JPH01229622A - High hardness painted steel plate excellent in stain resistance and antidazzling property and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a painted steel plate, which is very hard and has so excellent stain resis tance comparing with porcelain enamel as to be easily wiped off by washing even when stained and at the same time antidazzling property, by a method wherein a steel plate is covered with an electron radiation curing type paint film, the essential ingredients of which are specified substances. CONSTITUTION:A steel plate is covered with an electron radiation curing type paint film, which consists essentially of A: 90-10pts.wt. of oligo(meth)acrylate, one molecule of which contains more than one (meth)acryloyl group and at the same time the (meth)acryloyl group equivalent of which is 50 or less, B: 90-10pts.wt. of polyvalent alcohole (meth)acrylate, one molecule of which contains more than one (meth)acryloyl group and at the same time the (meth)acryloyl group equivalent of which is 150 or less, C: 0.5-20pts.wt. of silica-based extender pigment with respect to 100pts.wt. of the mixture of the components A and B, D: 1-20pts.wt. of polymer having the molecular weight of 5,000 or more and E: 1-40pts.wt. of glass powder with respect to 100pts.wt. of mixture of the components A, B, C and D. The action of the glass powder is to raise the hardness of the paint film (up to 9H or higher in pencil hardness) and to give antidazzling effect without impairing the stain resistance of the paint film. The proper size of spherical glass powder is 0.1-2.0 times as thick as the thickness of the paint film, when the thickness of the dry paint film lies within the range of 15-120mum and the preferable diameter of a sphere does not exceed 100mum.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a coated steel plate having a coating film hardened by electron beams that has high hardness, stain resistance, and excellent anti-glare properties that reflect less light. The present invention relates to a manufacturing method thereof.

Conventional technology In general, paints are soluble in solvents, and are made into insolubilized by scattering the solvent at room temperature or by heating, or by causing a crosslinking and curing reaction by heating, ultraviolet rays, infrared rays, etc., to form a cured coating film. shall be.

However, with these methods, the material is extremely hard, does not swell or discolor when exposed to any organic solvent, and has sufficient stain resistance against marker ink, whiteboard markers, and other contaminants. It is difficult to obtain the product.

The present inventors applied a paint system consisting of oligo(meth)acrylate, polyhydric alcohol(meth)acrylate, silica-based extender pigment, and polymer to a steel plate, as seen in JP-A No. 80-40189, and applied electron beams to the steel plate. By curing the coating film using a curing method, a coated steel plate with excellent solvent resistance and stain resistance and a highly hard coating film was obtained, but the maximum hardness was approximately 8H on a pencil hardness scale. .

Also, special public service No. 50-25485. Special Public Service 1977-8128
As shown in the above, the pencil hardness of pre-coated steel plates made by adding glass fibers and flaky glass to paints is about 6H at most, except for matte polyester, and the stain resistance is not necessarily good. There wasn't.

Furthermore, the reality is that sufficient research and development has not been carried out until now regarding anti-glare properties, which are required depending on the intended use.

Therefore, the present inventors developed a product that is extremely hard (pencil hardness <9H), can be easily wiped off by washing even if contaminated, has excellent stain resistance comparable to that of enamel, and eliminates anti-glare properties. We proceeded with the development of painted steel plates.

Problems to be Solved by the Invention The present invention solves the above-mentioned extremely hard (pencil hardness 9H),
The present invention aims to provide an unprecedented coated steel sheet that has excellent stain resistance and is suitable for applications requiring anti-glare properties as required, and a method for producing the same.

Means for Solving the Problems The gist of the coated steel sheet according to the present invention is as follows: (1) A: Contains two or more (meth)acryloyl groups in one molecule, and has a (meth)acryloyl group equivalent of 50
0 or less oligo(meth)acrylate 90 to 101 parts by weight, B: Polyhydric alcohol (meth)acrylate containing two or more (meth)acryloyl groups in one molecule and having a (meth)acryloyl group equivalent of 150 or less 90 ~10 parts by weight, and 100 parts by weight of the mixture of components A and B, C: 0.5 to 20 parts by weight of silica-based extender pigment, D: molecule 3
5000 or more polymer 1 to 20 parts by weight, and A, B
1 to 40 parts by weight of E glass powder per 100 parts by weight of the mixture of components C, D, and C are coated with an electron beam curable paint film as an essential component. Painted metal plate with excellent anti-glare properties.

(2) A: Contains two or more (meth)acryloyl groups in one molecule and has a (meth)acryloyl group equivalent of 50
0 or less oligo(meth)acrylate 90 to 10 polyhydric parts, B: polyhydric alcohol (meth)acrylate containing 2 or more (meth)acryloyl groups in one molecule and having a (meth)acryloyl group equivalent of 150 or less 80 to 10 parts by weight, and 100 parts by weight of the mixture of components A and B, C: 0.5 to 20 parts by weight of silica-based extender pigment, D = molecule
5000 or more polymer 1 to 20 parts by weight, and A, B
A paint containing 1 to 40 parts by weight of E glass powder as an essential component per 100 parts by weight of the mixture of components C, D, and C is applied to the object to be coated, and the paint is heated by electrons in an inert gas with an oxygen concentration of 1% or less. A coated metal plate with high hardness, excellent stain resistance and anti-glare properties, which is characterized by being wire hardened.

It is.

action The coated steel sheets of the present invention are A, B, and C described above.

It is obtained for the first time by coating with a coating film that has five essential components D and E, four of which are: ■Oligo(meth)acrylate, ■Polyhydric alcohol (meth)acrylate, ■Silica-based structure. Pigment, ■molecule 450
Regarding the effects of polymers of 00 or higher, see Japanese Patent Application Laid-Open No. 60-4
As stated in 0189, the combination of (1) and (2) allows a coating film with high crosslink density to be obtained; This makes it possible to compensate for the lack of stickiness of the resin system consisting of ■ and ■, allowing good coating with industrial coating machines (curtain flow coater, roll coater, etc.), and making the effects of silica-based extender pigments more pronounced. It is something that makes you become accustomed to it.

