JPS636064A - Coating composition having excellent function - Google Patents

Abstract

PURPOSE:To provide the title compsn. which gives a coating film having excellent wear resistance, surface smoothness, dyeability and antistatic properties when irradiated with actinic energy in an air atmosphere, by blending a specified monomer mixture with an org. solvent and a photopolymerization initiator. CONSTITUTION:7-50% (by weight; the same applies hereinbelow) polyfunctional monomer (a) having at least three (meth)acryloyloxy groups per molecule is mixed with 30-90% monomer (b) of formula I [wherein R1 is H or CH3; R2 is a 1-6C alkoxy or (meth)acryloyloxy; and n is a number of 5-30], 1-20% phosphoric ester monomer (c) of formula II (wherein R3 is R1; R4 is H or a group of formula III; R5 is R1; and m and p are each a number of 1-15), 1-10% monomer (c) of formula IV (wherein R6 is R1; R7 is H or a 1-8C hydroxyalkyl; and R8, R9 and R10 are each R7 or a 1-8C alkyl) and 1-10% ethanolamine compd. (e) of formula V (wherein R11 and R12 are each H, a 1-15C alkyl or CH2CH2OH) to obtain a monomer mixture (A). 100pts.wt. mixture of 5-90pts.wt. component A and 95-10pts.wt. org. solvent (B) is blended with 0-10pts.wt. photopolymerization initiator (C).

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is based on the method of applying active energy rays in an air atmosphere.
The present invention relates to a highly functional coating material composition capable of forming a cross-linked coating having excellent abrasion resistance, surface smoothness, and dyeability, as well as permanent antifogging and antistatic properties.

[Conventional technology]

Synthetic resin molded products made from polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, etc. are lighter than glass products.
Organic plate glass has various advantages, such as being not only a trivial material with excellent impact resistance, but also being inexpensive and easy to process into a bottom shape.

Applications are being developed in many fields such as optical applications such as lighting equipment covers, optical lenses, eyeglass lenses, reflectors and mirrors, decorative applications such as signboards and displays, and automobile parts.

However, these synthetic resin molded products lack abrasion resistance on the surface, so the surface may be damaged by contact with other objects, impact, or attraction during transportation or use. This may result in damage, lowering the product yield or impairing the aesthetic appearance.

In addition, these composite resin corrugated products have a high surface resistivity, so they are easily charged, and friction generates static electricity, which attracts dust, which significantly reduces the commercial value. When exposed to humid environments or conditions below the dew point, fine condensation forms on the surface, blocking light transmission and fogging eyeglass lenses and mirrors, often causing inconvenience and discomfort.

Many proposals have been made for improving the abrasion resistance of joint-soled resin-bottomed products, and the present applicant has been quick to develop more multifunctional (meta)
We have found that acrylate monomers have excellent cross-linking and curing properties when irradiated with active energy rays, and that acrylate monomers are effective in completely improving the abrasion resistance of the surface of synthetic resin shaped products and have made many proposals. 9 (Special Publication No. 4B-42211,
No. 49-12886, No. 49-22951, No. 49
-14859, 49-22952).

However, on the other hand, it has also been found that there are the following problems. That is, since the coating formed on the surface of the combined resin bottom-shaped product is a cross-linked cured coating, it is difficult for the dye to diffuse and dyeing cannot be performed.
Also, when it comes into contact with moisture, it generates fog υ. Furthermore, static electricity is generated due to friction, which causes dust to adhere, resulting in a significant reduction in commercial value, limiting the scope of use, and posing a major obstacle in practical use.

Conventionally, proposals have been made to incorporate compounds with a large number of dyeing seats or fd hydrophilic compounds into coating material compositions for the purpose of improving dyeability and antifogging properties. , the abrasion resistance deteriorates and it cannot be put to practical use. In addition, as a method to prevent the generation of static electricity, there is a method of blending an antistatic agent and a method of combining monomers with antistatic ability t-W.
I know how to match it. The former is easy to manufacture, but only the antistatic agent present on the surface is effective, and a high concentration is required to obtain sufficient antistatic ability, resulting in poor wear resistance. This results in a decline in sex and appearance.

In addition, since the inhibitor present on the surface easily falls off due to washing or friction, reducing the prevention ability, devises have been made to allow the inhibitor present in the matrix to gradually bleed out. In addition to causing the surface to become sticky and opaque, the resistance to cleaning and the like is temporary and not permanent.

In addition, the latter, that is, the copolymer type, exhibits no effect other than the monomers in the surface layer, so a large amount of monomers must be blended, which also leads to a decrease in wear resistance and appearance, which is a problem. Furthermore, the present inventors solved these problems by combining polyethylene glycol (meth)acrylate with an 11-phosphate monomer having a specific structure and an ethanolamine compound. (Japanese Unexamined Patent Publication No. 55-86848). However, even with these proposals, the performance deteriorates significantly under harsh conditions, and it is impossible to provide durable functions.

