JPS59142261A - Room-temperature curable traffic paint - Google Patents

Abstract

PURPOSE:To provide a room-temperature curable traffic paint which gives a coating film having excellent wear resistance, by mixing an org. polyisocyanate, a polyol, an amine, a filler, molten alumina powder and a thermoplastic resin in a specified weight ratio. CONSTITUTION:An org. polyisocyanate (A) (e.g. hexamethylene diisocyanate), a polyol (B) (e.g. acrylic resin), a tert. amine salt. a sec. or tert. amine (e.g. triethanolamine) or a metal salt of an org. acid (e.g. lead naphthenate) (C), a filler (D), molten alumina powder or glass powder (E) and a thermoplastic resin (F) are mixed together in such a quantity that the quantity of component E is 0-100wt% and that of component F is 0-300wt% based on that of component B with the proviso that at least one of components E and F must be contained in a quantity of at least 10wt% based on that of component B, thus obtaining the title traffic paint.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a traffic paint that can be cured at room temperature and has a coating film with excellent abrasion resistance.

Conventionally, heat-welding type traffic paint is known as traffic paint.

This is because the abrasion resistance of the paint film is poor, and even with room-temperature or heat-curing traffic paints containing polyisocyanates and polyols.

There was a problem that the wear resistance was insufficient.

The present invention solves these problems.

In other words, one aspect of the present invention is.

ta) Organic polyisocyanate.

(b) Polyol.

(C) Tertiary amine salt, secondary or tertiary amine or organic acid metal salt (d) Filler [excluding the component (Φ) below] (e)
It is a combination of fused alumina powder or glass powder and (f) a thermoplastic resin, and components (e) and ff) are 0 to 100% by weight and 0 to 100% by weight of component (b), respectively.
300% by weight, and at least one of component (e) and component (f) is 10% by weight relative to component (b).
This invention relates to a TraQuick paint that can be cured at room temperature and is made of the above ingredients.

The organic polyisocyanate of component (a) above is a compound having two or more incyanate groups, such as tolylene diisocyanate, cyfermethane-4,4'-
(MDI).

Crude MDI, xylylene diisocyanate.

Hexamethylene diisocyanate and dimers, dimers and prepolymers derived therefrom having terminal isocyanate groups are preferred, and in particular hexamethylene diisocyanate, dimers or prepolymers having terminal incyanate groups of hexamethylene diisocyanate are preferred. Polymer is good. The dimer can be obtained by reaction with water, and commercially available products include Coronate HL (trade name of Nippon Polyurethane).

The prepolymer is hexamethylene di(isocyanate and polypropylene glycol, polyethylene glycol,
Alkylene glycols represented by CnH2n (OH)2 where n is 2 to 10, glycerin,
Can be obtained by reaction with low molecular weight polyols such as poly(oxyethylene/oxypropylene) glycol, poly(oxyethylene/oxypropylene) derivatives of glycerin, poly(oxyethylene/oxypropylene) derivatives of sorbitol, castor oil, etc. .

Examples of the polyol as the component (b) include the above-mentioned low molecular weight polyols, alkyd resins, acrylic resins, and the like. In order to improve drying properties, it is preferable to use an alkyd resin or an acrylic resin as the polyol.

Here, the alkyd resin is obtained by reacting a polybasic acid, a polyhydric alcohol, and, if necessary, an oil, a fatty acid thereof, a synthetic fatty acid, or a glycidyl ester thereof.

Here, the above polybasic acids, maleic acid, fumaric acid, malonic acid.

Itaconic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, trimellitic acid, etc. can be used. For these, ester-forming derivatives thereof such as acid anhydrides may be used. The above polyhydric alcohol, ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1°6 hexanediol, 1,3 butanediol, glycerin,
Examples include trimethylolethane, trimethylolpropane, and pentaerythritol.

The above oils include soybean oil, safflower oil, tall oil, dehydrated castor oil, tung oil, coconut oil, and castor oil.

Kaashi 9 synthetic fatty acids such as rice bran oil and fish oil include monocarboxylic acids with tertiary alkyl groups having three alkyl groups having 1 to 7 carbon atoms (e.g., versatic acid, Shell Chemical Co., Ltd. product name). .

These components are converted into OH groups and C0OH groups.
The groups are blended in excess and reacted in a conventional manner. As the alkyd resin, a urethane-modified alkyd resin which is a reaction product of the alkyd resin thus obtained and a polyisocyanate can also be used. Here, as the polyisocyanate, those similar to the above-mentioned component (a) can be used.

