JP5619927B2 - Snow-sliding coating - Google Patents

Description

  The present invention relates to a snow-sliding coating film having a surface on which accumulated snow slides.

  As a material for this type of snow slidable coating film, polyorganosiloxane having a polymerizable unsaturated bond is provided (see, for example, Patent Documents 1 to 4).

Japanese Patent Laid-Open No. 11-256071 JP-A-10-265737 JP-A-6-264051 JP 2000-44863 A

  The snow slidable coating film has a problem that it has a relatively small molecular weight, is inferior in durability, and is not sufficiently adhesive to the substrate.

The present invention as means for solving the conventional problems described above, with respect to the heavy polymerizable polyester and / or polyether (meth) acrylate 100 parts by mass of the polymerizable (meth) acrylic group-containing polydimethylsiloxane 10 to 30 mass part was added, Ri further Do the UV absorbers and / or the mixture was added 1.0 to 1.5 parts by weight of an antioxidant of a cured product obtained by curing by electron beam irradiation, the cured product thereon in which the snow to provide a Namerayuki coating film, characterized in Rukoto that have a surface, such as falling off.
Becomes a mixture obtained by adding a polymerizable vinyl monomer of further 50 to 90 parts by weight of the above mixture of a cured product obtained by curing the morphism electron beam irradiation, the cured product surface, such as snow piled thereon to slide down it may be a Namerayuki coating film having a.

[Action]
Invention of Claim 1 When a mixture mainly comprising a polymerizable (meth) acrylic group-containing polydimethylsiloxane and a polymerizable polyester and / or polyether (meth) acrylate is irradiated with an electron beam, the polymerizable property in the mixture ( When the (meth) acrylic group-containing polydimethylsiloxane and the polymerizable polyester and / or polyether (meth) acrylate are rapidly copolymerized, the mixture becomes a large polymer and is cured. Such a curing reaction is carried out by electron beam irradiation at low temperature, low energy and in a very short time, thus saving energy and shortening the process, and easily forming a cured coating film on a non-heat-resistant substrate surface. can do. As described above, the cured product becomes a macromolecule having a large molecular weight, and the polydimethylsiloxane portion contained in the macromolecule imparts snow slidability to the cured product, and further, polyester and / or polyether. Adhesion with the substrate is provided by the (meth) acrylate moiety. And since this hardened | cured material coating film consists of a huge polymer as mentioned above, it is excellent in a weather resistance, stain resistance, and abrasion resistance.

Invention of Claim 2 When a polymerizable vinyl monomer is further added to the mixture and copolymerized by electron beam irradiation and cured, the hardness of the cured coating film can be adjusted depending on the type of the polymerizable vinyl monomer. The adhesion to the material can be improved.

〔effect〕
In the present invention, since the mixture can be rapidly cured at a low temperature and low energy, the energy required for forming a coating film is saved, and the cured product becomes a giant polymer, so that it is snow slidable and weather resistant. It is possible to obtain a coating film having excellent properties, stain resistance, and abrasion resistance.

The present invention is described in detail below.
[Polymethylsiloxane containing polymerizable (meth) acrylic group]
The polymerizable (meth) acrylic group-containing polydimethylsiloxane used in the present invention is produced by bonding acrylic acid and / or methacrylic acid to a polydimethylsiloxane having a hydroxyl group at one or both ends by an esterification reaction. . The hydroxyl group of the polydimethylsiloxane having a hydroxyl group at one end or both ends may be derived from a silanol group present at one end or both ends of the polydimethylsiloxane. In order to increase the molecular weight of the cured product, a hydroxyl group present at one or both ends of the polyester and / or polyether-modified polydimethylsiloxane obtained by modifying one end or both ends of the polydimethylsiloxane with polyester and / or polyether. It is preferable to select a polyester and / or a polyether-modified (meth) acrylic group-containing polydimethylsiloxane in which acrylic acid and / or methacrylic acid are bound to each other by an esterification reaction.

The polyester-modified acrylic group-containing polydimethylsiloxane has, for example, the following structure.

The polyether-modified acrylic group-containing polydimethylsiloxane has, for example, the following structure.

  As a commercially available product of the polyester-modified acrylic group-containing polydimethylsiloxane, there is BYK-371 (trade name; manufactured by BYK Chemie).