[Problem that the invention seeks to solve]

The present inventors have conducted extensive research with the aim of improving the above-mentioned problems, and as a result, have developed a phosphoric ester having a specific structure in polyfunctional monomer and polyethylene glycol di(meth)acrylate. The present invention was based on the discovery that a composition capable of imparting durable functionality can be obtained by blending a monomer, an ethanolamine compound, and hydroxyalkyl (meth)acrylamide. did.

[Means for solving problems]

The gist of the present invention is to use polyfunctional monomers (a) having 3 or more acryloyloxy groups and/or methacryloyloxy groups in the molecule (7 to SOW) and the following general formula % formula % (13 (formula Among them, RIFi hydrogen or methyl group, R2 has 1 or more carbon atoms
5 alkoxy group, acryloyloxy group, or methacryloyloxy group, n1j is an integer of 5 to 30. ) and 730 to 90% by weight of monomer (1) represented by the following general formula (% formula % (wherein, R3 is hydrogen or a methyl group, R4 is hydrogen or s C = O-C-0-( OHz) p group, R6 is hydrogen or methyl group, m and p are integers of 1 to 15. In the formula, R6 is hydrogen or a methyl group, R is hydrogen or a hydroxyalkyl group having 1 to 8 carbon atoms, and Rse R1° is hydrogen, an alkyl group having 1 to 8 carbon atoms, or a hydroxyalkyl group having 1 to 8 carbon atoms, respectively.
~B is a hydroxyalkyl group. ] 1 to 10% by weight of a phosphor (d) represented by n, and the following general formula % formula % (71) (wherein, R11 and RI2 are respectively n hydrogen, carbon number 1 to
15 alkyl group or OH, 0H20H group. ] Ethanolamine compound (θ) 1 to 10 times
5 to 90 parts by weight of a monomer mixture (A) consisting of Mk, and 95 to 10 parts by weight of at least one organic solvent (B) that is mixed with the monomer mixture (A) to form a homogeneous solution. part and photopolymerization initiator (C) 0 to 10 parts by weight of the monomer mixture (
Based on a total of 100 parts by weight of A) and organic solvent CB)]
A highly functional coating material composition comprising:

In the present invention, the polyfunctional monomer (a) having three or more (meth)acryloyloxy groups (meaning acryloyloxy group or methacryloyloxy group, hereinafter used in the same manner) in the molecule is used in the coating material composition. This is an essential component for improving abrasion resistance and scratch resistance, and the next step in obtaining better abrasion and scratch resistance is polyfunctional monomer (a).
is required to be in the range of 7 to 50% by weight in the monomer mixture (A).

The amount of polyfunctional monomer (IL) in the monomer mixture (N is 71!
If the amount is less than 50% by weight, a cured film with sufficient abrasion resistance cannot be obtained, and if the amount exceeds 50% by weight, permanent antifogging and antistatic properties may be obtained under severe conditions. I don't like it if I can't get it.

3 or more (methacryloyloxy groups't) in the molecule
- Examples of the polyfunctional monomer (a) include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaglycerol tri(meth)azilylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)azirylate, dipentaerythritol hexa Polyhydric alcohols such as (meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripenemeerythritol hexa(meth)acrylate + 7) IJ (meth)acrylate; malonic acid/trimethylolethane/(meth)
Acrylic acid includes methacrylic acid, malonic acid/trimethylolpropane/(meth)acrylic acid, malonic acid/glycerin/(meth)acrylic acid, malonic acid/pentaerythritol/(meth)acrylic acid, succinic acid/trimethylolethane/( meth)acrylic acid, succinic acid/trimethylolpropane/(meth)acrylic acid, succinic acid/glycerin/(meth)acrylic acid, succinic acid/pentaerythritol/(meth)acrylic acid, adipic acid/trimethylolethane/(meth) ) Acrylic acid, adipic acid / trimethylolpropane / (meth)acrylic acid, adipic acid / penmeerythritol / (methaneacrylic acid, adipic acid /
Glycerin/(meth)acrylic acid, glutaric acid/trimethylolethane/(meth)acrylic acid, glutaric acid/trimethylolpropane/(meth)acrylic acid, glutaric acid/glycerin/(meth)acrylic acid, glutaric acid/pentaerythritol /(meth)acrylic acid, sepacic acid/trimethylolethane/(meth)acrylic acid, sebacic acid/trimethylolpropane/(meth)acrylic acid,
Sebacic acid/glycerin/(meth)acrylic acid, sebacic acid/pentaerythritol/(meth)acrylic acid, fumaric acid/trimethylolethane/(meth)acrylic acid,
Fumaric acid/trimethylolpropane/(meth)acrylic acid, fumaric acid/glycerin/(meth)acrylic acid, hexamaric acid/pentaerythritol/(meth)acrylic acid, itaconic acid/trimethylolethane/(methaneacrylic acid, itacon) Acid/11methylolpropane/(meth)acrylic acid, itaconic acid/pentaerythritol/(meth)acrylic acid, maleic anhydride/trimethylolethane/(meth)acrylic acid, maleic anhydride/glycerin/
Saturated or unsaturated polyester poly(meth)acrylate by a combination of compounds such as (meth)acrylic acid: trimethylolpropane tolylene diincyanate, or a polyincyanate represented by the following general formula, ! I (in the formula, %!'Its is hexamethylene diincyanate, tolylene diincyanate, diphenylmethane diincyanate, xylylene diincyanate, a, e-
Acrylic monomer containing polyisocyanate such as methylene bis(cyclohexyl incyanate, inphorone diincyanate or trimethylhexamethylene diisocyanate) and active water X, fQ, tJf, 2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-
Urethane acrylate obtained by reacting 3-methoxyglobyl (meth)acrylate, N-methylol (meth)acrylamide, H-hydroxy (meth)acrylamide, etc. with 53 moles or more per incyanate molecule in a conventional manner; Examples include acryloyloxyethyl)in cyanurate, caprolactone modified tris[acryloyloxyethylcoin cyanurate, tris(methacryloyloxyethyl)in cyanurate, etc.].