The above acrylic resin is α having a hydroxyl group.

The α,β-ethylenically unsaturated monomer having 2-
Hydroxyalkyl acrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyalkyl methacrylate, and allyl alcohol can be used. Other copolymerizable monomers include alkyl acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate; acrylonitrile; Examples include vinyl cyanide compounds such as methacrylate trile, styrene compounds such as styrene and vinyltoluene, vinyl esters such as vinyl acetate and vinyl propionate, ethylene, and butadiene. Copolymerization of these monomers can be carried out by conventional methods.

The polyol of the present invention has a hydroxyl value (OH value) of 20 to 5.
50 is preferred. The hydroxyl value of the low molecular weight polyol is particularly preferably 50 or more.

The hydroxyl value of the alkyd resin and acrylic resin is particularly preferably 150 or less. If the hydroxyl value is too small, the curability will be poor, and if it is too large, the coating properties will be poor.

In the above component (C), as the tertiary amine salt.

1. Organic acid salts of bicyclic amidines such as 8-diaza-bicyclo(5,4,0)-undecene-7,1,5-diaza-bicyclo(4,3,0)-nonene-5.

Quaternary ammonium salts, metal complexes, etc. can be used. As the tertiary amine, general (however, R1
, R2, &, R4 and R5 each have 1 carbon number? l, 3
is an alkyl group, or a mono- or dihydroxyalkyl group, and at least two of these groups are mono- or dihydroxyalkyl groups having 1 to 3 carbon atoms.

n is 0, 1 or 2) It is a compound represented by

Examples Evagetanolamine, Triethanolamine, Diglobanolamine, Tripropaturamine, N, N
-jetanol-N/, N/diethylenediamine, N
, N'-dibrobanol-N.

N'-dipropylethylenediamine, N, N, N'
, N'-tetrapropanol ethylene diamine, N, N
.

N', N'', N-pentapropanol ethylene triamine, etc. can be used. As the organic acid metal salt.

For example, Pb in organic acids such as naphthenic acid and octenoic acid,
Metal salts such as Sn, Fe, Ni, Co, and Cu can be used. This includes dibutyltin dilaurate and the like.

As the filler of component (d), titanium dioxide, zinc white, white pigments such as lithopone, yellow pigments such as yellow lead, organic pigments, calcium carbonate, Merck.

Aggregates such as kaolin, silica powder, and insulator powder can be used.

I cut it. When the humidity is high, there is a possibility of foaming.
Gas absorbing agents such as slaked lime, quicklime, magnesium oxide, and cement may be used as fillers. When using gas absorbing agents.

It is preferable to use 5 to 30% by weight of component (b).

Examples of the thermoplastic resin of component (f) include raw rosin, maleic acid resin, ketone resin, phenol resin, terpene resin, and terpene resin, and those having a softening point of 100° C. or higher are used.

In the present invention, a plasticizer such as vegetable oil, mineral oil, or dialkyl phthalate may be added as appropriate.

The blending amounts of each component of the present invention will be explained next.

(a) component and (b) component are the NCO group of component (a) and f
The OH group of component b) is preferably OH/NC0 (equivalent ratio) of 0.5/1 to 1.5/1. Particularly preferably 0.9
/1 to 1.3/1. O
If H/NC0 (equivalent ratio) is too small, drying properties will be poor and foaming will occur easily, while if it is too large, coating film properties such as abrasion resistance will deteriorate.

Component (C) is preferably 0.1 to component (b).
~20% by weight is used. Among component (C), the tertiary amine salt is preferably 0.1 to 7% by weight, and the tertiary amine is preferably used in combination with an organic acid metal salt. If the amount of component (C) is too large, the coating workability will decrease.

If the amount is too small, curability will decrease.

Component (d) is preferably used in an amount of 10 to 400% by weight based on component (b). If it is too small, the concealment performance of Traquik Paint will decrease.

If the amount is too high, cracks are likely to occur in the coating film.

/ (e) component is O-da 00% by weight with respect to (b) component
used. If the amount of component (e) is too large, cracks tend to occur in the coating film.

3 (The fl component is used in an amount of 0 to 400% by weight based on the component (b). If the amount of the component (f) is too large, cracks are likely to occur in the coating film.

In the present invention, at least one of component (e) and component (f) is used in an amount of 10% by weight or more based on component (b) in order to improve wear resistance. When only component (f) is used, it is preferable to use a quantity of 20 M or more relative to component (b).

In the present invention, the plasticizer is for component (b).

You may use it in the range of 0-300 weight buns. If there is too much plasticizer, drying properties and abrasion resistance will decrease.

