MA over 100 against Myanmar
, 'jsis, two or more acryloyl oxyyl groups or methacryloyloxyl in one molecule,
I+! - A total of 100 urethane-based poly(meth)acrylate compounds → and (C) a poly(meth)acrylate of the polyepoxy compound (- and the polyurethane-based poly(meth)acrylate compound (b)) 0.0 for part
Polymerization initiator in the range of 1 to 20 parts by weight, ? The gist of the present invention is a curable wood composition 11 for resin coating, which is characterized by containing:

A poly(meth)acrylate of a polyepoxy compound (■(/i
, a polyepoxy compound formed from an aliphatic, alicyclic, aromatic or aromatic polyepoxy compound having at least two or more epoxy groups in one molecule and acrylic acid or methacrylic acid. It is a poly(meth)acrylate of an epoxy compound. Here, specific examples of polyepoxy compounds having at least two or more epoxy groups in one molecule include Nild, Me-F-L/N glycol, Ethylene glycol, Fry-F-L/N glycol, Fubrene glycol, and Pentyl glycol. Lengelicol, Beki/Lengericol, Octylene glycol, Tesylene glycol, Totesylene glycol, Glycerin, Trimethylolpropane, Pentaerythritol, Polyoquinoethylene glycol, Polyoquine propylene glycol, Sidaricerin,
polyglycidyl ether of tritrimethylolpropane, penquerythritol, tripentaerythritol polyol; 1,2-7 chlorohexylene glycol, 1,4-cyclohexylene glycol 1. , 2.2-bis(4-hydroxychlorohexyl)propane, 1.1-bis(4-hydroxychlorohexyl)ethane, and polyglycidyl ether of alicyclic polyols such as bis(4-hydroxycyclohexyl)methane; T for hydroquinone, resorcinol, catechol, and phlologulone.

Polyglydyl ethers of phenols, 2,2-bis(4-hydroxyphenyl)propane, 1.1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, novolac type phenol Disease fat,
Polydary of aromatic polyols such as polyglycidyl ether of aromatic polynuclear polyhydric phenols such as resol type 71 sole resin, polyglycidyl of aromatic polycarboxylic acids such as notaric acid, isophthalic acid, terephthalic acid, etc. Can you give all examples of esters? More specifically, the polyepoxy compound 7 includes ethylene glycol diglycidyl ether, glopylene glycol diglycidyl ether, butylene glycol diglycidyl ether, glycol triglycidyl/ruedel, chrycerin diglycidyl ether, and trimethylolpropane triglycidyl. Ether, trimethylolpropane cyclidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerys lJ tol diglycidyl ether, polyoxyethylene glycol diglycidyl ether, polyoxyethylene glycol diglycidyl ether, digcerin tetradary cydyl ether, 7glycerine l-IJglycidyl ether, cydaliserin 7 glycidyl ether, n) l) methylol o /: tetracrisyl ether, /trimethylolprobant l) propane dicline/ruether, /bentaerythritol hexacl) /sil ether, dibe/taerythritol pentaglycyl/ruether, /hentaerythritol tetraglynodyle ether, /pe/taerythritol trigly//ruether, pentaerythritol/cl aliphatic polyepoxy compound such as 7-dyl ether,
1,2-cyclohexylene glycol > ri) cydyl ether, 1,4-cyclohexyl/lene glycol dyl ether, 2,2-bis(4-hydroxychlorohexyl)furopane sigly/dyl ether, bis(4-cyclohexylene glycol)
-Alicyclic polyepoxy compounds such as hydroxyl chlorohexyl) methane sidalicidyl ether, hydroquinone/glycidyl ether, resolson diculinyl ether, catechol diglycidyl ether, phloroglucicin tricridyl ether, 70 Rochrun cyclocinyl ether, 2,2-bis(4-hydroxyphenyl)
Furopancrisi/ruedel, 1.1-bis(4-hydroxyphenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)methanecycline/ruedel, phthal order cyclicisol j~ster, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, Aromatic epoxy compounds such as polyglycidyl ether of novolac type nogonol resin and polyglycidyl ether of resol type phenol resin can be exemplified, and a mixture of two or more of these may be used.

A poly(meth)acrylate product of a polyepoxy compound (the phrase refers to a poly(meth)acrylate product of a polyepoxy compound formed from the polyepoxy compound and acrylic acid or methacrylic acid, which is blended into the curable resin composition for coating of the present invention. ) acrylate compound, and more specifically, the general formula [1] in which the epoxy group of the polyepoxy compound is ring-opened and a hytrogiful group and a (meth)acryloyloxyl group are bonded to adjacent carbon atoms. [In the formula, R1 represents a hydrogen atom or a methyl group.] It is a compound having at least two of these units in the molecule, and therefore 2 or more (meth)acryloyloxyl groups and 2 or more -
It is a compound with a hydroquine group. It can be produced by converting the polyepoxy compound into poly(meth)acrylate (or ablating) the polyepoxy compound and reacting the polyepoxy compound with acrylic acid, methacrylic acid, or a mixture thereof.