Among the polyfunctional monomers (a) having three or more (meth)acryloyloxy groups in one molecule as described above, -
General formula [■] (In the formula & Xu, X+tj:ts, Xn* Xs,
...Xn2 e Xn31 At least three of XI4 are acryloyloxy groups, the rest are hydroxyl groups, amine groups, alkyref groups, or substituted alkylene groups, n is 2 to
It is an integer of 5. ) Compounds represented by n, such as dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. are particularly preferred because they have excellent curing properties with ultraviolet rays in the air. .

Furthermore, in combination with a compound represented by general formula [■], - general formula [■] [VIE (wherein, at least three Y are acryloyloxy groups,
The remainder is hydrogen, hydroxyl group, amine group, alkylene group, or substituted alkylene group, nl-n4, ml-m4
is 0,1. or any n value of 2, and X is a positive integer of 1 to 10. ) When the compound represented by n is used as a polyfunctional monomer, the weather resistance of the resulting crosslinked cured film can be improved, especially changes in appearance such as roughening of the skin, cracks, peeling of the film, and adhering skin due to accelerated exposure can be prevented. Particularly preferred.

-Specific examples of compounds represented by the general formula (VIE) include malonic acid/trimethylolethane/acrylic acid, malonic acid/trimethylolprono(n/acrylic acid, cono-Aric acid/trimethylolethane/acrylic acid) Examples of esterification reactants include combinations of compounds such as , conolilic acid/trimethylolpropane/acrylic acid, adipic acid/trimethylolethane/acrylic acid, and adipic acid/trimethylolgloban/acrylic acid. It will be done.

The performance of the crosslinked film can be further improved by using a polyfunctional monomer (a) in combination with a compound represented by the general formula [v] and a compound represented by the general formula [■] as described above. The compounding ratio is preferably 20 to 70 parts by weight of the compound represented by the general formula [■] to 80 to 5 oxt parts of the compound represented by the general formula [■]. More preferably, the compound represented by the general formula [■] For 70 to 40 parts by weight of the compound,
-30 to 60 parts by weight of the compound represented by the general formula [■] is preferable.

The unit t represented by the general formula C1) used in the present invention
Body (11) has a ring-opening polymerization degree n of ethylene oxide of 5.
~30% polyethylene glycol (methacrylic acid mono- or diester).

When n is less than 4, hydrophilicity is low and the effect of the present invention on antifogging properties cannot be obtained. When n exceeds 30t, solubility in organic solvents decreases, resulting in poor smoothness and wear resistance of the cured film This is not preferable as it also lowers the amount of water.

Regarding the ester structure, either mono- or diester of (meth)acrylic acid may be used, but diester is more preferable from the viewpoint of wear resistance.

Specific examples of these monomers Cb) include polyethylene glycol Luna 400 diacrylate, polyethylene glycol Luna 400 dimethacrylate, polyethylene glycol◆600 diacrylate, polyethylene glycol Luna 600 dimethacrylate, and polyethylene glycol Luna 600 dimethacrylate. 1000 diacrylate, polyethylene glycol φ1
Examples include 000 dimethacrylate.

The proportion of monomer (b) used is 30% in the monomer mixture (A).
-90% by weight, and if it is less than 30% by weight, sufficient antifogging properties will not be obtained, and if it exceeds 9ON, the abrasion resistance of the crosslinked cured coating will decrease, so it is preferable. do not have. In the present invention, monomer (1)) is essential in terms of antifogging properties.

