JPS5865772A - Marking material - Google Patents

Abstract

PURPOSE:To provide a marking material suitable for use in road marking and having excellent mechanical strength, spreadability, flexibility, etc., by mixing an org. polyisocyanate, an unsaturated polyester resin and a filler in a specified weight ratio. CONSTITUTION:An org. polyisocyanate (A) having at least two terminal isocyanate groups, such as tolylene diisocyanate or hexamethylene dissocyanate, an unsaturated polyester resin (B) and a filler (C) such as titanium dioxide or calcium carbonate are mixed together in such a proportion as to give 5-60wt% component a and 5-70wt% component C based on the amount of component B to obtain the desired marking material. In using this marking material, a catalyst such as methyl ethyl ketone peroxide and an accelerator such as cobalt octenoate are added thereto. The mixture is cast into the desired mold, and cured at ordinary temp. or by heating it.

Description

[Detailed description of the invention] The present invention relates to marking materials.

Traditionally, road marking materials include Kumano resins (vinyl chloride, rubber, petroleum resins, etc.), polyurethane resins, epoxy resins,
Unsaturated polyester resins are used. However, Kumano resin is prone to deformation and is poor in staining and workability. TDI and MDI types of polyurethane resins are not suitable as road marking materials because they undergo significant discoloration. In addition, non-yellowing types such as HMDI and epoxy resins are expensive. Unsaturated polyester resin has low cost but low elongation rate.

It has the disadvantage of being prone to cracking due to lack of flexibility.

In general, unsaturated polyester resins have a contradictory relationship between elongation rate, malleability, and mechanical strength. Therefore, resins with excellent mechanical strength have poor elongation and flexibility and are relatively brittle, and resins with excellent elongation and flexibility have significantly low mechanical strength. The reinforcing effect of glass fiber or the like may impair the tlIT flexibility and the desired performance may not be obtained. A soft polyester with excellent elongation and malleability can be synthesized using diethylene glycol, adipic acid, etc., but even when wax is used, stickiness may remain on the surface, resulting in poor stain resistance.

Therefore.

The alcohols and acids that can be used are limited, and it may not always be possible to obtain the desired performance.

Therefore, since unsaturated polyester resin has the advantage of being low cost, attempts were made to prevent the disadvantage of unsaturated polyester resin, that is, to improve the elongation rate and flexibility, and to provide a new marking material.

In other words, the present invention is as follows.

(a) organic polyisocyanate tb) unsaturated polyester resin and (C1 filler to component (b), component (a) and component (C) in amounts of 5 to 30% by weight and 5 to 70% by weight, respectively) It relates to marking materials that are combined so that

In the present invention, the organic polyisocyanate of component ta) is a compound having two or more terminal incyanate groups, such as tolylene diisocyanate (TDI), diphenylmethane-4,4'-diincyanate (MDI), xylylene diincyanate (XD I), polyisocyanate compounds such as hexamethylene diisocyanate (HMDI), multimers formed from such polyisocyanate compounds, and polymers derived from such polyisocyanate compounds with two or more isocyanate groups at the terminals. However, aliphatic polyisocyanate compounds such as HMDI or prepolymers derived from these are preferred because they are less likely to yellow.

The prepolymer can be obtained by reacting the above polyisocyanate compound with an alcohol component used as a raw material for the unsaturated polyester resin of component (b) below.

The unsaturated polyester resin of component (b) refers to alpha and beta acids such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid.
- Unsaturated dibasic acids, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid.

It is obtained by reacting an acid component such as a saturated dibasic acid such as cepatic acid or benzoic acid with an alcohol component such as ethylene glycol, diethylene glycol, furopylene gellicol, dipropylene glycol, neopentyl glycol, trimethylolpropane, or hydrated bisphenol. unsaturated polyester, styrene, and methyl acrylate.

It is a mixture of polymerizable unsaturated monomers such as methyl methacrylate and vinyltoluene. Linear unsaturated polyesters are preferred from the viewpoint of flexibility of the coating film, but as raw materials for unsaturated polyesters, monobasic acids such as benzoic acid, trivalent or higher valent acids such as trimellitic acid, pyromellitic acid, etc. carboxylic acid.

A small amount of trihydric alcohol such as tris(hydroxyethyl)isocyanurate can be used as appropriate. Also,
The above polymerizable unsaturated monomer is.

