JPH09137081A - Emulsion coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above composition low in pollution and toxicity, high in solid content, improved in coating performance, excellent in preservation stability, wearing resistance, surface smoothness, heat resistance, chemical resistance, etc. SOLUTION: This emulsion coating material composition is obtained by blending 100pts. by wt. of a composition composed of the sum of (A) 10-70 pts.wt. of a mono- or a polypentaerythritol (meth)acrylate of the formula [at least three of X11 to X14 , Xm2 and Xm3 are CH2 =CR-COO (R is H or methyl) and the rest are OH; (n) is 0-4], (B) 5-50pts.wt. of a urethane poly (meth)acrylate compound containing at least two radically polymerizable unsaturated double bonds, (C) 0-50pts. by wt. of a radically polymerizable monomer or oligomer, (D) 0.1-10pts. by wt. of a photopolymerization initiator and (E) 2-24pts. by wt. of a radically polymerizable reactive surfactant with (F) 0-30pts. by wt. of UV rays absorber, (G) 0-5pts. by wt. of a hindered amine-based light stabilizer and (H) 10-900pts. by wt. of water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in abrasion resistance, surface smoothness, heat resistance, chemical resistance, water resistance, weather resistance and adhesion to a substrate by irradiation with active energy rays. The present invention relates to an emulsion coating material composition that forms a crosslinked cured coating.

[0002]

2. Description of the Related Art Synthetic resin moldings made of polymethylmethacrylate resin, polymethacrylamide resin, polycarbonate resin, polystyrene resin, AS resin, etc. are lightweight, have excellent impact resistance, and have good transparency. , As a plastic material for automobiles, headlights,
It is also used for glazing and covers for instruments. However, since the surface of these synthetic resin molded products lacks abrasion resistance, the surface of the molded product is easily damaged by contact with other hard objects, friction, scratching, etc. There is a strong demand for improved sex.

[0003] Various improvements have been hitherto made to improve the abrasion resistance of synthetic resin molded products. For example, a coating material made of a resin composition such as a silicone-based or melamine-based resin is applied to the surface of the synthetic resin molded product and heated. A method for forming a crosslinked film to improve wear resistance is proposed in Japanese Patent Laid-Open No. 122840/56. However, although abrasion resistance is improved to some extent by these methods, durability against heat shock, hot water, etc. and chemical resistance are insufficient, and there is also a problem in productivity because curing takes time. .

On the other hand, the active energy ray curable resin is
It is used in a wide range of fields because of its good productivity, low-temperature curability, low solvent pollution, and low pollution caused by its low solvent content. However, although these resins are solvent-free and low-solvent, when these resins are used as paints, a large amount of solvent is added for the purpose of adjusting viscosity.

In recent years, regulations on volatile organic solvents have been put into practice in Europe and the United States, and resin compositions using organic solvents have been forced to switch to solventless or nonsolvent type. Since environmental protection based on these regulations is carried out on a global scale, it is inevitable that the regulations will be tightened in Japan soon, and there is a demand for urgent development of alternatives to solvent-based resins. In addition, the use of volatile organic solvents poses a problem due to the large impact on the human body at the present time when improvements in the working environment are being further improved. Solventization and nonsolventization are required.

[0006]

Therefore, an emulsion resin composition using water instead of an organic solvent has been widely studied because it is easy to adjust the viscosity even at a high solid content, and is used as a substitute for a solvent resin. It has become possible to be.
However, in general, the resin required for expressing abrasion resistance, water resistance, etc. is hydrophobic, and it is not possible to obtain a stable emulsion resin composition as it is even by simply emulsifying in water. Since it is possible, the addition of a surfactant is being considered. However, since the added surfactant exists in the cured film in a free state, the weather resistance of the cured film,
There is a problem in that the water resistance is lowered.

The object of the present invention is to realize low pollution and toxicity, good coatability with high solid content, and excellent storage stability.
Emulsion coating material capable of forming a crosslinked cured coating on a substrate by irradiation with active energy rays, which has good abrasion resistance, surface smoothness, heat resistance, chemical resistance, water resistance, weather resistance, and adhesion to the substrate. To provide a composition.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that mono- or polypentaerythritol having a (meth) acryloyl group and urethane poly (meth) acrylate having a radical-polymerizable unsaturated double bond. Compound, and a resin composition containing a photopolymerization initiator in a specific ratio, the emulsion coating composition obtained by adding a radical polymerization reactive surfactant and water and forced emulsification is applied to a substrate, and then dried. Then, it was found that a cured coating having excellent wear resistance, weather resistance, water resistance, heat resistance, and chemical resistance can be obtained by curing by irradiation with active energy rays, and the present invention has been completed.