The phosphoric acid ester monomer (C
) has at least one (meth)acryloyloxy group in the molecule, as shown by the general formula (II), and specific examples include (meth)acryloyloxyethyl heptophosphate, di- Examples include (meth)acryloyloxyethyl phosphate, (meth)acryloyloxyethyl 7-phosphate, (meth)acryloyloxybutyl 7-phosphate, and the like. Other halogenated vinyl phosphates.

Those without (meth)acryloyloxy groups, such as alkyl-substituted vinyl phosphates, are unsuitable because they inhibit air curing properties and do not improve antifogging properties, antistatic properties, and dyeing properties. In the composition of the present invention, even if it has a (meth)acryloyloxy group, it is necessary to contain at least one OH group in the phosphoric acid group, and if there is no OH group, the general formula CI [ Monomer n shown in I) and -
It is not preferable because the effect of combined use with the ethanolamine compound represented by the general formula CF/] decreases.

The monomer represented by the general formula (1113) used in the present invention ((1) has at least one hydroxyl group t
V hydroxyalkyl (meth)acrylamides, specific examples include N-(hydroxyglobil)acrylamide, N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N-
-(1゜1-dimethyl-2-hydroxyethyl)acrylamide, N-(1-ethyl-2-hydroxyethyl)acrylamide, N-(1,1-dimethyl-3-hydroxybutyl)acrylamide, N-(hydroxymethyl) ) Methacrylamide, N-(hydroxyethyl)methacrylamide.

N-(hydroxypropyl)methacrylamide, N-(
1,1-dimethyl-2-hydroxyethyl)acrylamide, N-(2,2-dimethyl-2-hydroxyethyl)methacrylamide, ■-(1-ethyl-2-hydroxyethyl)methacrylamide, N-(1, 1-dimethyl-3-hydroxypropyl) methacrylamide, N
Monohydroxyalkyl (meth)acrylamide such as -(1,1-dimethyl-3-hydroxybutyl)methacrylamide: N-(1,1-bis(hydroxymethyl)ethylcoacrylamide, N,N-bis-(2- dihydroxyalkyl (methacrylamide: N-[2-hydroxy-1,1-bis(hydroxymethyl)ethylcoacrylamide), such as hydroxyethyl)acrylamide, N-[1,1-bis,(hydroxymethyl)ethyl]methacrylamide; Examples include trihydroxyalkyl (meth)acrylamides such as N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]methacrylamide.

Other monoalkyl (meth)acrylamides, dialkyl (meth)acrylamides, etc. that do not have any hydroxyl groups are mentioned above, and may reduce the effectiveness when used in combination with the hypophosphate monomer (c) and the ethanolamine compound (e). I don't like it.

In hydroxyalkyl (meth)acrylamide, N
-(Hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, and N-(2-hydroxypropyl)acrylamide monomodroxyalkyl acrylamides are particularly preferred because they have a large combined effect.

The ethanolamine compound used in the present invention (
8) - As shown in the general formula [IV], an alkylamine having at least one OH, 0H20H group and not having an OH, OH, OH group-N has antifogging properties and antistatic properties. It is not preferable as it shows almost no preventive property.

In addition, the number of carbon atoms in the N-substituted alkyl group is suitably 1 to 15, and 16
If it is more than that, the solubility in the solvent decreases, which is not preferable.

In carrying out the present invention, it is essential to use the above-mentioned phosphate monomer (C) together with hydroxyalkyl (meth)acrylamide ((1) and ethanolamine-based (8)), and each may be used alone. Even when used in this way, the desired effect cannot be obtained, and the antifogging properties, antistatic properties, dyeing properties, and storage stability are all inferior and only mediocre.

The phosphoric acid ester monomer (Q) and the ethanolamine compound (13) undergo an exothermic reaction when mixed to form a complex, which significantly improves hydrophilicity.
It exhibits antistatic properties and dyeing properties, and this point is one of the major features of the present invention.

However, the phosphoric acid ester monomer (Cl/jetanolamine compound (θ) is a polyfunctional monomer (a)/
- Due to insufficient copolymerization of polyethylene glycol represented by general formula CI with (meth)acrylic acid mono- or diester (1)) under active energy ray irradiation in air, the resulting crosslinking If a cured film is left in a harsh atmosphere such as high humidity, unreacted hydrophilic components may bleed onto the surface of the film, resulting in undesirable phenomena such as surface tackiness and clouding over time.

By using hydroxyalkyl (meth)acrylamide in combination with the following components, the copolymerizability under active energy ray irradiation is improved, surface tackiness and clouding over time are suppressed, and transparency is excellent. It is now possible to form a crosslinked cured film that has permanent antifogging properties, antistatic properties, and dyeability, and is also excellent in storage stability.