The reaction is carried out, if necessary, in the presence of a catalyst. Catalysts include primary amines, secondary amines, tertiary amines, their salts, quaternary ammonium compounds, organic acid salt compounds, Lewis acids and their complexes, and alkaline earth metals.
Rogenide or hydroxide, etc., can be found. In addition, u weight Ktd, butylamine, hexylamine, dibropyramine, trimethylamine, triethylamine, dimethylamine hydrochloride, diethylamine oxalate, tetramethylammonium chloride, tetraethylammonium bromide, sodium acetate, sodium trichloroacetate, phthalic acid sodium, sodium phthalate,
Potassium phthalate, tin chloride, zinc chloride, trifluoride ethylamine complex, trifluoride (motor cord alcohol complex, lithium chloride l1, sodium bromide, calcium chloride, calcium bromide, lithium hydroxide, sodium hydroxide, hydrogen chloride,
Examples include hydrogen bromide, and a mixture of two or more of these can also be used. The proportion used is usually 1.005 to 5 L per 10 parts by weight of the epoxy compound (J parts by weight).
This is a serious area. The usage ratio of the acrylic acid or methacrylic acid is 1, and the epoxy group of the polycyboxy compound is 1
It is usually in the range of 0.6 to 1.5 mol, preferably 0.9 to 1.1 mol.

The reaction is usually carried out at a temperature of -10 to 160°C.

The urethane-based poly(meth)acrylate compound (G) blended into the curable resin composition for sheet cutting of the present invention has one or more urethane bonds in one molecule and has an acryloyloxyl group of 21β] or more. Or (meth)bucrylate is a polyfunctional compound containing a methacryloyloxyl group. Specifically, a (meth)acrylic chloride isocyanate compound that does not have a hydroxy/ru group! A urethane-based poly(meth)acrylate compound formed by the reaction with I2, a polyurethane-based poly(meth)acrylate compound consisting of a poly(vine) acrylate of a polyurethane polyol, a polyurethane-based poly(meth)acrylate compound, a poly( Horsetail/tan based poly(meth)acrylate
Examples include meth)acrylate compounds. The polyol component units constituting these urethane-based poly(meth)acrylate compounds include aliphatic polyols, alicyclic polyols, aromatic polyols, polyoxyalkylene glycols, polyoxyalkane polyols, arylene bis[poly Oxyalkane polyol, polyester polyol, polyurethane polyol, polyester Jf urethane polyol,
Polyurea polyols can be shown as ethylene glycol, propylene glycol, ethylene glycol, hexylene glycol, A-cutylene glycol, chrycerin, trimethylol glycol, etc. ] Bread, pentaerythritol, ethylene glycol, l-1) ethylene glycol, /
Noropylene glycol, /butylene glycol, ndarycol, zohexylene glycol, tsukurisen, ditrimethylolpropane, /pentaerythritol, polyoxyenalene glycol, polyoxyenalene glycol, polyoxypropylene dalycol, Polyoxy〉゛Tyrendaricol, Tsuku■Kohex/Lengelicol, 2.2-bis(4-hydroxycyclohexyl)propa/, bis(4-hydroxycyclohexyl)methane,, 2.2-bis(4-hydroxyethyl) ), furono;, 212-his(4-hydroxyphenyl)ethane, bis(4-1j)"roxyphenyl)methane, bis(acryloki7ethyl)hydroxyethyl isocyanurate, bis(methacryloyl-published xoenal) Hydroxyethyl isocyanurate; angle 'I
Hc24ffli': Nota ((meth)acrylate of polyglycinol ether of Bll 7 alcohol; rI/J divinity's polyhydric alcohol component unit, succinic acid, gluta) L; acid, 'adipine, sheric acid, sebacin Acid, maleic acid, fumaric acid, itaconic acid, detrahydrophthalic anhydride [shun, hexahylphthalic anhydride, nthalic acid, phthalic anhydride, t. limeri, tonic acid, phthalic anhydride]
・Polyester polyols formed from one unit of polygonal carbonic acid with 1 and 1 waves; polyurethane polyols formed from the various polyol component units and the following 3 units of various /isonoanate components; can be exemplified. However, these 1 cretane poly(meth)acrylate compounds Q'lJ k ('4 diisocyanate component units are aliphatic diisocyanate'-) --
1., alicyclic diisocyanate, 'lj aromatic cyisozoanate, and of course, the dinitrile bistunobonate compound corresponding to these phyiso7anate component units Q or these A bisnow-7-bamate compound corresponding to a diisocyanate component type j>2 may also be used. h* Sonic acid component diiso/ana-1. Specific examples of fractional units include trimethylene diisoana-1, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and decamethylene diisocyanate. 7 anate, dodecamethylene 7' isocyanate, methyl/dibutyl hexane-2,
4-/Inocyanate, Ro-Inocyanato Methyl-5
,5,5-)IJ methylzochlorohexyl isocyanate-1
・, 4.4'-cycloheginylmethane diisocyanate, ingropirite/bis(4-zochlorohexolisonanate) phenylene diisocyanate, tolylene diisoana-1, diphenylmethane diisocyanate, bistri An example of this is the following. By mixing the polyurethane polyol and methacrylic acid diluted with acrylic acid according to a conventional method in the presence of a catalyst if necessary, the poly(meth)acrylate of the polyurethane poly; obtained,
Similarly, poly(meth)azilylate of polyester thread polyurethane polyol can be obtained by reacting the polynisder-based polyurethane polyol with acrylic acid-t or methacrylic acid.