That is, the present invention includes (A) 10 to 70 parts by weight of at least one monomer selected from the (meth) acrylates of mono- or polypentaerythritol represented by the following general formula [I]:

Embedded image (In the formula, among X ₁₁ , X ₁₂ , X ₁₃ , X _m2 , X _m3 , and X ₁₄ ,
At least three are CH ₂ = CR-COO- group (R is a hydrogen atom or a methyl group), the remainder -OH radical, n is an integer of 0-4. (B) 5 to 50 parts by weight of a urethane poly (meth) acrylate compound having at least two radically polymerizable unsaturated double bonds in one molecule, and (C) at least one kind of radically polymerizable monomer or oligomer 0 To 50 parts by weight, (D) 0.1 to 10 parts by weight of a photopolymerization initiator, and (E) 2 to 24 parts by weight of a radical polymerization reactive surfactant, and the total amount of components (A) to (E). To 0 to 30 parts by weight of the ultraviolet absorber (F) with respect to the composition of 100 parts by weight,
(G) 0 to 5 parts by weight of hindered amine light stabilizer,
(H) An emulsion coating material composition containing 10 to 900 parts by weight of water. In addition, in this invention, (meth) acrylate shall mean an acrylate and a methacrylate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The poly (meth) acrylate of mono- or polypentaerythritol, which is the component (A) in the composition of the present invention, exhibits good polymerization activity upon irradiation with active energy rays and has a high crosslinking density. Since a polymer having excellent abrasion resistance is produced, a crosslinked coating having excellent abrasion resistance can be formed on the surface of the base material. (A)
Specific examples of the component include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol Octa (meth) acrylate or the like is used. Moreover, these are used individually or in mixture of 2 or more types.

The content of the component (A) is 10 to 70 parts by weight, preferably 25 to 50 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). If the content of the component (A) is less than 10 parts by weight, a cured coating having sufficient abrasion resistance cannot be obtained, and if it exceeds 70 parts by weight, cracks easily occur in the cured coating, and the heat resistance of the cured coating is high. Sex decreases.

The urethane poly (meth) acrylate compound having at least two radically polymerizable unsaturated double bonds in one molecule of the component (B) is a cured film having toughness, flexibility, heat resistance and water resistance. Which is a component for improving the properties, and a urethanization reaction product of a (meth) acrylate having a hydroxyl group and a polyisocyanate compound having two or more isocyanate groups in the molecule, or two or more isocyanate groups in the molecule. A urethanization reaction product obtained by reacting a polyisocyanate compound with a polyol, polyester, or polyamide diol to synthesize an adduct and then adding a (meth) acrylate having a hydroxyl group to the remaining isocyanate group is used. , Especially the latter urethane poly (meth) acrylate compound is the toughness and flexibility of the cured film Preferable be further improved. Further, the urethane poly (meth) acrylate compound used preferably has a molecular weight of 1,000 to 5,000.

As the polyisocyanate compound used for the synthesis of the urethane poly (meth) acrylate compound, tolylene diisocyanate, ethylene diisocyanate,
1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis ( Cyclohexyl) isocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate,
Examples thereof include polyisocyanate monomers such as tetramethylene diisocyanate and dimer acid diisocyanate, burettes and trimers thereof, and adducts thereof with various polyols.

The polyol used for the synthesis of the adduct is not particularly limited, but examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, and glycerin. Examples thereof include alkyl polyols, polyester polyols such as these polyether polyols, polyester polyols synthesized from polyhydric alcohols and polybasic acids, and polyester polyols such as polycaprolactone polyols.

Specific examples of the urethane poly (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
Addition reaction products of (meth) acrylic acid with monoepoxy compounds such as hydroxybutyl (meth) acrylate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl methacrylate, and mono (meth) acrylic acid ester of polyethylene glycol polypropylene glycol , Mono (meth) acrylic acid esters of polycaprolactone diol, and the like.

A urethane poly (meth) acrylate compound comprising polyisocyanate, various diols, and a (meth) acrylate having a hydroxyl group has almost the same isocyanate group and hydroxyl group in the presence of a tin catalyst such as di-n-butyltin dilaurate. 60-70 ℃
It is synthesized by heating for several hours.