  More desirable as the polymerizable (meth) acrylic group-containing polydimethylsiloxane is a terminal polyester produced by polycondensation of a polyisocyanate and a polyester and / or a polyether at one or both ends of the polydimethylsiloxane. And / or a polyurethane-modified (meth) acrylic group-containing polydimethylsiloxane in which acrylic acid and / or methacrylic acid is bonded to a polyester of a terminal polyether polyurethane-modified polydimethylsiloxane and / or a hydroxyl group of a polyether terminal by an esterification reaction.

The polyurethane-modified acrylic group-containing polydimethylsiloxane has, for example, the following structure.

  As a commercial item of the polyurethane-modified acrylic group-containing polydimethylsiloxane, there is BYK-UV-3570 (trade name; manufactured by BYK Chemie).

[Polymerizable polyester and / or polyether (meth) acrylate]
In the polymerizable polyester and / or polyether (meth) acrylate used in the present invention, acrylic acid and / or methacrylic acid are bonded to hydroxyl groups at both ends and / or side chains of the polyester and / or polyether by an esterification reaction. Is. For example, the bifunctional polyester acrylate has the following structure ([Chemical Formula 4]), and the trifunctional or higher functional polyester acrylate has the following structure. ([Chemical Formula 5]).

  As a commercially available product of the bifunctional polyester acrylate, there is M-6250 (trade name; manufactured by Chisso Corporation), and as a commercially available product of the polyfunctional polyester acrylate, M-7100 (trade name; manufactured by Chisso Corporation) is available. is there.

(Polymerizable vinyl monomer)
In the present invention, polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxynonylene glycol, etc. are particularly used as the polymerizable vinyl monomer. Acrylic acid and / or methacrylic acid ester of trihydric alcohol such as acrylic acid and / or methacrylic acid ester of dihydric alcohol, trimethylolpropane, hexanetriol, glycerin. In addition to the polyhydric alcohol acrylic acid and / or methacrylic acid ester, or in place of the polyhydric alcohol acrylic acid and / or methacrylic acid ester, a reaction product of a polyether and / or polyester and a polyvalent isocyanate. A polyurethane (meth) acrylate obtained by esterifying acrylic acid and / or methacrylic acid to a polyurethane having a hydroxyl group at one end or both ends may be used, and as another polymerizable vinyl monomer, for example, methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydro Such as rufuryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate, lauryl methacrylate, etc. Aliphatic or cyclic acrylates and / or methacrylates, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, styrenes such as styrene and α-methyl styrene, acrylonitrile, methacrylate Nitrile monomers such as ronitrile, vinyl acetate, propionic acid Fatty acid vinyl such as vinyl, halogen-containing monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, olefins such as ethylene and propylene, dienes such as isoprene, chloroprene and butadiene, acrylic acid and methacrylic acid , Α, β-unsaturated carboxylic acids such as itaconic acid, maleic acid, crotonic acid, atropic acid, citraconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, Hydroxyl-containing monomers such as allyl alcohol, amides such as acrylamide, methacrylamide, diacetone acrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, di Amino group-containing monomers such as methylaminopropyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether, other water-soluble monomers such as vinyl pyrrolidone, vinyl pyridine, and vinyl carbazole, and γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilylstyrene, p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, γ -Acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N- [beta] (N-vinylbenzylaminoethyl- [gamma] -aminopropyl) trimethoxysilane, hydrochloride, etc. are exemplified.

[Combination]
The polymerizable (meth) acryl group-containing polydimethylsiloxane is usually added in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the polymerizable polyester and / or polyether (meth) acrylate. When adding the said polymerizable vinyl monomer, 50-90 mass parts is normally added with respect to 100 mass parts of the said polymerizable polyester and / or polyether (meth) acrylate. The above components are usually alcohol solvents such as methanol, ethanol, iso-propanol, butanol, cyclohexanol, ketone solvents such as acetone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, ethyl acetate, n-butyl acetate, amyl acetate. Ester solvents such as benzene, toluene, xylene aromatic solvents, cellosolve acetate, methyl cellosolve, ethyl cellosolve, cellosolve solvents such as n-butyl cellosolve, monophenyl glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether It is dissolved in an organic solvent such as an alkyl ether of a polyhydric alcohol such as a snow-sliding paint.
[Coating]
The snow-sliding paint of the present invention is applied to the surface of, for example, plywood, hard board, wood cement board, calcium silicate board, gypsum board, ceramic board, plastic board, etc., and is cured by irradiation with an electron beam. A snow-sliding coating film is formed on the surface.
The thickness of the coating film is usually about 50 to 150 μm, and the electron beam is usually irradiated with an intensity of 3 to 5 MRad in a short time of 0.1 seconds or less.

