JPS5993733A - Curing resin composition for coating - Google Patents

Abstract

PURPOSE:A coating composition, containing a poly[(meth)acryloyloxyalkyl](iso) cyanurate, a poly(meth)acrylate, etc. of an alkane polyol and a polymerization initiator, and having improved curability and film characteristics. CONSTITUTION:A composition containing (A) a poly[(meth)acryloyloxyalkyl](iso) cyanurate of formula I [X<1>, X<2> and X<3> are (meth)acryloyl, H or alkyl among which two or more thereof are (meth)acryloyl; R<1>, R<2> and R<3> are (poly)oxyalkylene] or formula II, (B) 0-1,000pts.wt., based on 100pts.wt. component (A), poly(meth)acrylate of a 2-12C alkane polyol or polyoxyalkylene di(meth)acrylate, and (C) 0.01-20pts.wt., based on 100pts.wt. total of the components (A) and (B) polymerization initiator. USE:Useful for coating thermoplastic resins other than polyolefins and polyesters.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides excellent curing properties in air by coating the base surface of a thermoplastic (31 resin) molded product, and improves the surface hardness, scratch resistance, abrasion resistance, and uJtL of the coating. Cured wax resin composition for thermoplastic resin coating with excellent coating properties such as surface properties, surface brightness, heat resistance, water resistance, solvent resistance, and weather resistance. Regarding.

In general, thermal plastic resin moldings are not only lightweight and have excellent impact resistance compared to metal products and mechanical glass products, but also various products such as cheap and easy to mold. It has the following advantages and is widely used in place of these additives in many fields such as automobiles, automobiles, household appliances, miscellaneous goods, and the like. but,
These thermoplastic resins generally have a lower surface hardness than metals, glass, etc., and are weak against drag and friction, so they have the disadvantage of being easily molded onto the surface. For example, removing parts of a molded body (=I work or transportation work,
Alternatively, the use of these molded bodies is severely restricted due to defects in surface properties such as susceptibility to surface damage due to contact, collision, scratching, etc. during use of the product.

Many proposals have been made to improve the above-mentioned drawbacks of the basic surface of a molded article made of thermoplastic resin. 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 the fat or resin-forming component include silicone polymers or compositions of these components and various polymers, resin compositions consisting of methylolmelamine and other curing components, polyfunctional acrylics, etc. Various types of carboxylic acid ester derivatives or compositions of these and other polymerization components have been proposed. Even if a layer IIi consisting of these film-forming elements is formed on the surface of the base of a thermoplastic resin molded product, the adhesion between the film layer and the base layer of the thermoplastic resin molded product is generally not good. There is a drawback that the coating layer easily peels off from the laminated molded product.

Furthermore, methods are known in which various treatments are applied to the surface of the base layer of a thermoplastic resin molded book in order to improve these drawbacks. For example, surface treatment using corona discharge and surface treatment using primer have been proposed. However, even after surface treatment, the base 14cWJ of the thermoplastic resin molded body and the frame
1 High hardening! 1) A coating layer made of resin that can withstand practical use.
However, it is often difficult to change one's personality to two. Moreover, among the film-forming elements mentioned above, silicone-based film-forming elements are expensive and have the drawback of being inferior to the previous ones.

In addition, among the film-forming elements described in 111j, one polyfunctional acrylic carboxylic acid ester derivative (many types of compounds have been proposed. Acrylates, polyoxyalkylene glycols, acrylates, aromatic (fu/-) polyhydroxylated crops, poly(
meth)acrylate, polyepoxy compound poly(/ri)acrylate-1, urethane polyol poly(meth)
It has been proposed to use various types of compounds as film-forming elements, such as acrylates. Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as film-forming elements to form a film on the substrate surface of a thermoplastic resin molded article, the curing speed of these films in air is low during curing. poor curing properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance and adhesion to substrates; However, many of these film-forming elements are often inferior in physical properties, and it has not been possible to fully satisfy the requirements for use in industrial standards. Attempts have been made to improve the drawbacks by using a mixture of thermoplastic resin moldings, but although these drawbacks can be improved to some extent, it is difficult to coat the substrate surface of a thermoplastic resin molded article. There was a new difficulty in the pond,.