The content of the component (B) is 5 to 50 parts by weight, more preferably 15 to 35 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). If the amount of this component (B) is less than 5 parts by weight, a cured film having sufficient toughness cannot be obtained, and the curability in an air atmosphere becomes poor. If it exceeds 50 parts by weight, a cured film is obtained. Wear resistance of is reduced.

The radical-polymerizable monomer or oligomer of the component (C) is an ester type (meta) obtained by a condensation reaction of an aliphatic, alicyclic or aromatic mono- or polyalcohol with (meth) acrylic acid. ) Acrylate (a-1), epoxy poly (meth) acrylate obtained by ring-opening reaction of a compound having two or more epoxy groups in the molecule with (meth) acrylic acid, and saturated or unsaturated polyvalent carboxylic acid Acid, polyhydric alcohol and (meth)
(Meth) acryloyl-functional monomers or oligomers such as polyester poly (meth) acrylate obtained by condensation reaction of acrylic acid, styrene, chlorostyrene,
Examples thereof include vinyl compounds such as bromostyrene, dibromostyrene and divinylbenzene, and (meth) allyl compounds such as diethylene glycol bisallyl carbonate and diallyl phthalate diallylbiphenylate.

Above all, since it shows good polymerization activity upon irradiation with active energy rays and can improve the toughness and heat resistance of the cured film without impairing abrasion resistance, the following general formula [II] or [(Meth) acryloyloxyalkyl] (iso) cyanurate represented by [III] is preferable.

[0020]

Embedded image(Where X₁, X_TwoAnd X_ThreeIs a (meth) acryloyl group,
Indicates a hydrogen atom or an alkyl group, and
At least two are (meth) acryloyl groups, R ₁, R_Two
And R_ThreeRepresents an oxyalkylene group having 1 to 4 carbon atoms
You. )

As the poly [(meth) acryloyloxyalkyl] (iso) cyanurate, di (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, di (2- Acryloyloxypropyl)
2-hydroxypropyl isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, di (2-acryloyloxyethyl) -2-hydroxyethyl cyanurate, tris (2-acryloyloxyethyl) cyanurate, di (2-acryloyl) Oxypropyl) -2-hydroxypropyl cyanurate,
Examples include tris (2-acryloyloxypropyl) cyanurate and the like. These may be used alone or in combination of two or more.

The amount of the component (C) is 0 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). This (C) component is 5
If it exceeds 0 parts by weight, the abrasion resistance of the cured coating is reduced.

Examples of the photopolymerization initiator of the component (D) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal and 2,2-diethoxy. Acetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, 2-hydroxy-2-
Carbonyl compounds such as methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, 2,
Examples thereof include acylphosphine oxide such as 4,6-trimethylbenzoyldiphenylphosphine. Particularly, benzoin isopropyl ether, benzophenone, benzyl dimethyl ketal, and methylphenyl glyoxylate are more preferable because they have good air curability and deep curability. These photopolymerization initiators are used alone or in a mixture of two or more.

The content of the component (D) is 0.1 to 100 parts by weight of the total amount of the components (A) to (E).
It is 10 parts by weight, preferably 1 to 5 parts by weight. If the amount of this component (C) is less than 0.1 parts by weight, the curability will be insufficient, and if it exceeds 10 parts by weight, the cured coating will be colored.

The radical polymerization reactive surfactant as the component (E) is an essential component for obtaining a uniform emulsion. Such a radical polymerization reactive surfactant is one having a radical-reactive unsaturated bond in the molecule, specifically, a (meth) acrylate-based, allyl-based, maleic acid-based, itaconic acid-based surfactant or the like. Agents.

Specific examples of the component (E) include sulfoethyl methacrylate sodium salt, sulfoethyl methacrylate ammonium salt, allyl group-containing polyoxyethylene nonylphenyl ether sulfonate, polyoxyethylene lauryl ether maleate and polyoxyethylene. Examples thereof include lauryl ether methacrylic acid ester, polyoxyethylene nonylphenyl ether acrylic acid ester, and allyl group-containing polyoxyethylene nonylphenyl ether. The component (E) can be used alone or in a mixture of two or more.

Among them, from the viewpoint of high emulsifying ability for radically polymerizable monomers or oligomers and good emulsion stability, the above general formula [IV]
And a radical polymerization reactive surfactant represented by the general formula [V] are particularly preferable.

