JPH03177464A - Coating agent - Google Patents

Abstract

PURPOSE:To obtain a coating agent showing excellent compatibility, providing a coating film having excellent stain resistance, antistatic properties, scratching resistance, etc., comprising an ethylenic double bond-containing monomer, etc., polymerization initiator and a specific quaternary ammonium salt. CONSTITUTION:The objective coating agent comprising (A) a monomer and/or oligomer [e.g. methyl (meth)acrylate] containing at least one polymerizable ethylenic double bond in the molecule, (B) a polymerization initiator (e.g. radical polymerization initiator) and (C) a quaternary ammonium salt shown by the formula (R<1> is >=8C long-chain alkyl or alkylene; R<2> is 1-4C alkylene; R<3> to R<5> are 14C alkyl or substituted alkyl; X<-> is anion to form quaternary ammonium salt).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a coating agent made of a curable resin composition, and in particular, a coating agent that can be applied to the surface of plastic materials in stain-proofing properties and has excellent scratch resistance. The present invention relates to a coating agent capable of forming a film.

(Conventional technology and its problems) Plastics are widely used in the fields of wooden products and metal products due to their workability and mass productivity. Among these plastics, transparent plastics such as acrylic resin, polycarbonate, and polyvinyl chloride are being used in some glass application fields, taking advantage of their light weight and resistance to breakage. However, plastic has a soft surface and is easily scratched. To improve this point,
Conventionally, surface modification has been investigated using a corrosion-resistant surface protection coating agent made of silicone-based or energy ray-curable resin.

By performing such treatment, a film with anti-corrosion properties is formed on the plastic surface, but the curing time for film formation is long, or the formed film is also plastic, so it is easily charged with static electricity. However, as it is, it has the disadvantage that it is difficult to coat glass products that dislike dirt and dust.

Methods for preventing static electricity on plastics include applying a conductive substance or a substance with antistatic curing to the plastic surface, or kneading it into plastic during molding. However, plastic has both properties of corrosion resistance and antistatic properties...! The former method requires a large number of steps in order to make the material more durable, and the latter method has the disadvantage that it is technically difficult to mold the material while achieving both properties, and the cost is also high.

Plastics such as acrylic resin and polycarbonate are used for AV @ equipment covers, nameplates, OA equipment covers, automobile parts, optical disk boards, etc. due to their excellent transparency and appearance characteristics. In such applications, it is particularly necessary to prevent surface stains, and furthermore, as mentioned above, it would be preferable if anti-corrosion properties could be added to compensate for the drawbacks of plastics.

(Objective of the Invention) The object of the present invention is to solve the above-mentioned problems of the prior art, and in particular, to easily form a coating with excellent stain resistance and rust resistance on the surface of plastic materials of arbitrary shape. The objective is to provide a coating agent that can be applied to.

(Disclosure of the Invention) The coating agent of the present invention includes monomers and/or oligomers having at least one polymerizable ethylenic double bond in the molecule, a polymerization initiator, and general =← (However, R1 is a long chain having 8 or more carbon atoms. Chain alkyl is an alkylene group, R2 is an alkylene group having 1 to 4 carbon atoms, R3,
R4 and R5 represent an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and X represents an anion that forms a quaternary ammonium salt. ) is characterized by consisting of a quaternary ammonium salt represented by