Among the urethane-based poly(meth)acrylate compounds, urethane-based poly(meth)azirylate compounds obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group with a diiso/ana-1 compound are used. Examples of the (meth)acrylic acid ester component unit having a hydroxyl group include a reaction between a polyhydroquine group-containing compound and (meth)acrylic acid, and a reaction product between Evokin Ibi@1 and (meth)acrylic acid. , specifically 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylate of glycidyl acrylate, methacrylate of glycidyl acrylate, methacryl Acrylic acid glycidyl ether 17-methacrylate, methacrylic acid glycidyl ether 1-methacrylate, glycerin monoacrylate, glycerin monomethacrylate, glycerin-1,6-diacrylate, glycerin-1,6-one methacrylate, trimethylolpropane diacrylate, trimethylolpropane monomethacrylate, trimethylolpropane diacrylate,
Trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, hentaerythritol acrylate, pentaerythritol amethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, /bentaerythritol monoacrylate, pentaerythritol monoacrylate IJ L monomethacrylate dipentaerythritol 7 acrylate, dipentaerythritol dimethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dihentaerythritol tetraacrylate 1-, dipentaerythritol tetramethacrylate, dipentaerythritol 1-lupentaacrylate, dipentaerythritol pentamethacrylate, bis(acryloyloxyethyl) hydroxyethyl in cyanurate, bis(methacryloyloxytyl) hydroxyethyl isocyanuride, methacrylate of propylene glycol diglycyl ether, propylene glycol/ Dimethacrylate of glycinol ether, Gl) Acrylate-1 of 7-1,6-sibricidyl ether, 7-methacrylate of glycerin-1,6-sibricidyl ether9 Of course, glycerin triglycidyl ether triacrylate of glycerin triglycidyl ether, diacrylate of pentaerythritol/glycidyl ether J, dimethacrylate L-1 of pentaerythritol/chrysyl ether, chemical formula 9, pentaerythritol tricrylate/ Triacrylate of dielether, trimethacrylate of pentaerythritol triglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane for diacrylate of 2,2-his(4-hydroxycyclohexyl)furopane diglycidyl ether. All examples include dimethacrylate of diglycidyl ether, diacrylate of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, dimethacrylate of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, etc. As the diynn anate component unit, the above-mentioned compounds can be exemplified. Among the urethane-based poly(meth)acrylate compounds (b), urethane-based poly(meth)acrylate compounds containing aliphatic alkylene diisocyanate component units and alicyclic diiricyanate component units as diisocyanate component units are used. ) The use of acrylate compounds is preferable because the color, weather resistance, and flexibility of the cured film are improved. The blending ratio of the urethane-based poly(meth)acrylate compound (c) is greater than 0 to 1000% with respect to the poly(meth)acrylate compound (a) of the polyepoxy compound (a). It is necessary for the content to be in the range of 0 parts by weight, and in the range of not more than 700 parts by weight, especially 2 parts by weight.
Preferably, the amount is in the range of 0 to 500 parts by weight.

Poly(meth)acrylate compound (a) of the polyepoxy compound of nuclear urethane-based poly(meth)acrylate compound υ) 1 [J O, blending ratio to parts by weight is 10
If the amount exceeds 00 parts by weight, the abrasiveness of the coating may be affected.
I started to play J&-.

The film-forming element component (main 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 merging monomer components. It is also possible to add and combine components. Other properly compatible monomer components include by-products or intermediates for producing poly(meth)acrylates of the polyepoxy compounds or urethane-based poly(meth)acrylate compounds, such as (meth)acrylates of monoevoquino compounds. In addition to acrylates, mono(meth)acrylates of polyepoxy compounds, and urethane-based mono(meth)acrylates, (meth)acrylic acid, metinope (meth)acrylic ethyl, (meth)acrylic Examples include (meth)acrylic esters such as 2-hydroxyethyl.