Here, the object of the present invention is high hardness (pencil hardness 9H<).
In order to obtain a coating film with high stain resistance and anti-glare properties, various studies were conducted, and the results revealed that it is best to additionally use glass powder.

That is, from the perspective of increasing hardness, materials that are hard themselves, such as metal powders such as iron powder, copper powder, stainless steel powder, brass powder, bronze powder, zinc powder, and nickel powder, can be considered.
Because it has a unique color, it is limited in the coloring of paint, or because it has a high specific gravity, it precipitates in paint and is not suitable for coating with industrial paint machines, or It has been found that both curtain flow coaters and roll coaters are unsuitable for industrial production because they have the disadvantage that they precipitate and accumulate in the pipes and hoses of the paint circulation system, making it difficult to clean the paint machine.

A glass powder that eliminates these drawbacks and meets the purpose of the present invention will be defined as component E in the present invention, and its effects will be described.

The glass powder used in the present invention refers to a spherical powder having a three-dimensional radius, and a fibrous powder having a two-dimensional radius and linear length in other dimensions. To define the phrase, it is obvious that whether it is spherical or fibrous, the radius is not exactly the same, and although there may be slight differences, it is natural that it may be elliptical, for example. .

The action of this glass powder increases the hardness of the coating (pencil hardness: 9
H<)L, which imparts an anti-glare effect without impairing the stain resistance of the coating film.

To provide an anti-glare effect, that is, to reduce gloss, extender pigments are generally added.If the amount is increased, the gloss decreases, but the stain resistance also decreases, which does not meet the purpose of the present invention. Generally speaking, it cannot be used as an additive that improves staining properties.

As a result of various studies, the present inventors found that if the glass powder is spherical, it will be relatively smooth even if it protrudes, and the contaminants will not form a clogged shape. It seems that this will not be a hindrance.

Here, I will talk about the size of glass powder. Whether it is spherical or fibrous, it will not be effective in increasing the scratch hardness of the paint film unless it is exposed above the paint surface.However, what is meant here is that the size of the glass powder This does not mean that it has to be larger than the film thickness, but even if it is smaller than the film thickness, it is sufficient as long as it floats in the film and is exposed above the surface of the film.

First, we will discuss the appropriate size of spherical glass powder. Although this may vary slightly depending on the viscosity of the paint during painting, the thickness of the coating film, etc., it has been found that the size shown by Ojiji is good. That is, when the paint viscosity during painting is 10 to 100 seconds for Ford Cup #4 and the dry coating thickness is 15 to 120, the diameter of the spherical glass is 0.1 to 2.0 times the coating thickness, and It has been experimentally found that the preferred condition for achieving the object of the present invention is that the sphere diameter does not exceed 100 JL. If the spherical diameter of the glass is smaller than the range of the present invention, the probability that it will be exposed from the coating surface will be small, and it will not be useful for improving hardness.
It was also found that there was not much reduction in gloss and the anti-glare properties were also poor. Furthermore, if the diameter of the glass sphere is larger than the range of the present invention, the dispersibility in the paint may be poor or the glass tends to settle in the paint, which may cause trouble during painting. In the case of spherical glass, the inside of the sphere may be hollow.

Next, we will discuss the appropriate size of fibrous glass powder.

Assuming that the paint viscosity and film thickness are within the ranges mentioned above, F
The diameter of the male a is 0.1 to 1.5 times the coating thickness, and the length is 2
It has been experimentally found that a range of 0 to 100 elongation is good. If it is outside these ranges, it is undesirable for the reasons mentioned above for spherical glass powder.

Here, the glass may be coated to improve its adhesion with the paint, such as silane treatment such as aminosilane, glycidosilane, acrylic silane, etc., chromium treatment, etc.

Incidentally, when comparing spherical glass powder and U-shaped glass powder, spherical glass powder often satisfies the purpose of the present invention, although it depends on the number of glass particles.

Regarding the amount of glass powder to be added, the objective of the present invention is to add 1 to 40 parts by weight, preferably 3 to 30 parts by weight, per 100 parts by weight of the paint consisting of components A, B, C, and D. It is possible.

The oligo(meth)acrylate which is component A of the present invention will be explained in more detail.

If the number of (meth)acryloyl groups and the equivalent weight of (meth)acryloyl groups are within the scope of the present invention, the polyhydric alcohol (
In combination with meth)acrylates, acrylics, epoxies, polyamides, silicones, urethanes, and other materials generally meet the performance of the present invention, but when considered in combination with polymers, polyesters also have preferred performance.

The oligo(meth)acrylate used in the present invention is
It is obtained by using a polyester skeleton in the main chain and esterifying it with (meth)acrylic acid.As for the material used in the present invention, it is necessary to have a sufficiently cross-linked network structure. 2 (meth)acryloyl groups inside
(meth)acryloyl group equivalent is 500 or less, more preferably 400 or less because the crosslinking density must be sufficiently high. In this case, two or more of these oligo(meth)acrylates may be mixed and used as long as they satisfy the requirements of the present invention described above.

Let's talk about this ingredient in more detail. Oligo(meth)acrylate with a polyester skeleton in the main chain is made of polyhydric alcohol and polycarboxylic acid, and the polyester has a hydroxyl group at the end, and is reacted with (meth)acrylic acid or its derivatives. (Meth)acryloyl groups are introduced here.Here, we will further discuss the synthetic raw materials that form the polyester skeleton.

