JPS60202159A - Road traffic paint composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent whiteness, stain resistance, etc., consisting of a urethane-modified alkyd resin and an acrylic resin contg. dimethyl (or diethyl) aminoethyl methacrylate and polypropylene glycol monomethacrylate. CONSTITUTION:At least 5wt% resin mixture consisting of 30-98wt% urethane- modified alkyd resin (A) having an oil length of 45-65% and 70-2wt% acrylic resin (B) having an average MW of 4,000-50.000 and a glass transition temp. of 60-130 deg.C composed of 0.3-8.5wt% dimethyl(or diethyl)aminoethyl methacrylate, 0.5-12.0wt% polypropylene glycol monomethacrylate having an average MW of 200-500 and other copolymerizable component such as methyl acrylate and additives such as pigment, dispersant for pigment, anti-foaming agent, etc. are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint composition for road markings that has particularly excellent performance in terms of whiteness, stain resistance, drying property, and bleed resistance. To explain in more detail, there are two types of road marking paints: heating type and room temperature type, and the road marking paint according to the present invention exhibits particularly excellent performance as a heating type.

Conventionally, many road marking paints have been coated with color vehicles such as alkyd resins, urethane-modified alkyd resins, acrylic resins, and vinyl acetate resins. Amid increasing demands for this, no coating material with satisfactory performance has yet been found. In other words, paints using Alkyra R-based resin as a color vehicle have good drying properties as they are heated, but the whiteness of the paint film and
Stain resistance and bleed resistance are extremely poor, and paints using vinyl acetate resin, acrylic resin, etc. as a color vehicle exhibit good whiteness, stain resistance, and bleed resistance at room temperature, but when heated When applied thickly as a mold (the durability of road marking paint is greatly affected by the coating thickness, the thicker the coating, the better the durability. Generally speaking, heated type paints have a 1. (It is possible to apply a film that is about 5 times thicker, and has been applied.) The drying properties are very poor, and it does not dry even after 20 or 60 minutes. There are some things that are unacceptable because they cause traffic jams.

The present inventors completed the present invention after intensive study in view of the above-mentioned problems.

That is, according to the present invention, urethane-modified alkyne F'' resin (5) with an oil length of 45 to 65%, 60 to 9 a3; .5 heavy lid% (relative to acrylic resin (B)) and average molecular weight 200-5
00 polypropylene glycol monomethacrylate 0
．． 5-12.0% by weight (based on acrylic resin (B))
Acrylic resin (B) containing as a comonomer 2-70
By using a paint composition for road markings comprising a resin mixture consisting of Wear. .

The urethane-modified alkyd resin used as the first component in the coating composition of the present invention includes oils and fats such as soybean oil fatty acids, tall oil fatty acids, safflower oil, and linseed oil, - pentaerythritol, glycerin, and trimethylolpronozone. Raw materials include polyalcohols, monobasic or polybasic acids such as benzoic acid, maleic acid, phthalic acid, and isophthalic acid, isocyanate compounds such as tolylene, diisocyanate, xylylene diisocyanate, cuphenylmethane, and diisocyanate, etc. As shown in the literature known as (1 Introduction to Synthetic Resins for Paints', Kyozo Kitaoka, Kobunshi Publishing Co., Ltd. (1976), etc.).

It is prepared by converting it into urethane through a transesterification reaction, a dehydration condensation reaction, etc., and is extremely common, requiring no special operations or raw materials. The urethane-modified alkyd resin used in the present invention has an oil length of 45 to 6.
If the oil length is less than 45%, the coating film becomes brittle and the drying properties are also adversely affected. Also oil length 65
% or more, adhesiveness tends to remain on the coating film, and stain resistance and dryness to the touch become extremely poor. Further, the amount of the resin used is preferably 60 to 98% by weight of the resin mixture. If the amount used is less than 0% by weight, the drying properties of the paint, especially when applying a thick film, will be significantly poor, and if the amount used is more than 98% by weight, the whiteness of the film, stain resistance, and bleaching resistance will be deteriorated. It is undesirable that the properties are reduced to the same level as those of alkyd resin-coated eaves, and the meaning of mixing and using acrylic resin is completely lost.