The curable resin composition for coating of the present invention is applied to the surface of the base of a resin molded body. In order to crosslink and cure the composition to form a film, a polymerization initiator (C) is added to the composition. It is necessary to mix them. As the curing method, a curing method using ultraviolet rays, a curing method using heat rays, etc. are usually employed. In the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator, and specific examples of the photosensitizer include benzoin, benzoin methyl ether, benzoin ethyl needle, benzoin (nobu b pyru ether, benzoin isobutyl ether, etc.). benzoin or its ether,
Benzophenone compounds such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone; benzyl compounds such as benzyl, benzyl dimethyl ketal, and benzyl dimethyl ketal; 1-(4-iapropylphenyl)-2-hydroxy-2- Methyl-1
- Hydroxyalkylphenyl ketone compounds such as propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, and 1-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propanone. I can give an example. In the case of curing by heat, a radical initiator is blended, and specific examples of the radical initiator include azo compounds such as azobisisobutyronitrile, penzoyl perio-V-cyto, and lauryl peroxide 1.
．． Examples include peroxides such as /1ert-phthyl peroxide, diq'ruber oxide, and cumene hydroperoxide. Furthermore, it is possible to add both a photosensitizer and a radical initiator to the curable resin composition for coating of the present invention, and adopt a method in which both the photosensitizer and the radical initiator are allowed to proceed at the same time. It is also possible to adopt a method of proceeding with heat curing after proceeding with curing.

Furthermore, it is also possible to adopt a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator) is as follows:
A total of 10 of the meth)acrylate compound (a) and the polyurethane-based poly(meth)acrylate compound (b)
The blending ratio of the polymerization initiator is necessary to be in the range of 0.01 to 20 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight. 0 parts by weight based on a total of 100 parts by weight of the poly(meth)acrylate of the BoIJ Epoquin compound (a) and the urethane poly(meth)acrylate compound (b)
．． If the amount is less than 0.01 parts by weight, the polymerizability of the composition will decrease, making it impossible to obtain a hard film, and if it is more than 20 parts by weight, the film obtained from the composition will turn yellow. .

The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, or may further include a non-compounding agent, a transparent filler, a pigment, a paint, a bath additive, Contains various additives such as UV absorbers, antioxidants, stabilizers, fluorescent brighteners, (reactive) oligomers such as methyl (meth)acrylate and polyester acrylate, and polymers such as polymethyl methacrylate. can do. The blending ratio of these additives is 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 cured film obtained therefrom.

The average particle size of the fine powder inorganic filler is arbitrary as long as it is in powder form, but it is usually between 1 ml and 10 ml.
μ, preferably in the range of 1.5 mμ to 1 μ. In addition, in order to maintain the transparency of the outer covering layer, the refractive index of the finely powdered inorganic filler is usually 1.40 or less.
60, preferably in the range of 1.42 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass peas, glass flakes, diatomaceous earth, anhydrous silica, water 2n silica, silica, silica sand, quartz, kaolinite, montmorillonite, and seri. Examples include silica, talc, chlorite, chinastone, and feldspar. In addition, CJ, silane couplers, and titanium couplers 1. in which the surface of these finely powdered inorganic fillers is made of alkyl carboxylates, silane couplers, and titanium couplers. Those surface-treated with Cl2Sl(CH,+)2, alcohol, etc. can also be used in the same way.

Further, it is also possible to use colloidal silica, methanol silica sol, ethanoyl silica sol, ingropanol silica sol, etc. in which the above-mentioned non-reactive optical filler is dissolved in water or alcohol. In these finely powdered inorganic fillers, blending imitative powdered silica significantly improves the surface hardness, scratch resistance, and abrasion resistance of the outer core layer and impairs the transparency and surface gloss. This is especially preferable because it does not cause any problems. The blending ratio of these finely powdered inorganic fillers is the total of the poly(meth)acrylate of the polyepoxy compound (1) and the polyurethane-based poly(meth)acrylate compound (2). Usually 0.5 parts by weight
0.5 to 200 parts by weight, preferably 0.5 to 100 parts by weight
This is the area of Shigeibe.

The curable resin composition for coating of the present invention is maintained in a solution state or a suspended state by adding a solvent as necessary to improve its coating workability.

The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specifically, solvents include hydrocarbons such as benzene, l-luene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane, methylene chloride, chloroform tetracarbonate, and bromoform. , tricrene, ethylene dichloride, haculene, ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobensenato halokenated hydrocarbons, methanol, ethanol, ingropanol,
Butanol, benotanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol mono; alcohols such as thyl ether and diethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl,
Ketono with cyclohexanone, diethyl ether, /
Ethers such as propyl ether, butyl ethyl ether, phthyl ether, ethylene glycol dimethyl ether, ethylene glycol/methyl ether, nitriles such as acetonitrile, propionitrile, capronitrile, notyl formate, xf fluoride, methyl kF acid, ethyl acetate , vinegar fjl'o pill, drunkenness R isobutyl,
Examples include Nisdel such as butyl acid, pentyl acetate, methyl benzoate, and ethyl benzoate. The amount is usually 5 to 6000 parts by weight, preferably 1 to 201 parts by weight, based on a total of 1130 parts by weight of the polyurethane-based poly(meth)acrylate compound 0).