That is, as dihydric alcohols, alkylene glycol types include ethylene glycol, propylene glycol, chloroboropylene glycol, butanediol (l,
3- or 1.4- or 2.3-), 3-methylbentanediol, 2,2-diethylpropanediol, pentamethylene glycol, l,6-hexanediol,
Pentamethylene glycol, octamethylene glycol, nonamethylene glycol, neopentyl glycol,
Hexamethylene diol, fatty glycol types include 1,4-cyclohexanediol, cyclohexane-1,4-dimetatool, hydrogenated bisphenol A, etc. polyalkylene gelicol types include diethylene glycol, triethylene glycol, polyethylene glycol, Dipropylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene diol, etc., and as aromatic glycol type, 2.
Flukylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.).

Examples of the 3- to 4-benzene alcohols include glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2. fl
-Hegosantriol, 1,2.3-butanetriol, 1,2.3-pentanetriol, 2-methyl-2,
3,4-butanetriol, 2-ethyl-2,3,4-
Butanetriol, 2-methyl-1,2,3-butanetriol, 2-ethyl-1,2,3-butanetriol, 2-3.4-hexanetriol, pentamethylene glycol, etc., erythritol, Pentaerythritol, Toilet, 1.2.
3.4-pentanetetrol, 2,3,4.5-hexanetetrol, 2.5-dimethyl-2,3,4,5-hexanetetrol, 1,2,3.5-pentanetetrol, 3-hexene-1,2,5,8-tetrol, 3-
Ether group-containing aliphatic triols such as hexyne-1,2,5,6-tetrol include triols obtained by adding fullylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) to glycerin, trimethylolpropane, etc. Examples of ether group-containing aliphatic tetraols include tetraols obtained by adding alkylene oxide to erythritol or pentaerythritol, and aromatic triols include triols obtained by adding alkylene oxide to pyrogallol.

Examples of carboxylic acids include chain or branched divalent carboxylic acids such as oxalic acid, malonic acid, and succinic acid.

Aliphatic dicarboxylic acids such as glutaric acid, itaconic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, toticanic acid, methylene glutaric acid, methylmaleic acid, methylsuccinic acid, dodecenylconolyric acid, tetrahydrophthalic acid, hexahydro Phthalic acid, 8-methyltetrahydrophthalic acid, 6-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endoisopropylidenetetrahydrophthalic acid, 1,4,5,8,7.
7-hexachloro-endo-5-fulbornene-2,3
-dicarboxylic acid (also known as het acid), 1,4,5,8,
7.7-Hexabromo-endo-5-norbornene-2
, 3-dicarboxylic acid, cyclohexane, 1,4-dicarboxylic acid, etc., and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, or anhydrides thereof. etc.

Specific examples of polyester oligomers containing two (meth)acryloyl groups include di(meth)acrylate of polyester diol of maleic acid and ethylene glycol, and polyester of maleic acid and diethylene glycol. di(meth)acrylate of polyester diol with adipic acid and diethylene glycol, di(meth)acrylate of polyester diol with tetrahydrophthalic acid and diethylene glycol, polyester diol with tetrahydrophthalic acid and propylene glycol Di(meth)acrylate, di(meth)acrylate of polyester diol of tetrahydrophthalic acid and butanediol (1,3- or 1,4-), polyester diol of tetrahydrophthalic acid and 1,6-hexanediol Di(meth)acrylate, di(meth)acrylate of polyesterdiol of tetrahydrophthalic acid and neopentyl glycol, di(meth)acrylate of polyester diol of tetrahydrophthalic acid and 1,4-cyclohexanediol, phthalic acid and Examples include di(meth)acrylate of polyester diol with diethylene glycol, and di(meth)acrylate of polyester diol with phthalic acid and neopentyl glycol.

Among these polyester oligomers, it has a structure of di(meth)acrylate of polyester diol of tetrahydrophthalic acid or adipic acid and alkylene glycol or cycloalkylene glycol having 3 to 6 carbon atoms, and has a number average molecular melt of 350 to 800. , (number average molecule ff1180 to 400 per metacoacryloyl group
The polyester oligomers are particularly suitable for the purposes of the present invention.

Further, specific examples of polyester oligomers having two or more (meth)acryloyl groups include tetra(meth)acrylate of polyester polyol of adipic acid and pentaerythritol, penta(meth)acrylate,
Acrylate, hexa(meth)acrylate, tetramethacrylate, penta(meth)acrylate of polyester polyol with tetrahydrophthalic acid and pentaerythritol
Acrylate, hexa(meth)acrylate, tetra(meth)acrylate of polyester polyol with phthalic acid and pentaerythritol, penta(meth)acrylate, hexa(meth)acrylate, tetra(meth)acrylate of polyester polyol with maleic acid and pentaerythritol acrylate, penta(meth)acrylate,
Hexa(meth)acrylate, tetra(meth)acrylate of polyester polyol of adipic acid and trimethylolpropane, penta(meth)7 acrylate, hexa(meth)acrylate, tetra( of polyester polyol of tetrahydrophthalic acid and trimethylolpropane) Examples include meth)7 acrylate, penta(meth)acrylate, hexa(meth)acrylate, tetra(meth)acrylate of polyester polyol of tetrahydrophthalic acid and glycerin, penta(meth)acrylate, and hexa(meth)acrylate.

Among these polyester oligomers, adipic acid or tetrahydrophthalic acid and trimethylolpropane,
Or a polyester polyol with pentaerythritol having a structure of tetra(meth)acrylate, penta(meth)acrylate or hexa(meth)acrylate, number average molecular weight 550-2000, number average molecular weight per (meth)acryloyl group 100- 350 polyester oligomers are preferred for purposes of the present invention.