The proportion of the phosphate ester monomer (C-) used is 1 to 20% by weight in the monomer mixture (A). If the amount is less than 1x, sufficient antifogging properties, antistatic properties, and dyeability cannot be obtained, and if it exceeds 20% by weight, fogging occurs in the film and transparency is reduced, which is not preferable.

The proportion of hydroxyalkyl (meth)acrylamide ((1) used is 1 to 1011 L in the monomer mixture (4). If it is less than 1% by weight, sufficient copolymerizability cannot be obtained, so the surface tack is There is the occurrence of clouding over time, and 10X amount%
If it exceeds , the adhesion of the film will decrease, which is not preferable.

The proportion of the ethanolamine compound <6) used is 1 to 10% by weight in the monomer mixture (A). If it is less than 1% by weight, sufficient antifogging properties, antistatic properties, and dyeability cannot be obtained;
Moreover, if it exceeds 10% by weight, the surface smoothness and abrasion resistance of the coating will decrease, which is not preferable.

The proportions of the phosphoric acid ester monomer (C) and the ethanolamine compound C8) are each within the above range of usage.
is not particularly limited, but (C) / (@1) = α5
A particularly preferred range is a weight ratio of /1 to 8/1.

Additionally, hydroxyalkyl (meth)acrylamide (d
) is not particularly limited as long as it is within the usage amount range above, but (C) + (e) / (d) = 1 / 1 to 1
A weight ratio of 0/1 is a particularly preferred range.

The organic solvent used in combination with the monomer mixture (A) constituting the alpha material of the present invention (mainly used in the coating operation when coating the coating material composition on the surface of the resin molded product) It is used to impart extremely favorable effects on the properties and uniformity of the coating, and to significantly increase the adhesion of the coating to the substrate.

The organic solvent used in the present invention is not particularly limited as long as it dissolves the monomer mixture (1) uniformly. good.

Specifically, ethyl alcohol, inglobil alcohol, n-gropyl alcohol, isobutyl alcohol
n-phthyl alcohol natono alcohols, benzene, toluene, xylene.

Aromatic hydrocarbons such as ethylbenzene, ketones such as acetone, methyl ethyl keto/, methyl in butyl ketone, ethers such as dioxane, ethyl acetate, vinegar
Esters such as in-butyl, inamyl acetate, and ethyl globionate, ethylene glycol monomethyl ether.

Examples include polyhydric alcohol-conducting conductors such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and N,N-dimethylformamide.

In addition, monomer monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene can be used in organic solvents if they have a specific purpose, meet the same conditions, and have the same effects as organic solvents. It can also be used as 1m.

The usage ratio of the organic solvent is the monomer mixture (A) mentioned above.
~901 [95 to 10 parts by weight based on negative part (total 100
11Lli1 part) is preferred. If the amount is less than 1 part IQ'IC, the viscosity of the coating material composition is high, resulting in poor coating workability, difficulty in adjusting the coating thickness, and poor smoothness resulting in poor uniform coating formation. This is not preferable because it may cause the film to become stained or the adhesion of the film to the base material may deteriorate.

- On the other hand, if it exceeds 95 mtll, it is not preferable because the film thickness of the coating decreases and sufficient wear resistance cannot be obtained.

As a means for crosslinking and curing the coating material composition, usually 20 to
An electron beam taken from a 2000KV electron beam accelerator,
Although it is possible to irradiate active energy rays such as α rays, β rays, and γ rays, ultraviolet rays with a wavelength in the range of 100 to 500 nm are preferred for economical and easy curing. The ultraviolet irradiation atmosphere includes nitrogen, carbon dioxide,
Of course, irradiation can be performed in an inert gas such as argon, but if a specific polyfunctional monomer is used as described above, it is possible to cure efficiently even in normal air, and this is the most preferable method. .

When ultraviolet 18t- is used as the active energy ray, it is necessary to incorporate a photopolymerization initiator into the coating material composition.

Specific examples of these include benzoin, benzoin methyl ether, benzoin ethyl ether, penzoin inglobil ether, benzoin butyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone-p-methoxybenzophenone, jetoxyacetophenone, α,α-dimethoxyα-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4. l-bis(dimethylaminobenzophenone), 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 1-(4-
inglobilphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-(4-(methylthio)phenyl-2-morpholino-propanone-1)
, etc., sulfur compounds such as tetramethylthiuram disulfide, tetramethylthiuram monosulfide, azobisin butyronitrile, azobis-2
, 4-dimethylvaleronitrile, and peroxide compounds such as benzoyl peroxide and ditertiary-butyl peroxide.

These photopolymerization initiators may be used alone or in combination of two or more.