The inventors of the present invention have excellent curing properties during curing by coating the basic surface of a molded product with a heat i+f (i7J) material other than polyolefin and polyester.
As a result of performing a hardening h52:ij on the r-property (fuzzy coating composition), poly[(meth)acryloyloxyalkyl](iso)cyanurate (a),
Specific '11'i: When using a composition containing a poly(meth)acrylate of a polyokine alkane polyol or a polyoxyalkylene(meth)acrylate) (+3) and a specific R polymerization initiator (0), It has been discovered that objective 1-1 is satisfied, and the present invention has been achieved.

According to the present invention, when the hardening type for coating of the present invention (3j resin composition is coated on the surface of a plastic resin molded body to form an outer coating film), it is possible to form an outer coating film on the surface of a plastic resin molded body. Excellent curing characteristics such as curing speed and surface hardness of the resulting coating,
Scratch resistance, abrasion resistance, machinability, surface light (ba), heat resistance,
It has the characteristics of being generally excellent in many film properties such as water resistance, solvent resistance, weather resistance, and basic adhesion.

4. The present invention has already been described. (d) General formula [J]
[In the formula, x', x: and x3 represent an axoloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (meth)acryloyl groups, R', R2 and R3 represents an oxyalkylene group or a polyoxyalkylene group. ] Poly[(meth)acryloyloxyalkyl](iso)cyanurate), (1)) the poly[(meth)acryloyloxyalkyl](iso)cyanurate) (a) 1 (
', 1 (poly(meth)acrylate or polyoxyalkylene(meth)acrylate I- of an alkane polyol having 2 to 12 carbon atoms in the range of 1 to 1000 parts by weight per 1 part by weight) 1 and (
c) A total of 10 of the poly[(methaneacryloyloxyalkyl)(iso)cyanurate (a) and the bobamethacrylate or polyoxyalkylene/(meth)acrylate-1(b) of the alkane polyol.
1 layer! A thermoplastic material other than polyolefins and polyesters containing a polymerization initiator in the range of BIS; 1 Curing mold for fat coating 4
31 fat composition.

The poly[(
tsuku) acryloyloxyalkyl] (i [in the formula, x'
, x'' and x3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (meth)acryloyl groups, and R'
, R'' and 1 (3 represents an oxyalkylene group or a polyoxyalkylene group) or poly[(meth)acryloyloxyalkyl] cyanurate, and tris [(meth)acryloyloxyalkyl](iso)cyanurate-1, bis[(meth)acryloyloxyalkyl](iso)cyanurate or a mixture of these J'L et al. Those whose main component is alkyl](iso)cyanurate are preferred.×1,×2 and
The alkyl group of 3 is usually an alkyl group having 1 to 4 carbon atoms. Further, R', 1' and R3 are oxyalkylene groups having 1 to 12 carbon atoms, preferably 2 to 4 carbon atoms, or the majority of the oxyalkylene group is 1, and usually 2 to 4. book or 12 quantity 1
Book, preferably 2 'j'Ji trees or 1 star body. Examples of the poly[(meth)acryloyl oxyne alkyl] in cyanurate include tris(acryloyloxyethylphyson anurate, tris(methacryloyloxyethyl) in cyanurate, tris(
2-Acryloyloxypropyl) incyanure-1.
, I. Lis(-methacryloyloxypropyl)in cyanurate, bis(acryloyloxyethyl)hydroquinethylisocyanurate-1, bis(methacryloyloxyethyl)methoxyethylisocyanurate-1,
Bis(2-acryloyloxypropyl)-ethoxypropylisocyanurate, Bis(2-methacryloyloxypropyl)-2-hydroxypropylisocyanurate, Tris[acryloyloxypropyl(oxyethylene)]in cyanurate, Tris(methacryloyloxypropyl)-2-hydroxypropylisocyanurate, Tris(methacryloyloxypropyl)-2-hydroxypropylisocyanurate (oxyethylene)]incyanurate can be exemplified, and a mixture of two or more of these can also be used.