In the composition of the present invention, a bath liquid composition or As a method for preparing a suspension composition, the above-mentioned raw material mixture is prepared, and then the mixture is prepared using a molar, banha'): Kiser, Borgol, Atreita, Innova, Oak mixer, Dinolvar, or homogenizer. , a colloid mill, a sand pill, a vibration mill, and a cross-wire mixing method using a mixer 1 mixing and stirring device, and these methods can provide a uniformly dissolved or dispersed composition.
do. Methods for applying the bath liquid AT composition and the cloudy liquid composition to the substrate surface of the resin molding include brush coating method, spray method, dipping method, bar code method, [7-coater method, spin coater method] Conventionally known methods such as the method and the gel coater method 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. In addition, examples of methods for curing the above-mentioned coating film and fully forming the WM include a method of polymerization crosslinking and curing with light, especially ultraviolet rays, and a method of crosslinking and curing with heat. 1. Among these merging crosslinking methods, in the photocuring method, light irradiation is usually carried out at a temperature of -10 to 150°C, preferably not to 130°C, and the time is usually 1.
sec to ihr, preferably 1 sec to 10 hours. In addition, in the thermosetting method, the temperature during curing is usually -1
07i: Temperature: 150°C to 150°C, preferably 5 to 130°C, curing time (usually 0.05 to 1[]
hr, preferably 0.1 to 8 hr.

The curable resin composition for coating of the present invention can be applied to thermoplastic resin 1i'
g z Can be coated on the base surface of any molded body made of thermosetting resin 1. The shape of the molded body may be film-like, sheet-like, plate-like, curved or uneven, or any other shape. There is rarely a difference in L7 in the molded product.

Specifically, the thermoplastic resin constituting the base layer is an α-olefin homopolymer or an α-olefin homopolymer.
-Kankawa fin? Examples include polyolefins, polyacrylic acid ester resins, polycarbonate resins, polyester resins, boria resins, etc., which are the main components. Among these thermoplastic P7 resins, The base resin layer constituting the laminate molded product is preferably made of polyolefins, polyacrylic acid ester resin, or polycarbonate resin.

Specifically, the polyolefins include V, ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
A homopolymer of α-olefins such as 1-pentene, 1-octene, and 1 to decene, a copolymer consisting of a mixture of two or more of the above α-olefins, or a copolymer consisting of the above Cj-olefin as a main component, and PMJ2 Vinyl, vinyl propionate, 1 metal, methyl, methacrylic acid, gold M, acrylic carboxylate, acrylic ester, acrylic carboxylic acid salt, etc. Examples include copolymers containing r and other components in small amounts (for example, 6 U molar ratio or less). Among these polyolefins, polyolefins having crystallinity are usually used. tiiJ fit'', specifically as a polyacrylic carboxylic acid ester resin,
Examples include daughter polymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, notyl methacrylate, and ethyl methacrylate. In these polyacrylic carboxylic acid ester resins 90, polymethyl methacrylate is preferably used in the thermoplastic resin layer of the present invention as a base horse resin layer.
1.3.1) Specific examples of the oral polycarbonate resin include Hisph, Nord A, Polycarbonate-1-Zr.
I can give an example. A'J Mr. Specifically, the polyester resin includes polyethylene terephthalate, polytetramethylenete I/phthalate, and bisfu. Nol A, isophthalic acid, terephthalic acid co-i1 (condensate, ogine benzoic acid 11 (condensate, etc.) can be referred to as ``□J Loco''. 6, Tsu・Ron 6.6, Nylon 10, Na-(
You can open O12 etc.

In addition to the above resins, polyacetal, polystyrene,
Acrylonitrile/styrene copolymer, Acrylic [Koni]
IJ le phtadiene styrene cotn combination 4, poly,
sulfone juzuki, borin enyren okhiito, modified borinoenishi'n oxai l-, borin enyrenza 7a.
Examples thereof include hydride resin and polyether sulfone resin.

Specific examples of the thermosetting resin (1-glyceride resin) constituting the base layer include unsaturated polyester resin, epoxy resin, melamine resin, diallyl phthalate resin, and polyallyl glycol carbonate resin.

When coating the base surface of a resin molded body with the curable resin composition for coating of the present invention, l'j is applied to the base layer 111 of the molded body.
Cleaning with various bath agents, cleaning with alkaline aqueous solution, cleaning with surfactant m1, ultrasonic anti-61, electrolytic cleaning d1, plasto treatment 11 Zandoplast treatment] j1,
Enopunda place with sakarin or alkali! Various surface treatments such as flame treatment, corona discharge treatment, arc discharge treatment, Darrow discharge treatment, plasma discharge treatment, and chemical conversion treatment can be performed.