Each of the above-mentioned components of the present invention is prepared by mixing components other than component (a) in advance to prepare (A) solution, adjusting component (a) as (Bl solution), and mixing both at the time of use. Preferably.The fA) liquid and the (Bl liquid) are adjusted with a solvent to have an appropriate viscosity from the viewpoint of workability and product homogeneity.The viscosity is 3000 CPS/20'C or higher, and the boiling point is 13
A temperature of 0°C or lower is preferable.

If the boiling point is high, drying properties may be poor. Examples of the solvent include xylene, toluene, acetone, methanol, ethyl acetate, butyl acetate, and the like.

As for the coating method, Example 1 alkyd resin (OHHBO2 Phthalkyd DX-619
H, Hitachi Chemical ■Product name, solid content 50%) 20 parts (solid content), softener (dioctyl phthalate) 10 parts, titanium dioxide 20 parts, calcium carbonate 20 parts, molten alumina powder 10 parts, dibutyl tin dilau Liquid (A) is prepared by kneading 0.5 part of 3-roll with a three-roll mill, adding about 5 parts of toluene, and adjusting the viscosity to about 20,000 PS/25°C. Next, hexamethylene diisocyanate trimer (
Coronate HL, Nippon Polyurethane) Product name, NC
The fBl solution has an O content of 18%. (A) liquid seal (B) liquid were mixed at a weight ratio of 100:5 and immediately applied to a plate with an applicator to obtain a test piece. Table 1 shows the curing time, abrasion resistance, and weather resistance at that time.

Example 2 Alkyd resin (OHHSO3 Phthalkyd 483T9 Hitachi Chemical ■ trade name, solid content 50%) 20 parts (solid content)
, 10 parts of softener (dioctyl phthalate), 20 parts of titanium dioxide, 20 parts of calcium carbonate, 10 parts of glass powder,
0.4 part of 1,8-diazabisif/(5,4,0) undecene (hereinafter referred to as DBU) was kneaded with a three-roll mill,
Add about 5 parts of toluene to this, and the viscosity is about 20,000P8/
The mixture adjusted to 25°C (liquid A3) is then mixed with trimethylolpropane and tolylene diisocyanate adduct (Coronet) L, Nippon Polyurethane, trade name, NCO content 1.
7%) as liquid B3. (A) Liquid sealing (B) liquid were mixed at a weight ratio of 100:7 and tested in the same manner as in Example 1. The results are shown in Table 1. .

Example 3 Approximately 50% of solution (A) and fBl solution of Example 2 were prepared in advance.
It was heated to 0.degree. C. and tested in the same manner as in Example 2. The results are shown in Table 1.

Example 4 Acrylic resin (OHHBO2 Hytaloid 3001° Hitachi Chemical ■ trade name, solid content 50%) 10 parts (solid content),
10 parts of softener (dioctyl phthalate), 20 parts of titanium dioxide, and 40 parts of calcium carbonate.

10 parts of fused alumina powder, 1,8-diazabicyclo(5
,4,0) Knead 0.4 part of undecene with three rolls,
Add about 5 parts of toluene to this, and the viscosity is about 3000 CPS/
The solution adjusted to 25°C is referred to as fAl solution. next.

The (B) solution used in Example 1 is referred to as (B) solution. (A) Liquid sealing (B) Mix the liquid at a weight ratio of 100:5,
The test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 5 Alkyd resin (Phthalkyd DX-615) 15 parts (solid content), dioctyl phthalate) 10 parts, titanium dioxide 20 parts, calcium carbonate 30 parts 9 Petroleum resin (Neopolymer TX, Nippon Oil ■ trade name) 10 parts and DBUo, 4
5 parts of toluene was added to this by kneading with three rolls,
The CAl liquid is adjusted to have a viscosity of approximately 30,000 PS/25°C.

Hexamethylene diisocyanate) tripartite (:'0 nate HL) is (B+ liquid. (A) Liquid seal CB+ liquid is 105
4 (weight ratio), and tested in the same manner as in Example 1. The results are shown in Table 1.