[0028]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
20 alkyl groups, p shows the integer of 8-40. )

[0029]

Embedded image (In the formula, R ₁ and R ₄ are a hydrogen atom or an alkyl group having 1 to 25 carbon atoms and may be the same or different,
R ₂ , R ₃ , R ₅ , and R ₆ are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, benzyl groups, and styrene groups, which may be the same or different, and R ₇ is a hydrogen atom or methyl. Indicates a group. q represents an integer of 5 to 15 and Y represents an alkali metal atom or ammonium. )

Among the compounds represented by the general formulas [IV] and [V], polyoxyethylene nonylphenyl ether methacrylate, ammonium sulfate ester ester of nonylphenol formaldehyde condensate obtained by addition polymerization of 10 mol of ethylene oxide, and ethylene oxide are used. Particularly preferred is ester sulfate sodium salt of a styrenated octylphenol formaldehyde condensate obtained by addition polymerization of 8 mol.

The content of the component (E) is 2 to 24 parts by weight, more preferably 4 to 16 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). If the amount of the component (E) is less than 2 parts by weight, a stable emulsion cannot be obtained, and if it exceeds 24 parts by weight, the water resistance and weather resistance of the cured coating are poor and the adhesion is lowered, or cracks are generated. Performance such as yellowing is reduced.

When the ultraviolet absorber of the component (F) is added to the coating material composition of the present invention, the obtained cured coating absorbs ultraviolet rays and protects the substrate and the inside of the substrate from ultraviolet rays. It is a component that can. Therefore, when the weather resistance of the substrate is poor, when high weather resistance is required,
The component (F) can be added for the purpose of adding the component (F) and protecting the substrate from ultraviolet rays. The component (F) used in the present invention is not particularly limited as long as it can be uniformly dissolved in the coating material composition of the present invention.
From the viewpoint of solubility, a UV absorber having a compound derived from a benzophenone type, a benzotriazole type, a phenyl salicylate type, or a phenyl benzoate type and having a maximum absorption wavelength in the range of 240 to 380 nm is preferable. Further, when it is necessary to include a large amount in the coating material composition of the present invention, a benzophenone-based ultraviolet absorber is particularly preferable, and from the viewpoint of preventing yellowing of a plastic substrate such as polycarbonate, a benzotriazole-based ultraviolet absorber. UV absorbers are preferred. Therefore, it is particularly preferable to use these two types in combination.

Specific examples of the component (F) include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone and 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-
Dihydroxy-4-methoxybenzophenone, 2,2 ′
-Dihydroxy-4,4'-dimethoxybenzophenone, phenyl salicylate, p-tert-butylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate, 3-hydroxyphenylbenzoate, phenylene-1, 3-dibenzoate, 2- (2-hydroxy-5'-methylphenyl) benzotriazole, 2- (2-hydroxy-5-ter
t-Butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4)
-Octyloxyphenyl) benzotriazole and the like.

Of these, benzophenone-based 2-hydroxy-4-octoxybenzophenone and 2,
4-Dihydroxybenzophenone and benzotriazole-based 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole are particularly preferable. Also,
The component (F) can be used alone or as a mixture of two or more kinds, but in order to express various performances, it is more preferable to use these in combination of two or more kinds.

The content of the component (F) is 0 to 30 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). (F) component is 30
When it exceeds the weight part, the curability of the coating material composition becomes insufficient, and the toughness, heat resistance and abrasion resistance of the cured coating deteriorate.

The component (G), a hindered amine light stabilizer, is a component that improves the weather resistance of the cured coating. (G)
Specific examples of the components include bis (1,2,2,6,6,-
Pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-tert-butyl-4-)
Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2 , 6,6-Tetramethylpiperidine polycondensate, 1- [2- [3- (3,5-di-
tert-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-te
rt-Butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine,
(Mixed 1,2,2,6,6-pentamethyl-4-
Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6
6-pentamethyl-4-piperidyl / β, β, β ′,
β ',-tetramethyl-3,9- [2,4,8,10-
Tetraoxaspiro (5,5) undecane] diethyl]
-1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like can be mentioned. Of these, bis (1,2,2,6,6-) pentamethyl-4-piperidyl) sebacate, bis (2,2,2), etc., have good weather resistance.
2,6,6-Tetramethyl-4-piperidyl) sebacate is particularly preferred.