In addition, 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 or the like is provided between the substrate layer and the outer core coating layer.・
By forming a three-layer laminate with one side, it is also possible to improve the adhesion between the two layers. When the base layer is a polyolefin, a modified polyolefin grafted with an α,β-unsaturated carbonic acid or a derivative component of (a) is usually used as the primer. The composition of the present invention is coated on the surface of the base layer of the treated or primer-treated resin molded article 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, examples include daylight panels, sky domes, panels for solar water heaters, glove box pipes, glass panels, hour 81 glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, and blood bags. , coffee maker shower door, coffee maker, water tank, lighting device cover, stereo device cover such as player, various meter dials and covers, car henotranzo or tail run horn bar, level sensor, crow. Various films such as anti-scattering filters, release films, insulating films, and agricultural films, original video discs, sight windows for various devices such as clothes dryers, electric washing machines, hair dryers, oil coats, and autopipes. Lice-proof glass for motorboats, motorboats, etc., automobile glass (windshields, rear windows, opera windows, triangular windows)
(Zanroof), window glass for greenhouses, arithmetic houses, aquariums, etc., tableware, mirrors, various containers such as oil bottles and makeup skin, relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, and screens. table cloth,
Waterproof and moisture-proof film, tarpaulin sheet, insulation film, floor tile, floor sheet, door, double board, wall tile, countertop decorative board, roof board, wall notebook, wallpaper, furniture, lightweight wallboard, tableware, chairs, hastab, Toilet bowl, /'88 warehouse, wall panel, water supply and drainage pipe, wiring pipe, duct l-, curtain lot, rain gutter, insulation material, waterproofing material, spring, window frame, car foil, various glaze containers, car Interior materials, vanity tables, flower boxes, birch, Ikuruhod, roof tiles, shutters, waterproof pans, pipes, wiring materials, kyacams, tsumi,
Electrical appliances (A valve plugs, fans, instrument panels, bumpers, brakes, etc.) In addition to the above, we also produce home appliances, automobile parts, motorcycle parts, auto parts, civil engineering dyeing materials,
It can also be used for general industrial materials, office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and atomic bombs: A-related parts.

Next, the present invention will be specifically explained with reference to Examples.

In addition, in the main text of the specification or the examples, evaluation 1iiiIi was performed by the following method.

(1) Add 2 wt % of a dried inorganic substance with a sufficiently high refractive index I, Ii to a liquid with a known refractive index, and after sufficiently dispersing it, visually check the transparency. It is assumed that the refractivity is the same as that of the most transparent liquid.

(2) Surface gloss (cross) According to 60 degree specular gloss in JIS K 5400-1979 -) □ (3) Light intensity 3 It was performed according to JIS K /) 714.

(4) Adhesion 1-13 The test was conducted in accordance with the round-eye test in JIS K 5400-1979. The judgment is based on how many of the 100 gobans were glued together.

(5) Sandfall abrasion according to JIS T 8147-1975 (7) method
800 g of silicon carbide abrasive material is dropped onto the coating. Abrasion resistance cannot be determined due to the difference in surface gloss (cloth) before and after the test. The smaller the number, the better the wear resistance.

(6) Taper wear According to ASTM D-1044 method, wear @C8-
10. Rotate the target 1000 times using a 500g cart.

Wear resistance is measured by the amount of wear it undergoes after the test.

The smaller the amount of wear, the better the wear resistance.

(Sword lead @ hardness Ill according to JIS K 5651! I decided.

(8) Flexibility Width: 5 m, length: 10 (1 strip-shaped test piece, the jaw piece is along the outer circumference VC of a cylinder with a diameter of 2 C1 n) 11 length Y, will the daughter be run over? , expressed as the angle when placed 471 degrees from the base.

The higher the value, the greater the flexibility.

After the test piece was immersed in pure water at 40°C for 240 hours, the appearance and compactness of the outer skin membrane layer were evaluated. .

00 Heat Resistance After holding the test piece in a Chiya-1 aging tester at 80° C. for 400 hours, the appearance and adhesion of the outer coating layer were evaluated.

αD 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.

(A 12+ 1lj4 gasoline-based test piece was immersed in regular Gaflin for 24 hours at room temperature, and then the appearance and adhesion of the outer skin film layer were evaluated.

03) After holding the surface j heat cycle test piece in an air oven at 80°C for 2 hours, it was left at room temperature for 1 hour, and then in a cold room at -60°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.

The weather resistance test piece was held in a sunzoyain weatherometer for 400 hours, and the appearance and adhesion of the outer coating layer were evaluated.

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

Reference Example 1 500 m
20 g (0.12 M) of xamethylene diisocyanate was added to a 14-meter flask under a nitrogen atmosphere, and stirred at room temperature for 1511 r to prepare a diacrylate of propylene glycol diglycyl ether xamethylene diinonoanate. Urethane-based polyacrylate-1-(PCAHI)-1 consisting of component units was synthesized.