The amount of these photopolymerization initiators added to the coating composition is as follows:
The amount is in the range of 0 to 10 parts by weight, preferably 101 to 10 parts by weight, based on a total of 100 parts by weight of the monomer mixture (Al and organic solvent CB). If the photopolymerization initiator is used in too large a quantity, it is undesirable because the appearance of the film and the weather resistance deteriorate.

Although the above is an essential structure constituting the present invention, the polyfunctional monomer having three or more (meth)acryloyloxy groups in one molecule in one feeding material composition is Many of them have a high viscosity, so a monomer having two or less (meth)acryloyloxy groups per molecule is blended in order to reduce the viscosity or give the film a high degree of surface smoothness. be able to.

Specific examples of these monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)azirylate, triethylene glycol di(meth)acrylate, and monomers having two (meth)acryloyloxy groups in the molecule. Examples include glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and the like.

Examples of monomers having one (meth)acryloyloxy group in the molecule include methyl (meth)acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl ac+7-late, cyclohexyl acrylate, and 2-hydroxyethyl acrylate. , 2-hydroxyethyl acrylate, glycidyl acrylate,
Examples include tetrahydrofurfuryl acrylate, benzyl acrylate), 1,4-7' ethylene glycol monoacrylate J ethoxy acrylate, and ethylcarpitol acrylate.

In addition, if necessary, a small amount of stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, and heat 1 inhibitors, leveling agents, colorants, etc. may be added to the present coating material composition. .

Methods such as brush coating, flow coating, spray coating, spin coating, or dip coating are adopted as methods for applying the present coating composition. The dip coating method is particularly preferred from the viewpoints of properties, adhesiveness of the cured film to the substrate, and the like.

The coating amount of the coating material composition is such that the thickness of the cured film is 1 to 1.
It is preferable to apply the coating to a thickness of 30 μm, preferably 2 to 20 μm. If the thickness of the cured film is less than 1 μm, the weather resistance will deteriorate and sufficient abrasion resistance will not be obtained, and if it exceeds 30 μm, the layering properties with the base material will deteriorate and FCV will not cause cracks.

In the present invention, the synthetic resin molded products used in the manufacture of the A7j synthetic resin molded products, which have excellent wear resistance, surface smoothness, antifogging properties, and antistatic properties, are thermoplastic resins, thermosetting resins, and gold. All kinds of synthetic resin molded products, such as polymethyl methacrylate resin, polycarbonate juzuki, polyallyl diglycol carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, p, Bs resin, These include sheet-like, hollow-shaped products, film-like molded products, rod-like shaped products, and various injection molded products manufactured from polyester resin. Among these molded products, polymethyl methacrylate resin is used. , manufactured from polycarbonate resin etc.
A wide variety of shapes, optical properties, and heat resistance.

It is often used to take advantage of its properties such as impact resistance.
In addition, there is a strong demand for improved wear resistance, antifogging properties, and antistatic properties, so these molded products are particularly preferred as synthetic resin molded products used in the present invention.

〔Effect of the invention〕

A synthetic resin molded article having a crosslinked cured coating on the surface produced using the coating composition of the present invention has excellent surface smoothness,
And wear and scratch resistant.

and has excellent surface hardness. Further formed on the surface n
The coating has excellent anti-α and antistatic properties, and does not fog up even when taken out from a high-temperature, high-humidity atmosphere or a low-temperature atmosphere to a room temperature atmosphere, and does not become dusty or dusty even when rubbed. There is no adhesion.

Furthermore, even if left in harsh conditions such as a high humidity atmosphere for a long period of time, there will be no tackiness or clouding over time due to surface bleed, and there will be no deterioration in performance even after washing with water, making it permanently anti-fogging. It has antistatic properties and antistatic properties.

Additionally, a cross-linked cured film that does not contain a phosphate ester monomer and an ethanolamine compound is difficult to dye regardless of the dye type, but the cross-linked cured film of the present invention can be dyed with most of the 3 types of dyes. Can be dyed.

Furthermore, the crosslinked cured coating of the present invention has excellent adhesion to substrates, making it extremely suitable for applications such as organic window glasses, lighting equipment covers, reflectors, spectacle lenses, sunglass lenses, and optical lenses. Useful.

〔Example〕

The content of the present invention will be explained in more detail below with reference to Examples. Note that the measurement and evaluation in the examples was performed by the following method.

(1) Attach steel wool with abrasion resistance ÷ 000 to the tip of a cylinder with a diameter of 25 mm, place it horizontally, and touch it with the surface of the sample.
0 was rotated 5 times (20 rpm) L with a load, and the degree of adhesion of scratches was visually observed.

O: There is almost no scratch on the sample surface.

Δ...The sample surface is scratched.