Example 6 Alkyd resin (hydroxyl value 30. Phthalkyd DX-61
5; Hitachi Chemical ■) 15 parts (solid content) Petroleum resin (Neopolymer TX; Nippon Oil ■ trade name) 10 parts, titanium oxide 20 parts, calcium carbonate 20 parts by weight, softening agent (dioctyl phthalate): DOP) 10 parts, fused alumina powder 10
dibutyl tin dilaure) (DBTDL) 0.5
1 part and 0.1 part of jetanolamine were kneaded using a three-roll mill, and 5 parts of toluene was added to the mixture to give a viscosity of about 3000 CPS/
The solution was adjusted to 25°C (aluminum solution).Next, a trimer of hexamethylene diisocyanate (HMDI) (Coronate HLS manufactured by Nippon Polyurethane ■) was used as solution (B). (A) Liquid seal (solutions were mixed at a ratio of 105:4 (weight ratio) and tested in the same manner as in Example 1. The results are shown in Table 1.

Example 7 Alkyd resin (hydroxyl value 50. Phthalkyd 483T'
10 parts (solid content) of Hitachi Chemical Co., Ltd. (trade name), 20 parts of ketone resin (Hitanol 111; manufactured by Hitachi Chemical Co., Ltd.), 20 parts of titanium dioxide, 10 parts of dioctyl phthalate, and 20 parts of calcium carbonate.

10 parts of glass powder and 4 parts of DBUo were kneaded using 3 rolls, and 10 parts of toluene was added to this to obtain a viscosity of approximately 30,000P.
The solution adjusted to S/25°C is called the CAl solution. Next, an adduct of trimethylolpropane and tolylene diisocyanate (Coronate L; Nippon Polyurethane (Kiku brand name)) was added to C
Use B+ solution. (A) liquid seal (B) liquid were mixed at a weight ratio of 110:3 and tested in the same manner as in Example 1. The results are shown in Table 1.

Example 8 Alkyd resin (Phthalkyd DX-615) 15 parts (solid content) 9 Petroleum resin (Neopolymer TX) 5 parts, titanium dioxide 20 parts, calcium carbonate 20 parts.

10 parts of dioctyl phthalate, 15 parts of molten alumina powder, and 5 parts of a mixture of jetanolamine and lead naphthenate at a ratio of 1:9 (weight ratio) were kneaded using three rolls, and 5 parts of toluene was added to give a viscosity of about 3000 CPS/ The solution adjusted to 25°C is called the CA1 solution. Hexamethylene diisocyanate trimer (Coronate HL) (referred to as B'l solution. False)
The liquid sealing (B) liquid was mixed at a weight ratio of 110:4 and tested in the same manner as in Example 1. The results are shown in Table 1.

Example 9 (A) and (B+ solution of Example 7) separately in advance.

The same test as in Example 7 was conducted after heating to about 60°C. The results are shown in Table 1.

Example 10 Allyl resin (hydroxyl value 30. Hytalloid 3001: manufactured by Hitachi Chemical Co., Ltd.) 10 parts (solid content) 9 Petroleum resin (Neopolymer TX) 10 parts, dioctyl phthalate 10 parts, titanium dioxide 20 parts, calcium carbonate 30 parts, 10 parts of molten alumina powder, and 4 parts of DBUo were kneaded with three rolls,
Add 5 parts of toluene to this to obtain a viscosity of approximately 30,000 PS/25
The solution adjusted to ℃ (will be referred to as Al solution. Hexamethylene diisocyanate trimer (Coronet) HL) will be referred to as +Bl solution. FA) Liquid seal (B) Mix the liquid at a weight ratio of 105:3.

The test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Alkyd resin (OHHBO2 Phthalkyd DX-619
H, Hitachi Chemical ■Product name, solid content 50%) 20 parts (solid content), shaving agent (dioctyl phthalate) 10L titanium dioxide 20 parts, calcium carbonate 25 parts, jetanolamine and lead naphthenate 1 3 parts of the mixture was mixed using a three-roll mill, sand mill, etc., and toluene was added.

The liquid whose viscosity was adjusted to 20,000 PS/25°C is called liquid (A). (B) solution used in Example 1 is referred to as (B) solution.

The CAl liquid vs. the liquid was mixed at a weight ratio of 100:7 and tested in the same manner as in Example 1. The results are shown in Table 1.

As is clear from the above, the traffic paint which can be cured at room temperature according to the present invention has excellent abrasion resistance of the coating film.

Claims (1)

[Claims] (a) Organic polyinsyanate. (b) Polyol. (C) Tertiary amine salt, secondary or tertiary amine or organic acid metal salt (d) Filler [following (excluding ingredients)] (e) Combination of fused alumina powder or glass powder and ifl thermoplastic resin Tenari l (el and (f) components are
0 to 100% by weight and 0 to 300% by weight relative to component (b), respectively, and at least one of component (e) and component (f) is blended (at least 10% by weight relative to component bl). Traffic paint that can be cured at room temperature.