Reference example 2 /Bentaerythritol lupe/'taacrylate 50g (
0,095 mol), dipentaerythritol detraacrylate 30g (0,064 mol) and dipenta]
50011 g of a mixture of 20 g of Nirisritol hexaacrylate and 120 g of O-methyl isobutyl ketone
17.6 g (0.08 mol) of 6-indianatomethyl-='+, 5.5-1-limethyl 7chlorohexylisonanate was added to a four-tube flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 15 hours. Methyl in butyl ketone of urethane polyacrylate (DPAiP) made from dipentaerythritol polyacrylate-1 component unit and 6-isocyanatomethyl-3.5.5-trimethylcyclohexol isocyanonate component unit. Synthesized in solution.

Reference Example 6 74 g (0.2 M) of bis(acl) oyl oxine ethyl)hydroquine ethyl isocyanurate and 100 g of methyl isobutyl ketone were placed in 4 soomg flasks, and 6--1 socyanatomethyl filtrate was added under a gold-metal atmosphere.5. 5-) Add 22 g (Q, IM) of Limethyl cyclohexyl isocyanate and heat for 15 hr451 under N1 m
; Stir to prepare a urethane polyacrylate (BA Engineering IP) consisting of bis(acryloyloxyethyl)hydroquine ethyl isocyanurate component units and 6-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate component units. Seven methyl isobutyl ketone solutions were prepared.

Implementation Reli 1 2.2-bis(4-human'r=ki7sik'cohexyl)
75 acrylates of 7 Panocidalicidyl L-j/l, 25 g of the urethane polyacrylate (PCAHI) described in Reference Example 1, 5 g of benzoin inglobil ether, and 110 methyl isobutyl ketone.
Pour 111g of the sample into a 500mA 4-lens flask at room temperature.
A transparent coating composition [8] was prepared by stirring.

On the other hand, an injection square plate (thickness: 5J-316, manufactured by Mikata Petrochemical Industries KK, trade name: Mikata Petrochemical Volip, 5J-316) was heated to 1.1.1-1-'J dichlorothane vapor. 1 minute, then dried at room temperature for 1 minute. Maleic anhydride modified Pi (propylene V
, bA 67 mol, maleinoic anhydride content 6wt)
The injection square plate was immersed in a 5 g/l toluene bath solution [B] for 20 seconds and slowly pulled up. After drying at room temperature for 5 minutes, it was heated and dried at 80° C. for 0 minutes. Next, the above osteoclast composition [A] was subjected to primer treatment.
The polypropylene square plate was immersed for 60 seconds, slowly pulled up, and then dried at room temperature for 1 minute and then at 60°C for 5 minutes.
Ivy. This test piece was irradiated with ultraviolet rays at a distance of 15 cnr for 50 seconds under a pressure mercury lamp (12-OW/'cr) to harden the outer coating layer 71r. The coating performance is shown in Table 1.

Example 2 In Example 1, the coating composition described in Example 1 [
Instead of using A'J, 75 g of 2,2-bis(4-hydroxyphenyl)furopane diglycidyl ether diacrylate, 50.5 g of the urethane polyacrylate (ppAIA) solution described in Reference Example 2, and benzoin isopropylene After using a coating composition consisting of 5 g of ether and 94.5 g of methyl isobutyl ketone, a test piece of polypropylene whose surface was coated with gold was prepared in the same manner as in Example 1. Results (C-shown in Table 1).

Example 6 In Example 2, instead of using the urethane-based polyacrylate ~1 solution described in Reference 2, h in Reference Example 6 was used.
Urethane polyacrylate (BA engineering IP) i
Test 1 test piece was prepared by coating the surface of polyzolopyrene by the method described in Example 2 except that the liquid was used.3 The results are shown in Table 1.
Shown below.

Examples 4 to 8 In Example 1, polyacrylates of polyepoxy compounds listed in Table 1, urethane thread poly(
The surface of polypropylene was coated in the same manner as in Example 1, except that a coating composition prepared using meth)acrylate, a polymerization initiator, and a bath angle of 7. A coated weeping test piece was prepared.

The results are shown in Table 1.

Examples 9 to 10 Polyacrylates of polyepoxy compounds listed in Table 1, urethane polyacrylates,
and 1,1.1-)-lichloroethane in the amount listed in Table 1, and stirred to this mixture one piece of fine powdered silica with an average particle size of 20 mμ and a refractive index of 1.45 (1 piece of Aerosil KK (product name: R-972) ffi was added gradually (1st dose is listed in 1) and thoroughly stirred with a whisk to obtain uniform dispersion. The mixture was transferred to a three-piece pressure oil tank p+ [), and while the tank was cooled with water, the tank was rotated at lbO:rpm and mixed for 6 hours.

The amount of n-phthanol listed in its body 1
lt, After 1b'LJ in the air for another 10 minutes, from the but'tricou' (take out R1 compound and apply composition CA)
And so. In Example '1, a test piece was prepared by coating the surface of polyzolopyrene in 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. Table 1 shows the history of A.