×...Extremely many scratches on the sample surface. (2) Adhesion cross cut joint peel test. Make 100 1-stitches, paste the Seronon tape on top of it, and peel it off sharply upwards. The remaining number at the time of seven is first expressed by the number of stitches.

Number of remaining squares Total number of squares (3) Appearance 1. Smoothness ○ Surface smoothness is good Δ Surface smoothness is slightly insufficient X Surface smoothness is poor 2. Cloudiness of transparent coating (4) Measurement of antistatic charge half-life The sample was kept at constant temperature and humidity of 20°C and relative humidity of 65 m2 for 24 hours, and then measured using a static honest meter (
(manufactured by Shishido Shokai), a voltage of 10 KV was applied for 30 seconds to measure the half-life.

(5) Anti-fog property - After holding the sample at a temperature of 20℃ for 5 minutes,
The sample was taken out under constant temperature and humidity conditions of 0°C and relative humidity of 65°C, and the time until dew condensed on the sandal surface was measured.

(6) Hot water resistance test sample tl - After immersing in hot water of 40℃ for 24 hours,
It was dried in an atmosphere at ℃ for 30 minutes, and its antifogging properties were measured using the method described above.

(7) Leave the test sample in an atmosphere with a temperature of 40℃ and a relative humidity of 90% for 2 hours.
After holding for 4 hours, the degree of clouding on the sample surface was measured using the haze meter described above.

Example 1. Comparative Examples 1 to 5 A coating material composition was prepared as shown in Table 1, and 2.
A thick methacrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite) was immersed in water to form a film at a pulling rate of α5α/8eC. Leave it as it is for 5 minutes,
A high-pressure mercury lamp (manufactured by Iwasaki Electric, 2 KW) in an air atmosphere.
HO2-L21) When using gold, irradiate for 15 seconds at irradiation distance of 20 mm. The results obtained are shown in Table 1.

As shown in Example 1, the coating material composition of the present invention exhibits good curability by ultraviolet irradiation in the air, and exhibits not only abrasion resistance, dense layer properties, smoothness, and transparency, but also antifogging properties. 8.It has anti-static properties, excellent dyeing properties, and has excellent durability with no deterioration in initial performance even under severe test conditions such as hot water resistance tests and storage tests under high temperature and high humidity. be.

In comparison, as shown in Comparative Examples 1 to 4, systems lacking either polyethylene glycol (meth)acrylate, phosphate ester monomer, or hydroxyalkyl (methacrylamide, ethanolamine compound) Although the abrasion resistance, adhesion and smoothness are good, the transparency is poor.

It is not possible to obtain a product that exhibits all of the antifogging properties, antistatic properties, and dyeing properties. Furthermore, even if the antifogging properties, antistatic properties, and dyeability are good, systems lacking hydroxyalkyl (meth)acrylamide do not exhibit surface bleeding or fogging in storage tests under high temperature and high humidity. Because of this, it is impossible to obtain a product with superior durability.

Furthermore, as shown in Comparative Example 5, the system using trifunctional acrylate 1 other than the present invention was not crosslinked and cured by ultraviolet irradiation in air. Examples 2 to 7. Comparative Examples 6-7 A coating material composition as shown in Table 2 was prepared.

It was treated in the same manner as in Example 1. Table the results obtained.
Shown in 2.

As shown in Comparative Examples 6 and 7, the following systems using polyethylene glycol (meth)acrylates other than those of the present invention have poor antifogging properties.

Examples 8-14. Comparative Examples 8 to 13 The preparations in Example 1 were processed in the same manner as in Example 1, except that the types of phosphate ester monomer, alkylamine, and acrylamide monomer were changed. The results obtained are shown in Table 3.

As shown in Examples 8 to 10, the following systems using the phosphoric acid ester monomer of the present invention had good performance, but the following systems (Comparative Examples 8 to 9) using materials other than the present invention had poor adhesion. and anti-fog properties,
Antistatic properties are insufficient.

As shown in Examples 11 and 12, in the system using hydroxyalkyl acrylamide, no clouding was observed in the storage test at high temperature and high humidity. ~11)'l1l-The next system used had clouding and did not have good durability.

As shown in Examples 13 and 14, N in which the alkyl group has 3 carbon atoms in the ethanolamine system of the present invention is added to the alkylamine.
- The following system using propylgetanolamine and 8 N-octylgetanolamine has good performance, but the system using alkylamines other than the present invention (Comparative Examples 12 to 15) has smoothness or antistatic properties. Poor quality.

Examples 15-16. Comparative Examples 14 to 17 All coating material compositions as shown in Table 4 were prepared, and treated under the same conditions as in Example 1 except that the base material was a polycarbonate resin plate (Mitsubishi Gas Chemical Exhibition Knee Pillon) 2 thick. The obtained NFC results are shown in Table 4.