The polyhydric alcohol (meth)acrylate as component B in the present invention refers to one in which a (meth)acryloyl group is introduced by reacting (meth)acrylic acid with the terminal hydroxyl group of a polyhydric alcohol, and oligo(meth)acrylate In combination with this, it serves to obtain an extremely high W density. In order to do this, one molecule must contain two or more (meth)acryloyl groups, and the (meth)acryloyl group equivalent is 1.
It is 50 or less, more preferably about 130 or less.

In this case, a mixture of the above-mentioned polyhydric alcohol (meth)acrylates may be used, and the polyhydric alcohol referred to herein refers to the following.

That is, as dihydric alcohols, alkylene glycol types include ethylene glycol, propylene glycol, chloropropylene glycol, butanediol (1,
3- or 1.4- or 2.3-), 3-methylbentanediol, 2,2-diethylpropanediol, pentamethylene glycol, 1.8-hexanediol,
heptamethylene glycol, octamethylene glycol, nonamethylene glycol, neopentyl glycol,
Fatty glycol types such as hexamethylene diol, 1,4-cyclohexanediol, cyclohexane-1,4-dimetatool, hydrogenated bisphenol A, etc., aryalkylene glycol types such as diethylene glycol, triethylene glycol, polyethylene glycol, Dipropylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene diol, etc., and as aromatic glycol type, 2
, 2°-bis(4-hydroxyphenyl)propane (also known as bisphenol A), bis(4-hydroxyphenyl)methane (also known as bisphenol F), 4,4-dihydroxyphenyl, hydroquinone, and resorcinol. Len oxide (ethylene oxide, propylene oxide, butylene oxide, etc.)
Examples include glycols obtained by adding .

Examples of trihydric or higher alcohols include glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, and 1,2.8-alkanetriol type alcohols.
Hexanetrione, L, 2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-2
, 3,4-butanetriol, 2-ethyl-2,3,4
-butanetriol, 2-methyl-1,2,3-butanetriol, 2-ethyl-1,2,3-butanetriol, 2-3.4-hexanetriol, pentamethylene glycol, etc., as alkanetetraol, erythritol , pentaerythritol, dipentaerythritol, toilette, 1,2,3.4-pentanetetrol, 2,3,4.5-hexantetrol, 2.5-dimethyl-2,3,4,5-hexantetrol troll, 1,
2,3.5-pentanetetrol, 3-hexene-1,
2,5,6-tetrol, 3-hexyne-1,2,5,
Ether group-containing aliphatic triols such as 8-tetrol include triols obtained by adding fullylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) to glycerin, trimethylolpropane, etc., and ether group-containing aliphatic tetraols. Examples of the ols include tetraols obtained by adding fullkylene oxide to erythritol, pentaerythritol, etc., and aromatic triols include triols obtained by adding fullkylene oxide to pyrogallol.

Of these, as a result, (meth)acryloyl base unit ¥1
Particularly preferred are those of 20 or less.

Furthermore, what is important is that adding a polymer is an essential condition of the present invention, and in this case, there is a possibility that performance such as hardness and stain resistance may be deteriorated. In order to prevent this performance deterioration, it is necessary to have an average (meth)acryloyl group equivalent of 100 to 200 in the system in which oligo(meth)acrylate and polyhydric alcohol (meth)acrylate are mixed.
It has been made clear in the present invention that the addition of a polymer is particularly preferable.

Here, we will discuss the blending ratio of oligo(meth)acrylate and polyhydric alcohol (meth)acrylate. Oligo (meth) acrylate/polyhydric alcohol (meth) acrylate is preferably in the range of 9/1 to 1/9 (weight ratio),
This is because oligo(meth)acrylate alone does not increase the crosslink density sufficiently, so polyhydric alcohol (meth)acrylate is added to increase the crosslink density, but in order to meet the purpose of the present invention, , lowest vs. oligo(
It is necessary to add at least 1 to 9 parts of meth)acrylate.

Here, the upper limit of polyhydric alcohol (meth)acrylate is 9 to oligo(meth)acrylate l, but if more than this is added and the coating film is cured, the , cracks will increase if the paint film is cracked or scratched. Therefore, it is preferably 9 or less.

The reason why the amount of polyhydric alcohol (meth)acrylate added can be increased compared to the case of JP-A-49-32488 is that the above-mentioned trouble can be prevented by adding a polymer with a molecular weight of 5000 or more, which will be described later. It is from.

Next, I will talk about the silica-based extender pigment, which is component C.
The materials that meet the purpose of the present invention are listed above, but the one that is particularly effective is silica, which has an oil absorption of 100 g and 7100 g.
As mentioned above, the more preferable one is 150.71 ong. Regarding the amount, the oligo(
The amount of silica is 0.0 parts per 100 parts of the total amount of meth)acrylate, polyhydric alcohol (meth)acrylate, and polymer.
Adding 5 parts or more, preferably 1.0 parts or more will meet the purpose of the present invention.

Specifically, the names are Thyroid series manufactured by Fuji Davison Chemical Co., Ltd., Mizuriki Sil series manufactured by Kizawa Chemical Industry, Milton series manufactured by Tokuyama Soda Co., Ltd., Triseal series, Fine Seal series manufactured by Geotsugi Pharmaceutical, and Carplex manufactured by Geotsugi Pharmaceutical Co., Ltd. series, Aerosil series manufactured by Nippon Aerosil, etc. In the present invention, a mixed system of two or more types of extender pigments may be used.

Next, 150 molecules added as component D in the present invention
Describes polymers of 00 or higher.

As long as the above requirements are met, acrylic, polyester, urethane, epoxy, polyamide, melamine, silicone, alkyd, etc., and modified products or combinations thereof may be used, but coating performance and coating materials may be used. Acrylic, polyester, and polyurethane, alone or in combination, work particularly well in terms of both properties. In this case, it may be a mixture of two or more of the same type of resin.