The content of the component (G) is 0 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). When the amount of the component (G) exceeds 5 parts by weight, the curability of the coating material composition becomes insufficient, and the toughness, heat resistance and abrasion resistance of the cured coating deteriorate.

The water as the component (H) is added for the purpose of reducing the viscosity of the composition comprising the components (A) to (G) and facilitating the coating. The water as the component (H) is mixed in an amount of 10 to 900 parts by weight, preferably 40 to 300 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (E). If the blending amount is less than 10 parts by weight, the viscosity is too high and it is difficult to apply. If it exceeds 900 parts by weight, it is not uniformly applied when applied to the base material and a smooth continuous film is formed. I can't get it.

The emulsion coating material composition of the present invention comprises:
If necessary, additives such as antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, defoamers, thickeners, anti-settling agents, antistatic agents, anti-fog agents, etc. are further added. May be.

In obtaining the emulsion coating material composition of the present invention, a composition comprising components (A) to (G) is added to the composition.
The water as the component (H) is emulsified by a method using a high speed disperser, a double cylinder homogenizer, an ultrasonic homogenizer, a blender, a mixer, or the like, or a method of film emulsification to obtain an emulsion.

The emulsion coating composition of the present invention can be applied to a substrate by brush coating, spray coating, dip coating, spin coating, curtain coating, etc., but the coating workability, the smoothness of the coating, and the uniform coating are obtained. From the viewpoints of properties, adhesion to the substrate, etc., it is preferable to appropriately adjust the coating material composition to have a viscosity suitable for each coating method, and apply the coating composition by a method according to the shape of the substrate. Further, in applying to the base material, a uniform coating film is formed on the base material, and it is quickly dried, and since the adhesion of the emulsion coating material composition is further improved, the base material is heated. It is preferable to set.

The emulsion coating composition of the present invention is applied to a substrate and then crosslinked by irradiation with active energy rays such as ultraviolet rays and electron beams to form a cured coating film. When curing by irradiation with active energy rays, the emulsion coating material composition has a cured coating film thickness of 1 to 50 μm on a substrate.
m, preferably 3 to 20 μm, for example, using a high pressure mercury lamp, a metal halide lamp, or the like,
Amount of ultraviolet light of wavelength 100-400 nm is 1000-50
Irradiation is performed so as to be 00 mJ / cm ² . The atmosphere for irradiation with active energy rays may be air, nitrogen,
It may be in an inert gas such as argon.

The base material to which the emulsion coating composition of the present invention is applied includes various base materials such as synthetic resin, metal, wood and paper, and the purpose of application is also waterproof, scratchproof, rustproof. ,
It can be used for various purposes such as surface protection such as antifouling and antiseptic, imparting functionality such as antistatic and antifogging, and improving appearance such as coloring, polishing and matting.

The emulsion coating material composition of the present invention is used for modifying the surface of various synthetic resin molded articles which are required to have abrasion resistance. Examples of the resin as the base material include polymethylmethacrylate resin, polycarbonate resin, polyester resin, poly (polyester) carbonate resin,
Examples thereof include polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, polyallyl diglycol carbonate resin, and the like, which may have a film shape, a sheet shape, a plate shape, or any other shape. . Among them, polymethylmethacrylate resin, polycarbonate resin, polystyrene resin,
Since the polymethacrylimide resin is strongly required to have abrasion resistance in order to maintain its excellent transparency, it is particularly preferable to use the emulsion coating material composition of the present invention.

[0045]

The present invention will be described below in more detail with reference to examples. In the examples, “parts” means “parts by weight”.
The evaluation items were evaluated according to the following method.

(1) Emulsion stability 100 ml of the emulsion immediately after re-emulsification was put in a test tube with a scale, and the emulsified state and the visual appearance were evaluated. ◯: It does not separate at all even after 3 months, or even if it separates, it easily returns to an emulsified state by shaking the test tube by hand to mix it. ×: Separates within 3 months and removes the test tube by hand What does not re-emulsify even if shaken and mixed

(2) Appearance of cured film Immediately after coating the composition, the appearance of the film after curing is visually evaluated, and those having a smooth surface and no defects such as pinholes and cissing are regarded as good, and other than that, the appearance is excellent. Described the problem.