Comparative Examples 1 to 2 The polyacrylate IJ of the polyepoxy compound listed in Table 1, -, l, urethane-based polyacrylate, polymerization initiator, and HLJ were weighed and weighed as described in Erosion 1 for 1 hour at room temperature. Coating composition CA prepared by stirring and mixing]'
A jaw piece with a constant surface coating of polypropylene was prepared by the method described in Example IK, except that the same method was used as described in Example IK. Conclusion - show the future'
Shown in 1.

Comparative Example 6 The coating composition of the present invention was made of uncoated polypropylene (Mikataishi γ111I manufactured by Kagaku Kogyo KK, 5J-ji'
The performance of 16) is shown below.

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

+11 P・GA・ Cyacrylate 1/-1・compound of propylene glycol diglycyl ether +2+ GGA... Triacrylate of chrycerin tricrine norether 9 but +31 BOHGA... 2,2-bis(4-hylic acid) −
Cyacrylate compound of Komaxin clohexynolypropane diglycine ether +41 B P G A...2,2-bis(4-
Hydroxyphenyl) propane diglycidyl ether diacrylate compound 1! 31 B Engineering E... Penzoin isoglopylether + 61 8 PH, pendinoenone (71IHP... 1-(4-isoglobylphenyl)- 2-Hydroxy-2-methyl-1-zolopanone ()3) ■ C=0 〇=0 Example 1'1 Poly-4-methyl-1-benzone (Mikata・1 Yukagaku Kogyo 5
KKI! A 6-cm thick injection molded sheet of TPX MXOO4) was coated with anhydrous maleic acid-modified EPR (maleic anhydride 1ν, 5γ; 7.ZWt) at a concentration of 157/β. 'I-trichloroethane bath liquid vc 'i
After waiting for o seconds, plasma treatment was performed. Immediately after 5 minutes at room temperature, the coating composition described in Example 10 was immersed in the coating composition described in Example 10 for 1 minute, then dried at 60°C for 5 minutes, and then coated in the method described in Example 10. A test piece was prepared by photopolymerizing the surface of poly-4-methyl-1-pentene. The results are shown in Table 2.

Examples '12 to'16 Poly-4 as the base polymer in m pieces 11
- Instead of using methyl-1-pentene, the method described in Example 1'1 was used, except that the pretreatment described in Table 2 was carried out. A test piece was prepared in which the polymer surface was graded.The results are shown in Table 2.

Comparative Examples 4 to 6 PoIJ-4-methyl-1-benzone (manufactured by Mikata Petrochemical Industry ■, '['P
XMXOO4), polycarbonate (manufactured by Invaginated Kasei KK,
Panrye l-L-1250)', polymethyl methacrylate L
/-1- (Mitsubishi Rayon KK, Acrylai L-L)
The performance of is shown in Figure 2.

/ / / / / / / /' Example 14, Comparative Example / In Example 1, instead of using the coating composition (A) described in Example 1, the coating described in Example 10 was used. Using the composition η [A] for molding, instead of using polyglopyrene as the molded body substrate 7, vesicles 5 with a thickness of 12n+m were used.
A test piece was prepared by covering the surface of an unsaturated polyester resin in the same manner as described in Example 1, except that a 11" polyester resin (Koranoku MC8-302 manufactured by Showa Nippon Kobunshi KK) was used. The film thickness of this test piece is 11μ, the surface gloss (cross) is δ6, the adhesion is 1uo/'ioo, and the lead hardness is 4.
4 liters with H (Example 14). On the other hand, the unsaturated polyester resin not coated with the coating composition of the present invention had a narrow surface gloss of 63 and a pencil hardness of 6H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Yamaguchi Kazu

Claims (1)

[Claims] tll (a) Poly(meth), a polyepoxy compound having at least two or more epoxy groups in one molecule
Acrylate compound, (1-”) Poly(meth)acrylic compound of N't polyepoxy compound / -1 □ compound (a) I LJ Ojk
%', 'tg15 K 74 (J i % + 1 oou 1 part of melon, 211!I in 1 molecule
A urethane-based poly(meth)acrylate compound having a methacryloyl oxidyl group and ■) a poly(meth)acrylate compound of the polyepoxy compound
UNN in the range of 0.01 to 20 parts by weight based on a total of 10 parts by weight of the meth)acrylate compound (a) and the polyurethane-based poly(meth)acrylate compound (b).
1. A curable resin composition for resin holding, characterized by containing an opening initiator. (2) Poly(meth)acrylate-l-compound (a) of the Borie small-oxy compound (a) and the polyurethane poly(meth)
Inorganic powder in a range of 0.5 to 200 parts per unit of acrylate compound (b)
Patent II with 11% iA agent! 'j range (1)
1 υ 1 j finger λ and I 戊 ((
Of course.