Furthermore, specific examples of the poly[(meth)acryloyloxyalkyl]in cyanurate include 1-lis(acryloyloxyethyl)cyanurate, tris(methacryloyloxyethyl)cyanurate, tris(2-
acryloyloxypropyl) cyanurate, ) lis(2-methacryloyloxypropyl) cyanurate,
Bis(acryloyloxyethyl)hydroxyethyl cyanurate, His(methacryloyloxyethyl)methoxyethyl cyanurate, Bis(2-acryloyloxypropyl)-2-ethoxypropyl cyanurate, Bis(2-methacryloyloxypropyl)-2-hydroxy Propyl cyanurate, Tris [acryloyl di(
Examples include oxyethylene)] cyanurate, 1lis[methacryloylno(oxyethylene)] cyanurate, and mixtures of two or more of these may also be used.

The alkane polyol poly(meth)acrylate or polyoxyalkylene (meth)acrylate 1(1)) blended into the curable coating 1ii7 composition of the present invention has a carbon atom number ranging from 1 to 12. The alkane polyol is polyacrylate-1 or polyoxyalkylene glycol rylate. 7) The alkane polyol constituting the acrylate is a dihydric alcohol, a trihydric alcohol, in the range of 2 to 12 carbon atom,
It is preferably a tetrahydric alcohol, a polyhydric alcohol, or a synthetic component of two or more thereof, and more preferably an alkane polyol having 2 to 8 carbon atoms. When the number of carbon atoms in the alkane polyol constituting the poly(meth)acrylate [•] exceeds 12, 1(j
The surface hardness, scratch resistance, and abrasion resistance of these coatings decrease. When the alkane polyol component constituting the poly(meth)acrylate of the alkane polyol is a trihydric or higher polyhydric alcohol, the poly(meth)acrylate of the alkane polyol has two or more dihydroxyl groups. If is (meth)acrylated, there is no problem even if free hydroxyl groups remain. Specifically, the (meth)acrylate of the alkane polyol is 1
．． 2-noacryloyloxyethane, ], ]2-methacryloyloxyethane 1,2-noacryloyloxypropane, 1,2-noacryloyloxypropane, 1
, 3-acryloyloxypropane, 1.

3-noacryloyloxypropane, 1,4-cyacryloyloxybutane, ], ]X1-methacryloyloxybutane 1,6-cyacryloyloxyhexane,
1,6-methacryloyloxyhexane, 1,8-
noacryloyloxyoctane, 1,8-nometaacryloyloxyoctane, glycerin-1,3-noacrylate, glycerin-1.