Implementation fl+17-19. Comparative Examples 18 to 23 The coating material compositions shown in Table 5 were prepared and treated under the same conditions as in Example 1 using the coating material compositions shown in Table 5. The obtained 1" Lfc results are shown in Table 5.

Example 20. Comparative Examples 24 to 25 The monomer mixture (N composition in the coating material composition shown in Example 1 was changed in the following manner). - Treated under these conditions.

2P5A (parts by weight) TAS (parts by weight) Example-2
0813 Comparative Example-24210 Comparative Example-25021 The product of Example-20 shows no particular change in appearance after 1000 hours of accelerated exposure to Sunshine Weather-Ometer.
Weather resistance was good. On the other hand, Comparative Example 24 showed insufficient weather resistance as no cracking was observed under similar conditions. From this result, 2P5
It is essential to use A/TAB together, and from the viewpoint of weather resistance, TA
B is an essential component.

Comparative Example 25 is a system containing only TAB and 2P5A, and the abrasion resistance of the crosslinked cured film is insufficient. Therefore, from the above results, the above results indicate that trifunctional or more [methacrylic acid] It can be seen that by mixing and using the monomers represented by the formula [■] and the general formula [■], a crosslinked cured film with excellent weather resistance and abrasion resistance and good friend performance can be obtained.

Claims (1)

[Claims] 1) 3 or more acryloyloxy groups and/or
or a polyfunctional monomer having a methacryloyloxy group (
a) 7 to 50% by weight and the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, R_1 is hydrogen or a methyl group, R_2 is a carbon number of 1
~5 alkoxy group, acryloyloxy group, or methacryloyloxy group, n is an integer of 5 to 30. ) 30 to 90% by weight of monomer (b) represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [II] (In the formula, R_3 is hydrogen or a methyl group, R_4 is hydrogen or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, R_5 is hydrogen or methyl group, m and p are integers of 1 to 15.) Phosphate ester monomer (C) 1 to 20% by weight , the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [III] (In the formula, R_6 is hydrogen or a methyl group, R_7 is hydrogen or a hydroxyalkyl group having 1 to 8 carbon atoms, R_8, R_1
Each of _0 is hydrogen, an alkyl group having 1 to 8 carbon atoms, or a hydroxyalkyl group having 1 to 8 carbon atoms. ) and the following general formula NR_1_1R_1_2(CH_2CH_2OH) [I
V] (where R_1_1 and R_1_2 are each hydrogen, an alkyl group having 1 to 15 carbon atoms, or CH_2CH_2O
It is an H group. ) Ethanolamine compounds (
e) a monomer mixture (A) consisting of 1 to 10% by weight;
90 parts by weight of at least one organic solvent (B) which is mixed with the monomer mixture (A) to form a homogeneous solution.
A highly functional coating consisting of 10 parts by weight and 0 to 10 parts by weight of a photopolymerization initiator (C) (based on a total of 100 parts by weight of the monomer mixture (A) and organic solvent (B)) material composition. 2) The polyfunctional monomer (a) has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] (In the formula, X_1_1, X_1_2, X_1_3, X_2
_2, X_2_3... X_n_2, X_n_3, X
At least three of _1_4 are acryloyloxy groups, the rest are hydroxyl groups, amino groups, alkylene groups, or substituted alkylene groups, and n is an integer of 2 to 5. ) and 80 to 30 parts by weight of at least one compound represented by the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [VI] (In the formula, at least three Y are acryloyloxy groups,
The rest are hydrogen, hydroxyl group, amino group, alkylene group, or substituted alkylene group, n_1 to n_4, m_1 to m_
4 is a numerical value of 0, 1 or 2, and X is a positive integer of 1 to 10. ) At least one compound represented by 2
A coating composition according to claim 1, which is a mixture of 0 to 70 parts by weight. 3) Monomer (b) is selected from the group consisting of polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol 1000 diacrylate, polyethylene glycol 400 dimethacrylate, polyethylene glycol 600 dimethacrylate, and polyethylene glycol 1000 dimethacrylate. The coating material composition according to claim 1, which is a composition according to claim 1. 4) The phosphate ester monomer (c) is selected from the group consisting of acryloyloxyethyl phosphate, methacryloyloxyethyl phosphate, diacryloyloxyethyl phosphate, and dimethacryloyloxyethyl phosphate. Claim 1
The coating material composition described in Section 1. 5) Monomer (d) is N-hydroxymethylacrylamide, N-(2-hydroxyethyl)acrylamide, N
The coating composition according to claim 1, which is selected from the group consisting of -(2-hydroxypropyl)acrylamide. 6) Ethanolamine compound (e) has 1 to 15 carbon atoms
The coating material composition according to claim 1, which is diethanolamine having an alkyl group of .