Here, the constituent components of the acrylic polymer will be described, but the present invention is not limited thereto.

For example, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-7 mil acrylate, n-hexyl acrylate, Acrylic acid alkyl esters such as n-octyl acrylate, alkyl acrylate halides such as 2-chloroethyl acrylate and 3-chloropropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate Acrylic acid-containing OH group esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
α-alkyl acrylic acid alkyl esters such as inpropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, %-n-octyl methacrylate, lauryl methacrylate, α-
α-halogenated acrylic esters such as methyl chloroacrylate and α-ethyl chloroacrylate; α-alkyl acrylic ugly halogenated alkyl esters such as 2-chloroethyl methacrylate and 3-chloropropyl methacrylate; 2-hydroxyethyl, 2-hydroxypropyl methacrylate, 1-methacrylate
~ α with OHi such as chloro-2-hydroxyethyl
- Acrylic monomers containing epoxy groups such as alkyl acrylic ugly esters and glycidyl acrylate glycidyl methacrylate, monomers having 7-mino groups such as dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, etc. included.

As component D of the present invention, it is preferable to use one or more of these acrylic monomers in an amount of 50 mol% or more of the total monomers, and any remaining monomers can be used as long as they can be copolymerized. It is.

Next, the constituent components of polyester will be described, but they are not limited to those exemplified below.

That is, as alcohols, alkylene glycol types include ethylene glycol, dipropylene glycol,
Chlorpropylene glycol, butanediol (l, 3
- or 1.4- or 2.3-), 3-methylbentanediol, 2,2-diethylpropanediol,
Pentamethylene glycol, 1,6-hexanediol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, neopentyl glycol, hexamethylene diol, etc., 1,4-cyclohexanediol, cyclohexane-1, etc. , 4-dimetatool, hydrogenated bisphenol A
Polyalkylene glycol types such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene diol, etc., and aromatic glycol types such as
2. Flukylene is added to phenols such as 2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), bis(4-hydroxyphenyl)methane (also known as bisphenol F), 4,4°-dihydroxyphenyl, hydroquinone, and resorcinol. Examples include glycols obtained by adding oxides (ethylene oxide, propylene oxide, butylene oxide, etc.).

Furthermore, as alkantriol type, glycerin,
Trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2.8-hexanetriol,
1,2.3-butanetriol, 1,2.3-pentanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-2,3,4-butanetriol, 2
-Methyl-1,2,3-butanetriol, 2-ethyl-1,2,3-butanetriol, 2-3.4-hexanetriol, pentamethylene glycol, etc., as alkanetetraols, erythritol, pentaerythritol , Toilet, 1,2,3.4-Pentanetetrol, 2,3,4.5-Hexanetetrol, 2.
5-dimethyl-2,3,4,5-hexanetetrol,
1,2,3.5-pentanetetrol, 3-hexene-1,2,5.6-tetrol, 3-hexyne-1,2,
Ether group-containing aliphatic tetraols such as ether group-containing aliphatic triols such as 5,13-tetrol include triols obtained by adding alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to glycerin, trimethylolpropane, etc. Examples of the ols include tetraols obtained by adding alkylene oxide to erythritol, pentaerythritol, etc., and aromatic triols include triols obtained by adding fullkylene oxide to pyrogallol.

Examples of carboxylic acids include chain or branched dicarboxylic acids such as oxalic acid, malonic acid, co/\hydric acid, glutaric acid, itaconic acid, maleic acid, fumaric acid, adipic acid,
Sepacic acid, dodecanoic acid, methylene glutaric acid, methylmaleic acid, methylsuccinic acid, dodecenylsuccinic acid, etc., as fatty dicarboxylic acids, tetrahydrophthalic acid, hexahydrophthalic acid, 8-methyltetrahydrophthalic acid.

6-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endoinpropylidenetetrahydrophthalic acid, 1,4,5,8,7.7-hexachloro-
Endo-5-norbornene-2,3-dicarboxylic acid (also known as het acid), 1,4,5,8,7.7-hexapromonit-5-norbornene-2,3-dicarboxylic acid, cyclohexane, 1.4 - Dicarboxylic acids, etc., and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid,
Examples include terephthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, and anhydrides thereof.

Next, let's talk about polyurethane. This may be any type such as urethanized oil type, moisture curing type, block type, catalyst curing type, two-component type, etc. Here, we will talk about isocyanate.

Constituent units of aliphatic diisocyanate include ethane,
Propane, butene, thiodiethyl, pentane, β-methylbutane, hexane, ω,ω゛-dipropyl ether, thiodipropylhebutane, 2,2-dimethylpentane, 3
-methoxyhexane, octane, 2,2.4-trimethylpentane, nonane, decane, 3-butoxyhexane,
1.4-butylene glycol dipropyl ether, ω,
Constituent units of aliphatic diisocyanates having a cyclic group such as ω9-undecane, dodecane, thiodiethyl, etc.
ω,ω゛-diisocyanate-1,3-dimethylpenzole, ω,ω゛-diisocyanate)-1,2-dimethylpenzole, ω,ω1-diisocyanate)-1,2-dimethylcyclohexane, ω,ω °−Diisocyaner)−
1,4-cyclohexane, ω, ω°-diisocyanate 1,4-diethylpenzole, ω, ω゛-diisocyanate) -1,4-dimethylnaphthalene, ω, ω°-diisocyanate)-n-propylbiphenyl , etc. Examples of aromatic diisocyanates include tolylene diisocyanate, 3,3′-bitricin-4,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3
．． 3°-dimethyldiphenylmethane-4,4°-diisocyanate, 2,4-tolylene diisocyanate dimer, and other structural units of aromatic incyanate 11
1,3-phenylene, 1,4-phenylene, l-methylpenzole 2,4-11,3-dimethylpenzole2.
4-, 1-ethylpenzole 2.4-51-isopropylopenzole, diisopropylpenzole, etc. Naphthalene isocyanate includes naphthalene 1.4-11.
1-dinaphthyl 2,2°-, biphenyl isocyanates include biphenyl 2.4°-13,3°-dimethylbiphenyl 4,4'-, 2-nitrobiphenyl 4,4
As the constituent units of diisocyanates such as °-1, di, triphenylmethane, diphenylmethane 4,4°-,2
, 2'-dimethyldiphenylmethane 4.4'-, etc., the structural units of tri- and tetraisocyanates are 1 to 4.
Methylpenzole 2,4.8-11.3.5-trimethylpenzole 2,4.6-, naphthalene 1.3.7-,
biphenyl 2,4,4'-, diphenylmethane 2,4,
4°-13-methyldiphenylmethane 4,6,4°-,
Triphenylmethane 4,4°, 4”-, diphenyl 4.
Other incynates include 4'-diisocyanate N-carbamic acid chloride, organophosphorus incyanate,
Examples include fluorinated isocyanate and sulfonyl isocyanate. In addition, in the skeleton of these incyanato,
A suitable molecular group or atomic group may be optionally introduced or modified.