3-noacrylate, glycerin 1-reacrylate,
Pentaerythritol acrylate, pentaerythritol no methacrylate-1, pentaerythritol triacrylate, pentaerythritol tritacrylate, pentaerythritol tetraacrylate-1, pentaerythritol/reterra methacrylate-1, trinotyrolethane triacrylate I, ) Limethylolethane trimecrylate, 1 Limethylolpropane triacrylate I
, trimenalol propane trimethacrylate, etc. can be used. Among these poly(meth)acrylates of alkane polyols, the number of alkane polyols with 17<or 2 to 8 atoms is longer. (meta)
Preferably, acrylates are used. In addition, polyoxyalkylene di(meth)acrylate is an acrylic ester or methacrylic ester of polyoxyalkylene glycol.
The oxyalkylene group constituting meth)acrylate-1 is
Usually, the general formula [wherein R', R:, 1<2 and R1 each represents a hydrogen atom or an azolekyl group having 1 to 12 carbon atoms] is used. ] The degree of polymerization of the oxyalkylene group is usually in the range of 2 to 1 (1), and the number average molecular weight (M n ) of the oxyalkylene diacrylate is Usually 230 (・shi30
00, preferably 2:sO to 2+-1(l
il range. Specifically, the polyoxydialkylene di(meth)acrylate includes polyoxyethylene noacrylate, polyoxyethylene noacrylate,
Examples of the polyoxypropylene di(meth)acrylate include polyoxypropylene noacrylate, polyoxypropylene dimethacrylate, polyoxyethylene polyoxypropylene diacrylate, and polyoxyethylene polyoxypropylene di(meth)acrylate. Among these, polyoxyalkylene(meth)acrylate or polyoxyalkylene(meth)acrylate is preferable.Moreover, poly(/)acrylate of the alkane polyol or polyoxydialkylene(meth)acrylate is preferable. In our case, it is an alkane polyol acrylate with 3 to 8 carbon atoms, and 3 or more (meth)acryloyloxyl! Most preferred are poly(meth)acrylates of alkane polyols having a long history. In the case of the combination of poly(meth)acrylate or polyoxydialkylene di(meth)acrylate 11) of the alkane polyol: 'iQ,
+III poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) 10 (needs to be in the range of 0 to 1000 parts by weight per 1 part by weight, and furthermore, 50() weight) range,
More preferably, it is in the range of 20 to 10 parts by weight.The poly(meth)acrylate or polyoxydialkylene (
The above poly[(meth)acryloyloxyalkyl](iso)cyanuride) (a) of meth)acrylate (lJ)
100 weight) Is the blending ratio in accordance with 1 capital] (11 0 0
When the amount exceeds 1 part by weight, the curing properties of the composition in air decrease, and the surface hardness, abrasion resistance, and other performances of the outer coating 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 in addition, the other essential polymerizable monomer component It is also possible to copolymerize by adding. The polymerization components in the pond include, for example, by-products or production intermediates during the production of poly[(/ri)acryloyloxyalkyl](iso)cyanurate (a) described in 01j, such as poly[(/)
/ri)acryloyloxyalkyl]bis(hydroxyalkyl)(iso)cyanurate, by-products or intermediates during the production of poly(meth)acrylates or polyoxydialkyl(meth)acrylates of the alkane polyols, such as alkane polyols Things (
Pond (meth)acrylate or polyoxyalkylene glycol mono(vine)acrylate etc.
Examples include (meth)acrylic acid esters such as acrylic acid, methyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate.

The curable resin composition for coating of the present invention is applied to the basic surface of thermoplastic fA (a composition consisting of fat) [4], and in order to form a film by crosslinking and curing the composition, this composition - It is necessary to incorporate a polymerization initiator (0).As curing methods, curing methods using ultraviolet rays, curing methods using heat rays, etc. are usually adopted.In the case of ultraviolet curing, photosensitization is performed as a polymerization initiator. Specifically, the photosensitizers include benzoin, benzoin ethyl ether, benzoin ethyl ether, hendiin isopropyl ether,
Benzoin or its ethers such as benzoin iso7-ethyl ether, benzo-7-ethyl ether, benzo-7-ethyl ether, benzyl, pennoltz methyl ketal, etc. , benzyl diethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-probanone, 1-phenyl-2-
Hydroxy-2-methyl-1-propane, 1-(-1-
Examples include hydroxyalkylphenylketone compounds such as Lerl-butylphenyl-2-hydroxy-2-methyl-1-propamene. 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, benzoyl peroxide, lauryl peroxide, di-Lert-7 tyl peroxide, and tsucumil. Examples include peroxides such as peroxide and cumene hydroperoxide. Furthermore, it is possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and heat curing proceed simultaneously. It is also possible to adopt a method of proceeding with heat curing after proceeding with ultraviolet 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 (c) is as follows: the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the poly(meth)acrylate) or polyoxyalkylene')( 0.0 per 100 parts by weight of meth)acrylate(l))
The amount of the polymerization initiator is preferably in the range of 1 to 20 parts by weight, and preferably in the range of 1 to 10 parts by weight.
Total of (meth)acryloyloxyalkyl](iso)cyanurate (a) and poly(meth)acrylate or polyoxydialkyloxyalkylene(meth)acrylate)(+)) of the alkane polyol] (l 0 parts by weight) When the amount is less than 1 part by weight, the polymerizability of the composition decreases and a hard coating cannot be obtained.
If the amount exceeds 0 parts by weight, the coating obtained from the composition will be colored yellow.