[Example 1]
The following formulation is prepared.
Polyester diacrylate 53.5 parts by mass Polyester-modified acrylic group-containing polydimethylsiloxane 10.0 parts by mass Tripropylene glycol diacrylate 20.0 parts by mass Hexamethylenediol diacrylate 15.0 parts by mass UV absorber 1.5 parts by mass A snow-sliding paint having a composition of paint NO. Set to 1.

[Example 2]
The following formulation is prepared.
Polyester diacrylate 50.0 parts by mass One-end methacryl group-containing polydimethylsiloxane 20.0 parts by mass Tripropylene glycol diacrylate 15.0 parts by mass Nonamethylenediol diacrylate 12.0 parts by mass UV absorber 1.5 parts by mass Oxidation Inhibitor 1.5 parts by weight A snow-sliding paint having the above composition is applied as paint NO. 2.

Example 3
The following formulation is prepared.
Nonamethylenediol diacrylate 40.0 parts by mass Trimethylolpropane triacrylate 38.0 parts by mass Polyester-modified acrylic group-containing polydimethylsiloxane 20.0 parts by mass UV absorber 1.0 part by mass Antioxidant 1.0 part by mass A snow-sliding paint having a composition of paint NO. 3.

Example 4
The following formulation is prepared.
Polyurethane diacrylate 54.0 parts by weight Polyester-modified acrylic group-containing polydimethylsiloxane 10.0 parts by weight Hexamethylenediol diacrylate 20.0 parts by weight Trimethylolpropane triacrylate 15.0 parts by weight UV absorber 1.0 part by weight A snow-sliding paint having a composition of paint NO. 4.

    The above paint NO. 1-NO. 4 was applied to the surface of the plywood to a film thickness of about 100 μm and dried, and then the electron beam diffractometer was irradiated with an electron beam of 3 MRad to 5 Mrad for 0.1 second to cure the coating film. Table 1 shows the physical properties of each paint.

[Comparative Example]
Snow sliding in which 5% by mass of hexamethylenediamine is added to a 40% by mass ethyl methyl ketone solution of a 70:30 mass ratio copolymer of dimethyl group-containing polydimethylsiloxane and 2-hydroxyethyl methacrylate. sex paint to cure the coating by applying heat of 0.99 ° C. 10 minutes after drying was applied to a thickness of approximately 100μm on the surface of the plywood. Table 1 shows the physical properties of the comparative paint thus prepared.

〔Test method〕
1. Gloss retention The gloss of the coating film before and after the test is measured with a gloss meter gloss checker (manufactured by Sato Shoji Co., Ltd.), and the gloss after the test is divided by the gloss before the test to obtain the gloss retention.
2. Snow sliding evaluation ◎ Almost remains
○ Some remaining
□ Some remaining
△ Almost no residue. Contact angle At room temperature (20 ± 1 ° C.), one drop of distilled water is dropped on the coating film with a microsyringe, and the contact angle is measured by an optical mirror method (contact angle meter manufactured by Kyowa Interface Science; DM-100).
4). Icing power A stainless steel ring for making ice was placed on the sample surface, cooled sufficiently to a predetermined temperature, distilled water at 5 ° C. was poured, and the ice was frozen by leaving it for a predetermined time. Thereafter, a load is applied to the stainless steel ring in the shearing direction to separate the material from the frozen surface. A value obtained by dividing the weight at that time by the adhesion area is defined as an icing force (kgf / cm ² ).

  According to Table 1, the snow-sliding paint of the present invention provides a coating film having excellent snow-sliding property and good durability, but the coating film of the comparative paint is inferior in snow-sliding property and insufficient in durability. It is done.

Since the present invention can form a snow-sliding coating film in an extremely short time easily and energy-saving, the process is shortened and streamlined, and the durability of the coating film is good, so that it can be used industrially. is there.

Claims (2)

For heavy polymerizable polyester and / or polyether (meth) acrylate 100 parts by mass of the polymerizable (meth) was added 10 to 30 parts by weight of acrylic group-containing polydimethylsiloxane, further UV absorbers and / or antioxidants A hardened product obtained by curing 1.0 to 1.5 parts by mass of a mixture obtained by electron beam irradiation, and the hardened product has a surface on which snow accumulated thereon slides down. Paint film. A mixture obtained by further adding 50 to 90 parts by mass of a polymerizable vinyl monomer to the mixture of claim 1 is cured by electron beam irradiation, and the cured product is such that snow accumulated thereon slides down. A snow-sliding coating film characterized by having a surface.