Then react with isocyanate or already
I will talk about the polyols or polyethers that are reacting. These have RCOOH, H, S at the end of the molecule.
, R2O, HCN, )IG, HO)l, RO
M, R(OH)2, NH3, RMH,,
R(+41(2)ri, R302N)12, C5H
& -M An active hydrogen compound such as CL13, that is, a compound having an active (or reactive) hydrogen group such as a hydroxyl group, a carboxyl group, an amino group, or an active methylene group.

For example, as polyester, HOOC-R'・CO
・0・R・0・CD・R゛・C0D)! or HO・R
It is represented by ・0・CO・R゛・CO・0・R・OH, and the units already mentioned can be used as its constituent units. As polyether, HO・R・0・R
・0...R・0・R・OH,
Its structural units include ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, α-methyltrimethylene oxide, 3.3-
Products manufactured by ring-opening polymerization or copolymerization of dimethyltrimethylene oxide, trimethylene oxide, tetrahydrofuran, dioxane, cyclic ether of dioxyamine, etc. (also called polyether glycol or polyoxyalkylene glycol), and other store hydrogen compounds Examples include polyols obtained by hydrogenation of -carbon oxide-olefin copolymers, formaldehyde-modified polymers thereof, phenolaldehyde polycondensates, aldehyde-polyol polycondensates, epoxy resins obtained by polycondensation of bisphenol A and epichlorohydrin, polyols, etc. Polyesteramides obtained from thioethers, dicarboxylic acids and diamines or amine alcohols are used alone or in combination with other polymers.

Above, the structural units of polyacrylic, polyester, and polyurethane have been described. What is ff1W here is that, although not mentioned above, these polymers may have a C=C bond that is active to electron beams in the molecular skeleton, in the side chain, or at the end of the molecule. It is. Regarding the amount of C=C, when introducing it into a polymer, it is difficult to introduce a large amount because it is difficult to synthesize, but conceptually, the more it is possible, the better the stain resistance and hardness. bring improvement.

However, the number of C=C bonds in the molecule may be zero.

Here, we will define the painted metal plate with high hardness, excellent stain resistance, and anti-glare properties, which are the performance targets of the present invention. , mustard, lipstick, tareyon, colored pencils, ink, whiskey, and other daily necessities, or substances commonly used in stain resistance tests, and leave them for 24 hours after applying, such as benzine alcohol, water, and chemicals that dissolve local contaminants. or,
It can be erased with cloth, gauze, etc. without leaving any traces, and even if characters or figures are written with a whiteboard marker, they can be erased with an eraser.

It also includes wiping away the contaminants by some cleaning method even if they are contaminated in the natural environment.

Anti-glare property means a gloss value of 70 or less.

Regarding hardness, the pencil hardness is 9H.

Here, oligo(meth)acrylate, polyhydric alcohol(meth)acrylate, silica-based extender pigment and molecular weight 50
The quantitative relationship of polymers of 00 or more will be discussed.

The above two components are necessary to maintain coating film properties such as excellent stain resistance and hardness. As a result of various studies, it has been found that although this method is effective in improving items (2) and (2), it is rather a negative factor with respect to the target coating film performance of the present invention. Further, although the polymer itself improves paintability, it is a negative factor in terms of coating film performance. This is because if the molecule has a large number of (meth)acryloyl groups that are active to electron beams, for example to the same extent as oligo(meth)acrylates and polyhydric alcohols (meth)acrylates, Although it is not negative,
Although something like this is theoretically possible, it cannot be synthesized in practice. Although the limit is not clear, for example, according to Ford Motor Company's Japanese Patent Publication No. 45-15630, there are about 3 (meth)acryloyl groups per 1000 molecular weight, which means that the double bond equivalent is about 330 or more.

Here, a quantitative relationship is necessary.As a result of various studies, the inventors of the present application found that, for 100 parts by weight of a mixture of components A and B, component C is 0.5 to 20 parts by weight, component D is 1 to 20 parts by weight. The object of the present invention is met if the range is within the range of 50%, including the coating film performance defined above.

Since the E component in the present invention has been explained previously, it will be omitted here.

Above, we have talked about the essential ingredients, but in addition to these, there are also plasticity,
Pigments, monofunctional diluent monomers, oligomers, solvents, etc. can be added.

Examples of plasticizers include dioctyl adipate, dioctyl phthalate, dibutyl phthalate, dioctyl sepacate, triisooctyl trimellitate, tri-2-ethylhexyl trimellitate, pyromellitic acid tetraester, 2,2-diphenolic acid ester, Epoxidized linoleic acid, epoxidized soybean oil lacquer type resin, etc., etc., should be kept to the minimum necessary for imparting workability to the coated board, and when using a flat board, for example, a white board, 0. is preferable.