Acrylic resin (B) constituting the second component of the coating composition of the present invention
) contains as essential components 0.3 to 8.5% by weight of dimethylamine ethyl methacrylate or diethylaminoethyl methacrylate (the latter being more preferred) and 0.5 to 12% of polypropylene glycol monomethacrylate with an average molecular weight of 1200 to 500. It is essential to contain .0% by weight as a comonomer, which is prepared by copolymerizing with other copolymerizable components. If the amount of methacrylic acid/coumetelaminoethyl or diethylaminoethyl methacrylate used is less than 0.3 weight jIk%, sufficient compatibility with the urethane-modified alkyd resin cannot be obtained,
During storage of the coating composition, separation, gelation, soft or hard caking, etc. tend to occur, and it becomes difficult to obtain a sufficiently tough coating film. If the amount used is 8.5% by weight or more, problems may occur in the preparation of the acrylic resin, and the water resistance, weather resistance, and whiteness of the resulting coating composition will be significantly deteriorated. If the amount of polypropylene glycol monomethacrylate with an average molecular weight of 200 to 500 is less than 0.5% by weight, the coating film will lack flexibility, become susceptible to chipping, and significantly deteriorate durability. If the amount used is 12.0% by weight or more, the coating film will become sticky at high temperatures (road surface temperatures can reach 50C or higher in summer), resulting in extremely poor stain resistance. The former methacrylic acid/quethylaminoethyl or methacrylic acid/quethylaminoethyl is preferably used to improve the compatibility between the acrylic resin (B) and the urethane-modified alkyl resin, and also improves pigment dispersibility. The average molecule of the latter is effective in densifying the paint film and improving its durability! Polypropylene glycol monomethacrylate having a molecular weight of 200 to 500 is extremely effective in imparting removability to the coating film, and its durability is dramatically improved. Furthermore, due to its chemical structure, it exhibits excellent performance in the storage stability of paints, especially in preventing precipitation, to the extent that it does not require any other general paint additives.

Other copolymerizable components constituting the acrylic resin (B) include methacrylate, methyl pyrate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate. , (meth)acrylic esters such as ethylhexyl acrylate and isononyl acrylate, and styrene, vinyl chloride, and vinyl acetate.These monomers can be used alone or as a mixture of two or more. good.

Acrylic resin (E is 60 to 160C using a radical polymerization initiator such as benzoyl peroxide
Preferably, the preparation is carried out by a solution polymerization method at a polymerization temperature of .

Acrylic resins (B) having an average molecular weight of 4,000 to 50,000 and a glass transition temperature of 30 to 66 tll' are preferably used. If the average molecular weight is less than 40, the coating film will be brittle and prone to chipping, resulting in poor durability.If the average molecular weight is more than 5000, a large amount of diluting solvent will be required, making it difficult to achieve the desired high film thickness. Either it will not work, or the spray pattern will become poor, resulting in poor stain resistance and durability. Glass transition temperature is 30t
If the glass transition temperature is 65C or higher, the paint film will become hard and brittle, easily chipping, and the durability will deteriorate significantly. It is in.

Acrylic resin (acrylic resin is preferably used in an amount of 2 to 70% by weight of the resin mixture. If the amount used is less than 2% by weight, the whiteness, stain resistance, and bleaching resistance of the coating will be poor, % or more indicates that the drying properties of the paint are extremely poor, and are completely out of the scope of evaluation, especially for heated types.

As long as the road marking paint composition according to the present invention contains 5% by weight or more of the resin mixture, pigments such as titanium white and calcium carbonate, which are generally used as paint raw materials, and paint additives such as pigment dispersants and antifoaming agents can be used. I need medicine! If present, the urethane-modified alkyd resin used in the Examples and Comparative Examples of the present invention, which exhibits its excellent performance without any problem even if it is used in combination with other resins, plasticizers, etc. used for paints, Acrylic resin will be explained.