(3) Abrasion resistance # 0000 steel wool was attached to the tip of a cylinder having a diameter of 25 mm and brought into contact with a horizontally placed sample surface to
After reciprocating abrasion for 50 rotations under a load of Kg, the diffuse transmittance (haze value) was measured, and the abrasion resistance was determined according to the following criteria. ◯: Increased haze value 0 to 0.5 (almost no scratch or slight scratch) Δ: Increased haze value 0.5 to 3.0 (slightly scratched) ×: Increased haze value 3 0.0 or more (severely scratched)

(4) Adhesiveness Cross-cuts reaching the surface of the substrate are placed at 1 mm intervals in the cured film to make 100 1 mm ² squares, on which adhesive tape is adhered and rapidly peeled off, and the peeled squares are cut. I counted the number. ◯: No peeling Δ: 1 to 25 peeled ×: 26 or more peeled

(5) Heat resistance The coated plate sample was heated with a hot air dryer at 120 ° C. for 24 hours, and the appearance change of the cured film was visually observed. ◯: No change x: Crack occurred

(6) Water resistance The coated plate sample coated with the coating material composition was heated in a water bath at 80 ° C. for 2 hours and 10 hours, and the appearance change of the cured film was visually observed, and the appearance and cracks were visually observed. And the adhesion was tested. -Crack: According to the evaluation of (5). Adhesion: According to the evaluation of (4).

(7) Weather resistance A sunshine carbon weather ometer (manufactured by Suga Test Instruments Co., Ltd., WEL-SUN-HC-B type) using a weather resistance tester, a black panel temperature of 63 ± 3 ° C., irradiation rainfall for 12 minutes,
Exposure tests were carried out for 300 hours and 1000 hours in a 48 minute irradiation cycle.・ Appearance: ΔYI value (ΔYI =
YI (after weathering test) -YI (initial) was measured. ◯: 0 ≦ ΔYI <1 Δ: 1 ≦ ΔYI <3 ×: 3 ≦ ΔYI ・ Crack: According to the evaluation of (5). Adhesion: According to the evaluation of (4).

(8) Environmental pollution resistance: No solvent was generated in the film forming process, and some were evaluated as x.

[Examples 1, 3 to 7, 9 to 13, Comparative Examples 1, 3, 5 to 8, 12 to 14] Coating materials using the ultrasonic homogenizer with the components and compounding ratios shown in Tables 1 to 4. A composition was prepared. This composition is preliminarily dried in a dryer at 80 ° C. for 30 minutes.
3 mm thick polycarbonate resin plate (Made by General Electric Co., trade name: Lexan L)
S-II) was spray-coated so that the cured film had a thickness of 8 μm. After evaporating the water content by heating, a high-pressure mercury lamp was used in the air to irradiate with ultraviolet rays having a wavelength of 340 to 380 nm and an integrated light amount of 1000 mJ / cm ² , to obtain a cured film. The evaluation results of the obtained coating films are shown in Tables 1 to 4.

[Examples 2, 8, 14 and Comparative Examples 2, 4, 9
~ 11] A coating material composition was prepared using an ultrasonic homogenizer with the components and compounding ratios shown in Tables 1 to 4. This composition was applied to a polymethylmethacrylate resin plate (made by Mitsubishi Rayon Co., Ltd .; trade name: Acrypet VH) having a thickness of 3 mm, which had been heated in advance at 80 ° C. for 30 minutes with a drier. It was spray-coated so as to have a thickness of 8 μm. After evaporating the water content by heating, a high pressure mercury lamp is used in the air, and the accumulated light quantity of wavelength 340 to 380 nm is 1000 m.
Ultraviolet rays of J / cm ² were irradiated to obtain a cured film. The evaluation results of the obtained coating films are shown in Tables 1 to 4.

[Comparative Example 15] Isobutanol / normal butyl acetate / butyl cellosolve / cellosolve acetate 1 was used as a solvent for a coating material composition having the components and compounding ratios shown in Table 4.
A 3 mm thick polycarbonate resin plate (manufactured by GE; brand name: Lexan LS) which was completely dissolved in a mixture having a ratio of 40/50/20/10 and previously heated in a dryer at 80 ° C. for 30 minutes -II) was spray-coated so that the cured film had a thickness of 8 μm. After evaporating the solvent by heating, use a high pressure mercury lamp in air to
Ultraviolet rays with an integrated light amount of 0 to 380 nm and 1000 mJ / cm ² were irradiated to obtain a cured film. Table 4 shows the evaluation results of the obtained coating films.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