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 pigment, a dye, a solvent, and ultraviolet light. Stabilizers such as absorbers, antioxidants, optical brighteners,
Methyl (meth)acrylate, polyurethane acrylate
Various additives such as (reactive) oricomers such as 1 and polymers such as poly/methyl methacrylate can be blended. The blending ratio of these additives is appropriate.

Curable resin set for coating Jt1 of the present invention. As long as the transparency of the resulting cured film is maintained,
If necessary, a finely powdered inorganic filler may be added. The average particle size of the finely powdered inorganic filler is arbitrary as long as it is in the form of a powder, and usually ranges from 1 mμ to 10μ, preferably from 1°5illμ to 1μ. In addition, in order to maintain the transparency of the outer coating layer,
The refractive index of the fine powder is usually 1,4 (
+na,・shi], 60, preferably 1.42 to 1.5
The range is 8. 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, Examples include sericite, talc, chlorite, pottery stone, and feldspar. In addition, the surface of these finely powdered inorganic light colorants can be coated with an alkyl carboxylate, a silane coupler, a titanium coupler, C1,s i(C1lJ)r,
Those whose surfaces have been treated with alcohol or the like can also be used in the same way. Further, it is also possible to use colloidal silica, methanol silica sol, ethyl silica sol, isopropyl silica sol, etc. in which the inorganic filler is suspended in water or alcohol. When finely powdered silica is blended among these fillers, the surface hardness, scratch resistance, and abrasion resistance of the outer coating layer are significantly improved, and the surface is transparent and glossy. The proportion of these finely powdered inorganic optical fillers is the same as that of the poly[(meth)acryloyloxyalkyl](iso)cyanuride-1<a) and the poly(meth)acrylate or polyol of the alkane polyol. Usually (), 5 to 2 (10 parts by weight, h' or in the range of 0.5 to 100 parts by weight) to a total of 100 weight 1f14 of pheasant alkylene di(meth)acrylate (1) be.

In order to improve the coating workability of the curable 4A1 resin composition for coating of the present invention, a solvent may be added as necessary to maintain it in a solution or suspension state.

Solvents are also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specifically, as a solvent,
Hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, 70 moform, trichlene, ethylene dichloride, perchloren, Halogenated hydrocarbons such as ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, 70 mobenzene, methanol, ethanol, inpropar 7
Alcohols such as -ol, butyl, pentyl, hexyl, cyclohexanol, ethylene/glycol, propylene glycol, chrycerin, ethylene glycol monomethyl ether, noethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexyl ether, noethyl ether,
Ethers such as nprobyl ether, butyl ethyl ether, nophnal ether, ethylene glycol methyl ether, noethylene glycol methyl ether, nitriles such as acetonyl, propionyl, cabronyl, methyl formate, ethyl formate , methinoacetate, ethyl acetate, propyl acetate, iso7tyl acetate, butyl acetate,
Examples include esters such as pentyl acetate, AnJJ, methyl fragrant, and ethyl benzoate. The blending ratio of these organic solvents is as follows: the poly[(meth)acryloyloxyalkyl](iso)cyanuride) (a) and the poly(meth)acrylate or polyoxydialkylene di(meth)acrylate)(+) of the alkane polyol. ))
Total of 10 (usually 5 to 30 parts per part by weight)
(1 (11 parts by weight), preferably in the range of 10 to 200 () parts by weight).