(20 to 60% by weight in the bl component - used. 20% by weight -
Less than #! If the weight exceeds 60% by weight, the coating film tends to shrink, which is not preferable. The hydroxyl value of the unsaturated polyester is 1 to 200 (DaK) in order to react with component (a).
OH/P) is preferably 9% to 20 to
o (WvKOH/)) is preferred.

The filler of component (C) is titanium dioxide.

Inorganic pigments such as zinc white, lithopone, and yellow lead, organic pigments, and extender pigments such as calcium carbonate, talc, kaolin, and silica powder are used.

Tal~(The blending amount of the C1 component is as follows.

(5 to 60% by weight of the organic polyisocyanate as the component (a) is used with respect to the unsaturated polyester resin as the BL component, and 9% is preferably 1θ to 40% by weight.

The lid to be used is appropriately determined within this range, taking into consideration the hydroxyl value of component (b). Less than 5% by weight.

Although the stickiness of the surface was eliminated, no significant effect was observed on mechanical strength. Moreover, if it exceeds 60% by weight, the elongation rate tends to decrease.

The filler is used in an amount of 5 to 70% by weight based on component (b). When the number of 5 layers is less than 1, the hiding property of the coating decreases, and 70
If the weight exceeds t*, the coating film becomes brittle and easily breaks down.

In curing the above composition, organic peroxides commonly used in unsaturated polyester resins, such as methyl ethyl ketone peroxide and benzoyl peroxide, can be used as catalysts.

Furthermore, octenoates and naphthenates of cobalt, manganese, lead, etc. may be used as accelerators. These catalysts,
The amount of accelerator to be used is not particularly limited, but is preferably 0.2 to 2 weight per weight of each unsaturated polyester resin. As a polymerization inhibitor.

Hydroquinone, paratertiary butylcatechol, etc. which are commonly used may also be used.

Curing is usually carried out by pouring into an arbitrary shape and curing at room temperature or by heating.

(a), (bl and (C) components are added to (b) component (
After dispersing component C), it is preferable to further mix component (a) and a curing agent immediately before using the composition. From the viewpoint of storage stability, it is preferable that the tal component or the curing agent and the component (b) are not mixed in advance.

The composition of the present invention can be obtained by using an unsaturated polyester resin in combination with an organic polyisocyanate, resulting in a reaction between hydroxyl groups and incyanate groups in the unsaturated polyester resin.

Alternatively, a structure with excellent elongation, flexibility, and mechanical strength is formed through a reaction between isocyanate and water mixed therein. Also, by adding organic polyisocyanate, the surface becomes less sticky. This may be because the organic polyisocyanate acts as a wax, or because the organic polyisocyanate reacts quickly.

This is thought to be due to the formation of a film of some kind of reactant on the surface layer.

The marking material of the present invention can be used as a road marking material with excellent mechanical strength, elongation rate, and flexibility.

Next, an example of the present invention will be shown.

Example 1 Diethylene glycol 111.3) (1.05 mol).

Adipic acid 43.8) (0.3 mol), phthalic anhydride 7
4f (0.5 mol), hydroquinone o, osy 50
The mixture was reacted in a 0 ml flask at 200°C for 5 hours, 19.6i (0.2 mol) of maleic anhydride was added, and the mixture was reacted at 200°C for 5 hours to obtain an unsaturated polyester with an #R value of 15. 40 parts by weight of styrene was added to 60 parts of unsaturated polyester to obtain an unsaturated polyester resin. To 74.5 parts by weight of this resin, 10 parts by weight of titanium white, 15 parts by weight of calcium carbonate, and 0.5 parts by weight of cobalt naphthenate were added and dispersed using a triple roll to obtain a paint pellet.

1.0 parts by weight of methyl ethyl ketone (-oxide) and 10 parts by weight of HMDI trimer were added to 90 parts by weight of the paint mixture, poured into a prescribed mold, heated at 120°C for 30 minutes, and made into a 1.0 part by weight mixture.
．． A cured coating film of 5.9 was obtained. Table 1 shows the tensile strength, tear strength, elongation rate, flexibility, and presence or absence of surface stickiness of this coating film.

Example 2 1.0 part by weight of methyl ethyl ketone peroxide and 15 parts by weight of HMDI polymer were added to 85 parts by weight of the paint powder obtained in Example 1, poured into a prescribed mold, heated at 120°C for 30 minutes, and made into a 1.0 part by weight coating material obtained in Example 1. A cured coating film of .51111 was obtained.