As the monomer and/or oligomer having at least one polymerizable ethylenic double bond in the molecule used in the present invention, components conventionally used as components of polymerizable curable resin compositions can be used as appropriate. 6 Usually, a combination of an oligomer having two or more ethylenic double bonds on average and a monomer having one or more ethylenic double bonds is preferably used. Specific examples of oligomers include acrylates such as polyurethane (meth)acrylate, epoxy (meth)acrylate, and polyester (meth)acrylate, as well as oligomers modified with vinyl groups, allyl groups, etc.; Monomers can be used in place of these oligomers, but are not limited to these, but in order to lower the viscosity of the oligomers, improve adhesion to materials, and improve the surface condition, Monomers having at least one polymerizable ethylenic double bond are often added, and these monomer components include (meth)acrylics such as methyl (meth)acrylate, ethyl (meth)acrylate, and hydroxyethyl (meth)acrylate. Acid esters, (meth)acrylamides including acryloylmorpholine, vinyl monomers such as styrene, N-vinylpyrrolidone, N-vinyloxazolidone, N-vinyl or cinimide, and allylbenzene, allylmorpholine, etc. Examples include, but are not limited to, monomers, and when monomers having an average of three or more polymerizable ethylenic double bonds in the molecule are used in combination, the rust resistance is further improved.

Specific examples of these include trimethylolpropane tri(
meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)
Acrylate, dipentaerythritol tetra(meth)
Acrylate, dipentaerythritol penta(meth)
Acrylate, dipentaerythritol hexa(meth)
Examples include acrylate.

The monomers and oligomers having a polymerizable ethylenic double bond in the molecule as disclosed above are usually used in two types depending on the characteristics of the material to be coated and its intended use.
In the present invention, when a monomer and/or oligomer having a hydroxyl group in the molecule, such as hydroxyalkyl (meth)acrylate, is contained as one component, the quaternary Particularly favorable results are obtained in combination with ammonium salts.

The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization or ionic polymerization depending on the nature of the double bond contained in the resin used, and any known polymerization initiator may be used as appropriate. can. Examples of the former include inorganic peroxides, organic peroxides, combinations of peroxides and reducing agents, azo compounds, and photoradical polymerization initiators; Examples include polymerization initiators. The amount of the polymerization initiator added is based on the total amount of the oligomer component and monomer component mentioned above.
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
The range is 0.05 to 5 parts by weight.

The coating agent of the present invention contains a quaternary ammonium salt represented by the above general formula in these curable resin compositions.

In the above general formula, specific examples of R1 include long alkyl or alkylene groups such as oleyl, stearyl, myristyl, etc., and usually have 16 to 20 carbon atoms, preferably 18 carbon atoms, and R2 has (CH2) 1 to 4, especially - CH2CH2CH2 is preferred, R3, R4, R5 include methyl, ethyl, propyl, hydroxyethyl, hydroxypropyl, etc.
In particular, one of them is preferably hydroxyalkyl such as hydroxyethyl.

X- is preferably an anion that forms an inorganic salt such as a halide, sulfate, or nitrate.These ammonium salts are usually in the form of water and/or alcohol solutions.The amount of this ammonium salt added is The solid content is 0.1 to 5 parts by weight based on 100 parts by weight of the oligomer component and monomer component. 0.1
If the amount added is less than 5 parts by weight, a sufficient antistatic effect cannot be obtained, and if it is more than 5 parts by weight, the surface becomes sticky after the resin is cured.

Although it is known that these ammonium salts themselves have antistatic properties, the more common antistatic agents used in the curable resin compositions of the present invention cannot achieve the desired purpose. It is quite surprising that the above-mentioned ammonium salts exhibit remarkable selective effects.

The essential components of the coating agent of the present invention are as described above, but it goes without saying that organic solvents, various additives, etc. may be used in combination as appropriate. Organic solvents are effective in controlling viscosity. Examples of additives that can be used in combination include leveling agents, antioxidants,
There are UV absorbers, etc.

(Example) Examples of the present invention will be shown below and will be described in more detail.

Note that all parts in the examples are parts by weight.

Examples 1 to 5 and Comparative Examples 1 to 5 As shown in Table 1 below, oligomers having polymerizable double bonds,
Each part of the monomer, photoinitiator, 41f1 ammonium salt or other surfactant, and solvent were mixed and dissolved. The obtained UV-effective resin composition was applied by dipping onto a polycarbonate substrate, and then placed in a constant temperature layer at 60°C for 3 to 30 minutes.
After leaving it for 5 minutes to volatilize the solvent,
Ultraviolet light with a wavelength of m (UV illuminance 180mW/cd)
The resin composition on the surface was cured by irradiation for 0 seconds.