The symbols in Tables 1 and 2 have the following meanings. DPHA: dipentaerythritol hexaacrylate UA1: 2 mol of dicyclohexylmethane diisocyanate, 1 mol of nonabutylene glycol, 2 mol of 2-hydroxyethyl acrylate Urethane acrylate having a molecular weight of 2500 UA2: 2 mol of isophorone diisocyanate, 2,2 '
-(Hydroxyethyloxyphenyl) propane urethane acrylate having a molecular weight of 2200 synthesized from 1 mol of 2-hydroxypropyl acrylate TAIC: tris (2-acryloyloxyethyl) isocyanurate DAIC: bis (2-acryloyloxyethyl) -2
-Hydroxyethyl-isocyanurate BNP: Benzophenone MPG: Methylphenylglyoxylate MS-60: Bis (polyoxyethylene triphenyl ether) methacrylated ammonium sulfate salt (manufactured by Nippon Emulsifier Co., Ltd., trade name Antox MS-60) RMA: Polyoxyethylene nonyl phenyl ether acrylate (Nippon Emulsifier Co., Ltd., trade name RMA-50)
6) EM50: polyoxyethylene nonylphenyl ether EO addition 50 moles HBPB: 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole DHBP: 2,4-dihydroxybenzophenone BTMS: bis (2,2,6,6) 6-tetramethyl-4-
Piperidyl) sebacate BPMS: bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate PC: polycarbonate resin PMMA: polymethylmethacrylate resin

The emulsion coating material composition of the present invention comprises
It is possible to form a crosslinked cured coating having excellent abrasion resistance, heat resistance, and chemical resistance on the surface of the base material by irradiation with active energy rays, and also having excellent water resistance, weather resistance, and adhesion to the base material.
In addition, since it does not require the use of a solvent, it is a low-pollution and low-toxicity, does not have an adverse effect on the environment, and has excellent storage stability, and a cross-linking cured film with good coatability even at high solid content. Can be formed.

Claims (3)

[Claims] 1. (A) 10 to 70 parts by weight of at least one monomer selected from the (meth) acrylates of mono- or polypentaerythritol represented by the following general formula [I]: (In the formula, among X ₁₁ , X ₁₂ , X ₁₃ , X _m2 , X _m3 , and X ₁₄ ,
At least three are CH ₂ = CR-COO- group (R is a hydrogen atom or a methyl group), the remainder -OH radical, n is an integer of 0-4. (B) 5 to 50 parts by weight of a urethane poly (meth) acrylate compound having at least two radically polymerizable unsaturated double bonds in one molecule, and (C) at least one kind of radically polymerizable monomer or oligomer 0 To 50 parts by weight, (D) 0.1 to 10 parts by weight of a photopolymerization initiator, and (E) 2 to 24 parts by weight of a radical polymerization reactive surfactant, and the total amount of components (A) to (E). To 0 to 30 parts by weight of the ultraviolet absorber (F) with respect to the composition of 100 parts by weight,
(G) 0 to 5 parts by weight of hindered amine light stabilizer,
(H) An emulsion coating material composition containing 10 to 900 parts by weight of water. 2. The emulsion coating material according to claim 1, wherein the component (C) is poly [(meth) acryloyloxyalkyl] (iso) cyanurate represented by the general formula [II] or the general formula [III]. Composition. Embedded image (In the formula, X ₁ , X ₂ and X ₃ are (meth) acryloyl groups,
A hydrogen atom or an alkyl group, and at least two of them are (meth) acryloyl groups, and R ₁ and R ₂
And R ₃ represent an oxyalkylene group having 1 to 4 carbon atoms. ) 3. The component (E) is a polyoxyethylene alkylphenyl ether (meth) acrylate represented by the general formula [IV] and / or bis (polyoxyethylene polycyclic phenyl represented by the general formula [V]. The emulsion coating material composition according to claim 1, which is an ether) (meth) acrylated sulfate ester salt. Embedded image (In the formula, R ₄ is a hydrogen atom or a methyl group, R ₅ is a carbon atom of 1 to
20 alkyl groups, p shows the integer of 8-40. ) [Chemical 4] (In the formula, R ₆ and R ₉ are a hydrogen atom or an alkyl group having 1 to 25 carbon atoms and may be the same or different,
R ₇ , R ₈ , R ₁₀ , and R ₁₁ are hydrogen atoms or have 1 to 25 carbon atoms.
Which are the same as or different from each other. R ₁₂ represents a hydrogen atom or a methyl group. q is an integer of 5 to 15, and Y represents an alkali metal atom or ammonium. )