Pigments include rust prevention, coloring, and others. Solvents include xylene, butyl acetate, methyl cellosolve, ethyl cellosolve, toluene, isopropyl alcohol, butyl alcohol, ethyl acetate, anone, morpholine, methyl ethyl ketone, acetone, These are olefin-based solvents, etc., and one or more of them may be used as a mixed solvent.

In the pre-painted steel sheet of the present invention, the original sheet may be a cut or coiled iron sheet, an electrogalvanized steel sheet, a hot-dip galvanized steel sheet, or a chemical conversion treatment such as chromic acid or phosphoric acid treatment that has already been carried out in the steel sheet manufacturing process. Aluminum plate, stainless steel plate, steel plate, etc. can be used, but considering the balance of surface appearance, cost, corrosion resistance, etc., galvanized steel plate is one of the most suitable. be.

In addition, in the production of the present invention, the metal plate can be pretreated, if necessary, by various known methods. For treated steel plates, it is sufficient to pre-treat only the cleaning treatment, and for those that have not been chemically treated, use a chemical conversion treatment agent 1 depending on the material.
Examples include phosphate treatment agents, chromic acid treatment agents, composite oxide film treatment agents, and heavy metal replacement treatment agents.

Moreover, between this original plate and the layer of the resin composition in the present invention,
It is better to use a primer.

It shows better performance when a primer that has good adhesion to the base plate, has rust prevention properties, and has good adhesion to the top coat resin composition is applied between the base plate and the resin composition of the present invention. .

The composition of this primer may be epoxy, modified epoxy, vinyl phenol, epoxy acrylic, polyester, etc., and the curing method for the primer may be any of heat, electron beam, ultraviolet rays, infrared rays, and ultrafast infrared rays.

The primer can be applied using conventional methods such as natural roll coating, reverse roll coating, curtain flow coating, and spray coating.
The thickness of the coating film is about 1 to 10 g, preferably 2 to 10 g.
It is desirable that the resin be in the 5 elongation position, and appropriate curing conditions are used depending on the respective curing method or resin components.

Furthermore, depending on the coating method, film thickness, and formulation conditions, a solvent may be added to the coating resin composition of the present invention in order to obtain an appropriate coating viscosity; in this case,
It is desirable to scatter the solvent before applying it and irradiating it with an electron beam.

The conditions for scattering this solvent are, for example, 300 m
Baking at very high temperatures near ℃ for long periods of time is different from the hardening conditions, and requires only scattering of the solvent, for example:
A drying hot air temperature of 150°C and a plate temperature of 120°C or less are sufficient.

Alternatively, if the setting is sufficient, the solvent may be scattered by leaving it alone, and heating may not be necessary.

To explain the electron beam irradiation method after coating the resin composition of the present invention, any known irradiation device can be used, such as a DC high voltage electron gun or an electron beam irradiation device with an acceleration mechanism. Currently, devices with capacities of accelerating voltages ranging from 100 kilovolts to several megavolts have been developed, but in the present invention, devices with accelerating voltages of several hundred kilovolts are sufficient. Regarding the output current.

From the viewpoint of high-speed productivity, a large current is particularly desirable, and a current of 100 milliamperes/one accelerating tube or more is desirable.

Regarding the appropriate irradiation dose in the present invention, approximately 0.5 to 1
A rough guideline is around 0 Mrad, but 1 to 5 Mrad.
Although it depends on the resin composition, it shows good performance.

In general, when curing a coating film by irradiating electron beams, oxygen is known to act as a polymerization inhibitor, so it is preferable to block this out, and to replace the atmosphere with an inert gas, etc. Among these, it is desirable to perform electron beam irradiation, especially when the surface hardness, stain resistance/chemical resistance, water resistance, and weather resistance of the coating film are important. 1!
have righteousness

Examples of the inert gas include nitrogen gas, carbon dioxide, argon, helium, krypton, etc., but the oxygen concentration during irradiation is approximately 1% or less, preferably 0.
．． A condition of about 1% or less is sufficient.

A protective film may be bonded to the pre-coated steel sheet of the present invention under pressure and heat in order to prevent the coating film from being scratched during loading, transporting, or processing of the coated product by the user. Examples of protective films include polyethylene,
Examples include vinyl chloride, polypropylene, polyester, and acrylic.

There are many uses for the pre-coated steel sheet in the present invention, such as whiteboards, outer panels of home appliances,
Or, it is hard and scratch resistant because it is cleaned with a brush by a cleaning vehicle using a wet or dry method, and contaminants such as oil smoke and dust from automobiles can be easily cleaned, and it is also required to have anti-glare properties. It is particularly useful as a tunnel interior material (line-of-sight guide reflector).

Example I A, an oligomer (acryloyl group 155) in which the condensation molar ratio of phthalic acid, trimethylolpropane, and acrylic acid is approximately 1:2:4.

B. Trimethylolpropane trimethacrylate (
Copolymerization mole of acryloyl group equivalent (11O), C, silica-based extender pigment (Fuji Davison Chemical Co., Ltd. "Syroid 308" oil absorption 170g/100g), D, ethyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, acrylic acid The ratio is 70:2
Acrylic copolymer consisting of 4:3:3 (number average molecular weight: 20,000).

E1 spherical glass powder (spherical diameter 18 l), and the overlap ratio of A, B, C, D, titanium white and E is 18.8: 18.8: 1.8: 4.4:
30% xylene (vs. the former) was added to the system consisting of 44.2710 to prepare a paint. This paint system was applied to a 5tlS3Q4 stainless steel plate (1500 x 8 (t.