A pencil hardness test, a rust resistance test, an adhesion test, a cigarette ash adhesion test, and an electrostatic voltage measurement were conducted on each test piece having the thus obtained cured film. The results are shown in Table 2.

Compatibility test: Visually evaluated whether the resin blended composition turned into a -like solution using the following two steps.

○・・・Transparent and homogeneous solution without turbidity.

X: Turbidity and precipitation are observed. Items with a rating of X will not be tested further.

Pencil hardness test: 1k according to JIS K-5400
! The coating film hardness is measured by applying a load of r.

Scratch resistance test: The coating film was scratched with a fingernail, and the degree of scratching was evaluated with the naked eye on the following two scales.

○...No scratches observed.

X...I recognize the wound.

Adhesion test @: According to JIS K5400, 1 +n+
In order to create 100 corners, a cut was made to penetrate the paint film and reach the fabric surface of the test piece, and the cellophane tape was completely adhered to the cut, and then the cellophane tape was instantly pulled away. The remaining number of base items at that time is expressed as number of remaining base items/100.

Grass ash adhesion test: After rubbing the surface of the test piece with the cured film 10 times with a cotton cloth, the test piece was brought closer to the cigarette ash and the height at which the ash adhered was measured.

Electrostatic voltage measurement: Similar to the cigarette ash adhesion test, after rubbing the surface of the test piece with the cured film 10 times with a cotton cloth, use a static electricity meter (Statiron M manufactured by Daisei Shokai Co., Ltd.)
) was used to measure the electrostatic pressure on the surface of the test piece. The results are shown in Table 2.

As is clear from the results in Table 2, the coating agent of the present invention has excellent compatibility, and the coating film obtained therefrom exhibits excellent properties such as antifouling properties, antistatic properties, and anti-corrosion properties. The fact that these performances can be easily imparted not only simplifies the work compared to conventional technology, but also shortens line tact and reduces costs, especially when forming a cured film by irradiating ultraviolet rays. The coating agent of the present invention also has antifogging properties and can be effectively used in fields where antifogging properties are required.

Claims (1)

[Claims] 1. Monomers and/or oligomers having at least one polymerizable ethylenic double bond in the molecule, polymerization initiators, and general formulas ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^ 1 is a long chain alkyl or alkylene group having 8 or more carbon atoms, R^2 is an alkylene group having 1 to 4 carbon atoms, R
^3, R^4, and R^5 represent an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and X^- represents an anion that forms a quaternary ammonium salt. ) A coating agent comprising a quaternary ammonium salt represented by: 2. The coating agent according to claim 1, wherein the monomer and/or oligomer comprises (meth)acrylate and/or its oligomer. 3. The coating agent according to claim 1 or 2, wherein the monomer and/or oligomer contains hydroxyalkyl (meth)acrylate and/or its oligomer as at least a part thereof. 4. The coating agent according to claim 1 or 2, wherein the monomer and/or oligomer contains (meth)acrylamide and/or substituted (meth)acrylamide units as at least a part thereof. 5. The coating agent according to claim 1 or 2, wherein the monomer and/or oligomer contains a nitrogen-containing heterocyclic compound unit having an N-vinyl group as at least a part thereof. 6. R^1 in the general formula is an alkyl group having 16 to 20 carbon atoms,
R^2 is an alkyl group having 2 to 4 carbon atoms, R^3, R^4,
The coating agent according to any one of claims 1 to 5, wherein R^5 is an alkyl and/or hydroxyalkyl group having 1 to 3 carbon atoms. 7. The coating agent according to claim 1, wherein R^3 and R^4 are alkyl groups and R^5 is a hydroxyalkyl group. 8. Claims 1 to 8, wherein X^- in the general formula is an inorganic salt anion.
7. The coating agent according to any one of item 7.