In the composition of the present invention, a composition containing the above-mentioned essential components and various additive components such as an inorganic or organic filler, a solvent, a stabilizer, etc. added as necessary, a solution composition or a suspension composition can be prepared. As a method for preparing the liquid composition, the above-mentioned raw material It compound is blended, and then a normal roll, a Banbury mixer, a ball mill, an attritor, a whipper, an oak mixer, a dilbar, a bomonizer, a colloid mill, a sand mill, a vibration mill, or a mixer is used. Examples include kneading and mixing methods using 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 resin molding include brush coating method, spray method, dipping method, bar code method, roll coater method, spin twoter method, del coater method, etc. It is best to use a conventionally known method. In addition, the method of drying the coating film - ζ is the natural drying method, the forced drying method using a carrier gas*
Examples include a Z drying method, an infrared oven, a far-infrared oven, and a heating drying method using a hot air oven. Further, examples of methods for curing the above-mentioned coating film to form a film include a method of polymerization crosslinking and curing using ultraviolet rays, a method of polymerizing and crosslinking and curing using heat, and the like. Among these methods of polymerization and crosslinking curing, the photocuring method is 1 to 15o'0, or 5 to 13.
Light irradiation is carried out in a heated garden at 0°C, and the duration is usually 1.
sec to 111r, preferably +3 (・C to]
It's a tatami mat. In addition, in the thermosetting method, the temperature during curing is usually -1() to 50°C, preferably 5 to +50°C.
3 +1 ”C, and the time required for curing is usually 0
,' (15 to] Obr, preferably (), 1 to 8 hr.

The curable resin composition for coating of the present invention can coat the entire basic surface of any molded article made of a thermoplastic resin other than polyolefin and polyester. The shape of the molded product may be a film, a sheet, a plate, or any other shape. Thermal temperature excluding polyolefin and polyester constituting the base resin layer
Specifically, the JqJ resins include polyacrylic carboxylic acid ester, polycarbonate tree II Kuma styrene polymer, polyphenylene oxide resin, and polysulfone 43.
Examples include 1 fatty acid, polyether sulfonic acid resin, polysulfide (3) Tomokuma polyacetal resin, polyamide 13 + fatty acid. Examples of the polyacrylic carboxylic acid ester include methyl acrylate, methacryl Homopolymerizability or copolymerization of acrylic carboxylic acid ester with methyl acid, ethyl methacrylate, etc. Examples include polymethyl methacrylate, polymethyl acrylate, etc. 3. Specific examples of the polycarbonate 1 resin Examples include Bisphere/-A polycarbonate, Bisphere/F polycarbonate, Bisphere/D polycarbonate), and the like. +iii styrenic polymer specifically,
Borisnarene, polyα-methylstyrene, acryloni I
- Examples include styrene copolymer, acrylonitrile/ftatsuene/styrene copolymer, etc.

Polyphenylene oxide tree III? Specifically,
Examples include polyphenylene oxide and modified polyphenylene oxide. The polysulfone 141
Specifically as fat, 1, 5, 7, 2. Examples include AX /, t, a, --de, and box. Specifically, the polyether sulfone 4j + fat is l.IE
Examples include a. Specific examples of the polysulfide resin include polyphenylenesal 7i F and the like. Specific examples of the polyacetal resin described in 11η include polyoxymethylene (side fat, etc.). Examples of the polyamide resin include nylon 61, nylon 6/6, nylon 1]
, nylon 12, and the like.

When coating the basic surface of the thermoplastic 414 resin molded body with the curable resin composition for coating of the present invention, the base surface of the molded body is washed with various solvents, washed with an aqueous alkaline solution, and subjected to surface activity. cleaning agent, ultrasonic cleaning, electrolytic cleaning, 7-last treatment, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. Various surface treatments can be applied. Further, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the base surface of the molded article made of the thermoplastic resin, a primer may be used between the base layer and the outer coating layer. It is also possible to improve the adhesion between the two layers by forming a three-layer laminate by placing an intermediate adhesive layer consisting of the following. In this manner, the composition of the present invention is coated on the surface of the base layer of the thermoplastic resin molded body, which has been subjected to surface treatment or primer treatment as necessary, by the above-described method, and is subjected to a curing treatment.