Xo, 6 intestinal layers).

The painted surface was beautiful, and there was hardly any dust visible.

This coated plate was cured by scattering the solvent and electron beam under conditions such that the plate temperature was 80°C with hot air at 150°C (furnace time: about 50 seconds).

Curing conditions: Voltage 300KV, current 25mA/Goes
The dose was 3 Mrad, the oxygen concentration during irradiation was 150 ppm (in a nitrogen stream), and the cured coated plate was subjected to the coating film tests for stain resistance, hardness, etc. as described above.

(Stain Resistance) When magic ink (red, blue), curry, mustard, lipstick, crayon, colored pencil, ink was applied to a painted board and wiped with gauze soaked in ethanol after 24 hours, it was easily wiped off without any traces. .

Also, even if I wrote on it with a Pilot ■ whiteboard marker, I could completely erase it with an eraser.

Furthermore, assuming that there is oil smoke from automobiles that is a contaminant in the tunnel, it is easy to mix 10 g of carbon black with 20 g of olive oil, apply this, and wipe it 10 times with gauze soaked in 0.3% detergent water after one month. It was wiped away without a trace.

(Pencil hardness) 9H (gloss) 51 (JIS standard applicable film thickness) 50 l (scratch resistance) Polypropylene 1 m (1 am φ, same as the cleaning brush installed in the tunnel cleaning vehicle) 5 x 5
A 5 am3 copper piece was sprinkled on the coated plate without any gaps, and the plate was rubbed with the copper piece 1000 times while dripping 0.3% soapy water onto the coated plate, but no scratches were observed.

Example 2 An oligoacrylate in which the condensation molar ratio of A, adipic acid, pentaerythritol, and acrylic acid is approximately 1:2:4 (
Acryloyl group equivalent: 122), B, diethylene glycol dimethacrylate (acryloyl group equivalent: 121), C, silica-based extender pigment (Mizukashiru MP manufactured by Mizusawa Chemical Industry)
-8, oil absorption 280 g (7100 g), D, polyester (molecular weight 15,000) consisting of terephthalic acid, sebacic acid, ethylene glycol) LA condensation molar ratio of approximately 3:7:10, E, @ male glass powder ( (diameter 13 l, average length 50 l),
A paint was prepared using components A, B, C, D, and E under exactly the same conditions as in Example 1, and after painting, the coated board was irradiated with an electron beam.

(Stain resistance) The carbon black/oil mixture in Example 1 was applied to the coated plate, and after one month, the mixture was stained with gauze soaked with 0.3% detergent water.
When I wiped it 0 times, it was wiped away without a trace.

(Pencil hardness) 9H (Gloss) 65 (Film thickness) 45JL (Scratch resistance) Scratch resistance was tested in the same manner as in Example 1, and the results were exactly the same.

Comparative Example 1 A paint with only component E removed from the composition in Example 1,
A paint was prepared under exactly the same conditions as in Example 1, and after painting, the coated plate was irradiated with an electron beam.

(Stain Resistance) A test was conducted in the same manner as in Example 2, and the results were the same.

(Pencil hardness) 8H (Gloss) 65 (Film thickness) 48 (Scratch resistance) When scratch resistance was tested in the same manner as in Example 1, it was found to be 7
There were five scratches several centimeters long on the painted board of X15c■2.

Effects of the Invention As described above, according to the present invention, an electron beam curable coating material A: an oligo(meth)acryloyl group containing two or more (meth)acryloyl groups in one molecule and a (meth)acryloyl group equivalent of 500 or less meth)acrylate, B: polyhydric alcohol (meth)acrylate containing two or more (meth)acryloyl groups in one molecule and having a (meth)acryloyl group equivalent of 150 or less, C: silica-based extender pigment, D: min-IHooo or more novolimer.

E-niglass powder is hard (pencil hardness: 9H), allows easy removal of contaminants, and provides anti-glare properties. This makes it possible to obtain coated steel sheets that did not previously exist. In the present invention, the lowest coating film gloss value can be produced up to about 5th place.

Claims (2)

[Claims] (1) A: 90 to 10 parts by weight of oligo(meth)acrylate containing two or more (meth)acryloyl groups in one molecule and having a (meth)acryloyl group equivalent of 500 or less; B: (meth)acrylate containing two or more (meth)acryloyl groups in one molecule; ) 90 to 10 parts by weight of a polyhydric alcohol (meth)acrylate containing two or more acryloyl groups and having a (meth)acryloyl group equivalent of 150 or less, and 100 parts by weight of a mixture of components A and B, C: 0.5 to 20 parts by weight of silica-based extender pigment, D: 1 to 20 parts by weight of polymer having a molecular weight of 5000 or more, and A, B
, C, and D components, and coated with an electron beam curable paint film containing 1 to 40 parts by weight of E: glass powder as an essential component, with high hardness, stain resistance, and Painted metal plate with excellent anti-glare properties. (2) A: 90 to 10 parts by weight of oligo(meth)acrylate containing two or more (meth)acryloyl groups in one molecule and having a (meth)acryloyl group equivalent of 500 or less; B: ) 90 to 10 parts by weight of a polyhydric alcohol (meth)acrylate containing two or more acryloyl groups and having a (meth)acryloyl group equivalent of 150 or less, and 100 parts by weight of a mixture of components A and B, C: 0.5 to 20 parts by weight of silica-based extender pigment, D: 1 to 20 parts by weight of polymer having a molecular weight of 5000 or more, and A, B
A paint containing 1 to 40 parts by weight of E: glass powder as an essential component per 100 parts by weight of the mixture of components , C, and D is applied to the object to be coated, and this is heated in an inert gas with an oxygen concentration of 1% or less. A coated metal plate with high hardness, excellent stain resistance, and anti-glare properties, which is cured by electron beams.