Table 1 shows the tensile strength, tear strength, elongation rate, III-flexibility, and presence or absence of surface stickiness of this coating film.

Example 3 Paint obtained in Example 1 (180 parts by weight of A, 1.0 parts by weight of methyl ethyl ketone peroxide, 20 parts by weight of HMDI trimer)
Parts by weight were added, poured into a predetermined mold, and heated at 120°C for 30 minutes to obtain a cured coating film with a thickness of 1.5 mm.

Table 1 shows the tensile strength, tear strength, elongation rate, flexibility, and presence or absence of surface stickiness of this coating film.

Example 4 Propylene glycol 2L8) (0.3 mol).

Diethylene glycol 79.5N (0.75 mol).

Phthalic anhydride 103.6) (0.7 mol) and adipic acid 14.6 SL (0.1 mol) were prepared in a 500 d flask.
React at 00°C for 3 hours to produce 0.05? ,
Add 19.6f (0.2 mol) of maleic anhydride and add 200
The mixture was heated at 5° C. to obtain an unsaturated polyester having an acid value of 20 and a hydroxyl value of about 75. This unsaturated polynistiff 0
30 parts by weight of styrene was added to the dense portion to prepare an unsaturated polyester resin. 74.5 parts by weight of this resin and 1 part of titanium white.
0 parts by weight, 15 parts by weight of calcium carbonate, and 0.5 parts by weight of cobalt octenoate were added and dispersed with three rolls to form a coating material (
B) was obtained.

Paint (B) Add 1.0 parts by weight of methyl ethyl ketone (-oxide) to 90 parts by weight, and 10 parts by weight of HMDI
The mixture was poured into a predetermined mold and heated at 100°C for 60 minutes to obtain a cured coating film with a thickness of 1.5 cm. The tensile strength, tear strength, elongation rate, flexibility, and presence or absence of surface stickiness of this coating film are shown in Table 1.

Example 5 Paint obtained in Example 4 (185 parts by weight of B, 1.0 parts by weight of methyl ethyl ketone peroxide, 15 parts by weight of HMDI Sannitai)
Parts by weight were added, poured into a predetermined mold, and heated at 100° C. for 60 minutes to obtain a cured coating film with a thickness of 1.5 mm.

Table 1 shows the tensile strength, tear strength, elongation rate, toughness, and presence or absence of surface stickiness of this coating film.

Example 6 To 80 parts by weight of the paint (B) obtained in Example 4, 1.0 parts by weight of methyl ethyl ketone peroxide and 20 parts by weight of HMDI trimer were added.
Parts by weight were added, poured into a predetermined mold, and heated at 100° C. for 60 minutes to obtain a cured coating film with a thickness of 1.51111 mm.

Table 1 shows the tensile strength, tear strength, elongation rate, flexibility, and presence or absence of surface stickiness of this coating film.

Comparative Example 1 1.0 part by weight of methyl ethyl ketone peroxide was added to 100 parts by weight of the paint body obtained in Example 1, poured into a predetermined mold, heated at 120°C for 30 minutes, and a thickness of 1.51111 was obtained.
A cured coating film was obtained. The tensile strength of this coating film.

Table 1 shows the tear strength, elongation rate, toughness, and presence or absence of surface stickiness.

Comparative Example 2 16 parts of methyl ethyl ketone peroxide was added to 100 parts by weight of the paint obtained in Example 4 (Bl), poured into a predetermined mold, heated at 100°C for 60 minutes, and made to a thickness of 1.5 I
A cured coating film of II was obtained. Table 1 shows the tensile strength, tear strength, elongation rate, flexibility, and presence or absence of surface stickiness of this coating film.

In addition, as the HMDI royal polymer used in Examples 1 to 6, Coronate tic (trade name of Nippon Polyurethane) was used.

As is clear from the following margins, the coating film obtained from the marking material according to the present invention has excellent elongation and flexibility of the unsaturated polyester resin without changing.

Tensile strength and tear strength are significantly improved.

Road marking materials that have excellent durability are required to have high physical properties and excellent elongation and flexibility.9 The marking material of the present invention has these properties.

Claims (1)

[Claims] 1. Component (a) and component (C) are each 5 to 60% by weight of (al organic polyisocyanate (b) unsaturated polyester resin and (C1 filler) to component (b). and 5 to 70 weight.