A 4,51 resin molded book laminated with a film made of the curable resin composition for coating of the present invention is used for various purposes. Soldier (
For example, for fishing, there are lighting boards, sky domes, panels for solar water heaters, panels for glow 7 boxes, "1L
Glasses for illumination, various lenses such as glasses, cameras, and lenses, optical prisms, blood bags, shower domes and coffee containers for coffee makers, water tanks, covers for illuminators, covers for players and stereo equipment -1
Dials and covers for various types of motors, covers for automobile front lights and tail lights, level sensors, shatterproof films and release films for power glass, insulation films, agricultural films, and other films for light regeneration. Video discs, clothes dryers, electric washing machines, screwdrivers,
Peepholes for various equipment such as oil tanks, auto highs and noses,
Jilt-proof glass for motor boats, automobile glass (windshields, rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, tableware, mirrors, oil, bathrooms, cosmetic skin, etc. Various containers, relay cases, fuse hooks, motorcycle site covers and mudguards, fenders, curtains, screens, chiffle cloth, waterproof and moisture-proof films, tarpaulin sheets, insulation films, floor tiles, floor sheets, doors, chiffle boards,
Wall tiles, countertop veneers, shelves, wall stickers
, 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 coatings, curtains, window frames,
Automotive foil, various containers, automobile interior materials, vanity tables,
Flower hooks, particle board, roof tiles, shutters, waterproof pans, pipes, wiring materials, kiyaka l
1. Knob, solenoid valve frame, fan, instrument panel, bumper,
7 rakes can be opened. The ponds mentioned above also include home appliances, automobile parts, motorcycle parts, automatic sales (components), civil engineering and construction fees, general industrial waste, office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and nuclear power related products. It is also possible to use it for parts.

Next, the present invention will be explained based on examples.

In addition, evaluations in the main text or Examples were performed by the following method.

(1) Add 2 L% of the inorganic material, which has been thoroughly dried and strained with a refractive index, into a liquid with a known refractive index, and after dispersing it for 1 minute,
Check transparency visually. The refractive index is set to be the same as that of Liquid 1IZ, which was the most transparent.

(2) Light transmittance, measured by illuminating JISK 671□l.

(:() Dense I T sex J I S K 54 (, -1fl -] 97
9 out of 7 (7) Koba> I went to the 7th stroke if+1.

The 'l'lJ constant is expressed as how many of the (1+) pieces were glued together.

(・1) Taper wear lXS i-M +') -10...For method 1 and 4!
(ξ, wear ring C3it), load, 500 B t'
The coating was rotated 100° (', 1 rotation). The abrasion resistance of the coating after the test was evaluated. The smaller the amount of 4-0+'p, the better the abrasion resistance.

(j3) Pencil hardness JIS K 565].

＼ ＼ ＼ Example 1 25 g of tris (j'cri[1yl-ogyethyl] isocyanurate-1-759,1,6-hexanediol diacrylate, benzoin isopropyl ether 5QJ5 and 110 g of toluene were added to 1 500 m 14 turofuras pipe 1)
．． 1 and stirred at room temperature 11) to prepare a transparent coating composition [A].

On the other hand, a 3+++m thick injection square plate made from polycarbonate (Panlite-1250, manufactured by Yojin Kasei KK) (
10 x 10 cm) was degreased with isopropyl alcohol, and then immersed in the coating composition [A] for 10 seconds at room temperature. After slowly pulling up at room temperature for 1 minute, then at 60"C
After drying for 5 minutes at
The outer coating layer is cured by irradiating it with ultraviolet light for 30 seconds at a distance of
! 7: o The film performance is shown in Table 1.

To Example 2/4 In Example 1, the coating composition described in Example 1 [
A] Instead of using poly[acryloyloxyalkyl]isocyanurate, alkane polyol polyacrylate or polyoxyalkylene diacrylate, and photopolymerization initiator listed in Table 1, for coatings prepared by using the suspension listed in Table 1. Composition 1. Δ] was used to prepare a test piece in which the surface of the sheet was coated with Polymer Sea-1 in the same manner as in Example 1. The results are shown in Table 1.