(a) Urethane-modified alkyd resin soybean white oil, glycerin, pentaerythritol, phthalic anhydride, TDI-80 () lylene diisocyanate,
A urethane-modified alkyd resin was prepared using a urethane-modified alkyd resin (manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.). This was diluted with toluene so that the heating residue was 55.011.0% to obtain a urethane-modified alkyd resin used in Examples and Comparative Examples of the present invention. Table (1) shows the properties of each urethane-modified alkyd resin.

In addition, in Table (1), each resin name is represented by the serial number in Table 11, a-1 and a-2 are urethane-modified alkyd resins suitable for the present invention, a-3, a
-4 is an inappropriate resin.

(bl) 2409 toluene and 4.8 g of tert-buternopenzoate were charged into an 11-four-bottle flask equipped with an acrylic resin stirring device, a nitrogen gas inlet tube, a thermometer, and a backflow condenser, and 112 tons of
Next, the raw material mixture shown in Table (2) was added dropwise into the flask over 180 minutes, and then heated at 112C for 12 hours.
Polymerization is carried out for 0 minutes. A mixed solution of toluene ao, o, p and tertiary buterperpenzoate 2.4Ii was added dropwise into the flask in three portions every 60 minutes, and after all the drops were completed, polymerization was further carried out at 112C for 180 minutes. After that, it was cooled to room temperature to produce an acrylic resin. Here, each resin name is represented by the serial number in Table (2).

Table (2) (Book 1) Polypropylene glycol monomethacrylate (manufactured by NOF JJi1■) In Table (2), b-1 and b-2 are acrylic resins suitable for the present invention. 4, b-5, and b-6 are acrylic resins that are not suitable.

Examples and Comparative Examples Resin mixtures of 1° Examples and Comparative Examples prepared by stirring and mixing the resin mixtures of Formulation 1, Examples and Comparative Examples shown in Table (3) using Paint Decilper for 5 to 10 minutes. A compatibility and drying test was conducted using 5. The test method and evaluation method are as follows.

It was applied on a compatible glass plate with a 10 mil applicator, and after drying for one day, the transparency of the film was examined: ○ Completely transparent, △ Slightly cloudy, × Cloudy 1
The coating was applied with a 60 mil applicator onto a dry glass plate and the time required for the film to become immobilized was determined.

The test results are shown in Table (4) 1. Table (4) Next, using the resin mixtures of Examples 1 and 4 and Comparative Examples 1 and 5, the composition of Table (5) was applied to a paint dissolvent with a particle size of 60μ. By dispersing the pigment until the
A road marking paint (white, heating type) was produced.

Table (5) Road marking paints obtained using the resin mixtures of Examples 1 and 4 and Comparative Examples 1 and 5 were classified into EC-1 and EC-1, respectively.
-2, RC-1, and RC-2 for simplicity.

These paints are drying, abrasion resistant, and smudge-resistant.

Various tests of whiteness (JISK-5665) were conducted.

The results are shown in Table (6).

Table (6) Table (4) 1 Table (6) K 9. The road marking paint composition according to the present invention fully exhibits its excellent performance as a road marking paint, especially as a heating type. You can see that

Claims (1)

[Claims] Urethane modified alkyd resin with oil length 45-65% (5)
30-98% by weight and 0.6-98% dimethylaminoethyl methacrylate or methacrylic acid, queteraminoether
8.5% by weight (based on acrylic resin (B)) and polypropylene glycol monomethacrylate with an average molecular weight of 200-500 0.5-12.0! A road marking coating composition comprising a resin mixture comprising 2 to 70% by weight of an acrylic resin (B) containing 2 to 70% by weight of an acrylic resin (B) as a comonomer component (based on the acrylic resin (B)).