Examples 5-6 In Example 1, the coating composition described in Example 1 [
Instead of using coating composition [A] described in Table 1, and instead of using polycarbonate sheet, polymethyl methacrylate sheet (manufactured by Mitsubishi Rayon KK, Acrylai 1 to L) was used, and degreased. A test piece was prepared by covering the surface of a polymethyl methacrylate sheet in the same manner as in Example 1, except that ethyl acetate was used.

The results are shown in Table 1.

Examples 7 to 11, Comparative Examples 1 to 2 Poly[acryloyl A xyalkyl] isocyanurate, alkane polyol polyacrylate, photoinitiator, solvent d3 and methanol silica sol (
Made by Nissan Chemical KK, 30% anhydrous silica methanol with an average particle size of about 1501μ and a refractive index of about 1.50! A coating composition [A] was prepared by weighing out the amount of the solution shown in Table 1 and stirring and mixing at room temperature for 211 r.

On the other hand, real IJ1! ! a5 in Example 1, instead of using the coating composition [Δ] described in Example 1, the above coating composition [Δ] was used, and the polymer substrate was used as the polymer sheet 1 described in Table 1. A test piece was prepared by coating the surface of the polymer sheet using the method described in Example 1, except that the polymer sheet was degreased with isopropyl alcohol in the case of polycarbonate and with ethyl acetate in the case of polymethyl methacrylate. . The results are shown in Table 1.

Comparative Examples 3 to 4 Table 1 shows the physical properties of polycarbonate sheet J5 and polymethyl methacrylate sheet alone that were not coated with the coating composition of the present invention.

The following abbreviations used in Table 1 below indicate the following compounds, respectively -0 TAEfC...Tris(acryloyloxyethyl)
Isocyanurate BAEIC...Bis(acryloyloxyethyl)hydroxyethyl isocyanurate BDA...1,4-butanediol diacrylate 1
-ID A...1,6-hexanediol diacrylate DEGDA...Diethylene glycol diacrylate PETRA...Pentaerythritol triacrylate PE-A...Pentaerythritol tetraacrylate
1- GT△... Glycerin triac 1 route BIE...
Benzoin iso7-robyl ether B P l-1...
・Benzophenone 11-I P...1-(4-isopropylphenyl 2
-Hydroxy-2-methyl-1-bropanone "-X+1)" Shine City 11L!苧 (,) し゛゛〈ヱ,Q゛14158Q month/[1 'll+1;'I' l i' 1,2 昌, Otsushi
Jn person Kuma 1-□old) l: [/) ,,,', Kokai Jl15740 Toki Pl' 19j No. 202076 No. 2
, Invention A'1.1! l, Handling 1: Ngawa 1] History (114, j Riyi () finger A; 11 product 3, i+li i ding 4-zu 2 shinichi, “l+
l'l and O) Leap 1°1% 'l! 1. i'l Applicant name (5B 8', 1 Mitsui E 1ura Chemical Industry Co., Ltd./
;'': Company 4, agent (S100 East Urinary 81', r (e III lbe complaint) y, ni
;

Claims (2)

[Claims] (1) General formula [1] [In the formula, X',
. The poly [(close)
Acryloyloxyalkyl (iso)cyanuride)
(a> 100 parts by weight) to 1000 parts by weight, poly(alkaline) acrylate or polyoxydialkylene di(meth) of an alkane polyol having 2 to 2 carbon atoms; acrylate, and (C) the poly[(meth)acryloyloxyalkyl](iso)cyanuride) (a) and the poly(meth)acrylate or polyoxydialkylene di(meth)acrylate (b) of the alkane polyol, total of 1
．． 1. A curable resin composition for coating thermoplastic resins other than polyolefins and polyesters, comprising: a polymerization initiator in a range of 0.01 to 20 parts by weight per 00 parts by weight. (2) The poly[(meth)acryloyloxyalkyl]
(iso)cyanuride) (a) and the alkane polyol poly(meth)acrylate) or polyoxydialkylene di(di)acrylate 1)) total of 1 o 0.5 to 0.5 to A curable 431 fat composition for coating according to claim 1 of the patent, characterized by a powdered inorganic filler in the range of 20□ parts by weight.