JPH01201371A - Composition for surface coating - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in an ability to disperse a pigment and being capable of exhibiting water resistance and cracking resistance, by decreasing the content of unreacted polymerizable unsaturated monocarboxylic acid in an unsaturated epoxy resin below a specified value. CONSTITUTION:60-30pts.wt. polymerizable monomer (B) such as styrene is added to 40-70pts.wt. unsaturated epoxy ester (A) containing at least 0.5 equivalent, desirably, at least 0.7 equivalent of the carboxyl groups of an unsaturated carboxylic acid such as (meth)acrylic acid per equivalent of an epoxy resin (generally, bisphenol diglycidyl ether) and containing 10<-4>mol./g, desirably, 5X10<-5>mol./g or below of unreacted unsaturated monocarboxylic acid and 1-5 pts.wt. (for gel coating) or about 15-25pts.wt. (for surface coating) pigment is added to the above obtained mixture to obtain the title composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a surface coating composition, and further relates to a composition for surface coating such as HT or gel coat or decorative board having good pigment dispersibility.

[Conventional technology]

It has long been widely known that unsaturated epoxy ester resins have excellent water resistance and crack resistance, and these properties can be used to create gel coats and makeup products. Applications to surface coating applications have been investigated.

However, the conventional unsaturated 1 boxy 1 sulfur resin has a poor color balance and as a result, uneven coloring occurs, making it difficult to use alone.

In order to solve this problem, conventionally, an unsaturated 1 boxy 1 sl resin was blended with an unsaturated poly 1 sl resin.

Japanese Patent Publication No. 47-19.880 discloses a composition in which an unsaturated polyvarnish resin is blended with an unsaturated 1-boxy"-sprue resin for gel coating of FRP for bathtubs.

(Problems to be Solved by the Invention) The conventional H method-C, which prevents color unevenness by blending unsaturated polyester resins, causes color unevenness when the content of unsaturated polyester resin is too high. Problems may occur, so there is a practical limit to the blending of unsaturated polynisder resins.Furthermore, blending with unsaturated polyester resins overcomes the inherent water resistance and crack resistance of unsaturated polynisder resins. A problem arises in that the 11mm decreases.

On the other hand, in surface coating applications such as glue-1 and temporary makeup, a higher level of performance has been sought in terms of color unevenness, water resistance, crack resistance, etc.43. In the case of a blend of 1 stell resin, it becomes impossible to satisfy the 1 yen (k).

The object of the present invention is to provide an excellent dispersion of face 11 without blending unsaturated polyester resins, and therefore to
The 114 water quality and crack resistance inherent to the series resin are demonstrated! (An object of the present invention is to provide a composition for coating surfaces.)

(First step to solving the problem) In order to solve this problem, the Ministry of the Invention and others conducted intensive Qgi research (
As a result, the present invention was completed by discovering that an unsaturated 1-bo-1 diester resin containing less unreacted polymerizable unsaturated monocarboxylic acid gives good results.

In the present invention, the unreacted component of the polymerizable unsaturated monocarboxylic acid is 0.
．． 0001 mole/Si or less
Inlet face consisting of resin, polymerizable 7-terminal and face t1
! It is a silk composition for covering.

The amount of unreacted components in the polymerizable unsaturated nocarboxylic liquor is preferably 0.00005 mol/g or less.

The epoxy resin or epoxy compound used as the unsaturated 1-bo-1-syl stellate resin raw stone used in the present invention must contain at least Evo V Lt- pieces in the molecule.

The most commonly used is a diglycidyl ether type of bisphenol synthesized from bisphenol △ and epichlorodidolino.

An example of this is the product name "1 Piquat #827. #828. #834. #8E3/l" from Shell Oil in the United States.

#1001. #1004. #1007゜#1031 etc. Bisphenolbe! One bottle can be listed as one resin.

In addition, phenols and formaldehyde are reacted under an acidic catalyst (Tsurare r'Ji so-called novolac and ↓ Pira 1).
- V-dinovolac resin which can be reacted with -ruhydrin to 1:1 can also be used.

An example of this is the product name DEN-
438, D[EN-448'! An example is q.

Furthermore, by oxidizing the intramolecular divalent bond (waruru, amine, amine), one is rather reactive with fJ organic acid and its anhydride (
By using a rich so-called over-drunk type epoxy resin, or by mixing it with other types of epoxy resin, color retention, surface hardness 11, and air drying in medium temperature curing can be improved. It can be used for right-handed people in terms of sex regulation.

An example of this is 3.4 B) C6- known as Yusox 201 from Ni-A Carbide Company, USA.
Methylsic[l-1-1-nisylmethyl-3',4'
- Ebot Sea 6' - Meburu cyclohekirin carbo 4
: to Syley 1, vinyl cyclohenyl hinge 1-cyto known as Conox 206, dicyclopentagendio, 1-cyto known as Junox 207, etc., J3
As an example, the product name Araldy G sold by FBA of Switzerland is used to improve air drying properties.
Y 245 1bo diacetal resin and US F
One example is 1-boxylated polybutadiene thin film known as Oxilon, sold by MC Company.

Among the above-mentioned epoxy resins, there are Glucoat, IT
Types that cannot be used as rough stones for a.
For example, the US dollar? j Urasha's 1 Pi''-1・#827,9
828”7 is also included, but these t are more molecule r
a17) High ■-Bo:) Resin, i.e. the same? 10) ■Bicoat #1001. #1004. #1007 or the like, or by using an unsaturated polybasic acid that has the property of imparting air drying properties to the unsaturated ester resin, the drying properties can be improved to a sufficient degree for carrying out the present invention. These can also be used in the present invention.

There are also reaction products of epoxy resins or compounds with two or more L-1-cy groups in the molecule and polyester resins with carboxylic acid at the end, which have epoxy groups in the molecule. Can be used as epoxy base F1.

The above polyester resin is a reaction product of dicarboxylic acid and glycol. Examples of dicarboxylic acids include fumaric acid, maleic anhydride, tele, ortho or isophthalic acid, adipine l! 12 etc.; Examples of glycols include commonly known glycols such as blen-glycol, propylene glycol, di-[brene glycol, dipropylene glycol, ne-A-benf-glycol], bisf-L-nor, etc. is used (゛saru.

Furthermore, if necessary, a trifunctional hexamer such as Trimeb Ll-Lube 1' bread may be used.

These (1)-1-1 resins or L-1-1 resins can be used in combination with Class A or in combination.

The polymerizable unsaturated L-nocarboxylic acid is a compound having a T-run double bond and a carboxylic acid in the molecule, and examples thereof include acrylic acid and methacrylic acid.

(meth) Acid components other than acrylic acid (meth)
It is used for adjusting the molecular lattice of acrylate or improving the physical properties such as flexibility, thermal properties, and combustion FI of the cured product. ? If it is a carboxylic acid or carboxylic anhydride, it can be used selectively.

Examples of carboxylic acids and carboxylic anhydrides are 4.
M acid, acetic acid, A acid, naphthenic acid, acetic acid,
1 tI of Noriflic acid or flaxseed fat M'S
Carvone M of IIi; Maleic acid, 21-huccinic acid, adipic acid, phosphorus acid, phthalic acid, fumaric acid, detrahydride, 3゜6-1
Ndomebrende 1 herahit l] phthalic acid, gain-agony,
Alknyl di] succinic acid, itrazo[-1 muphthalic acid,
Detrachlorphthalic acid, 4,5-reso-1111te]-rahido[l phthalic acid, 3.6-[ndomebren] natalophthalic acid, 5-sulfoisofucle resistant 1 helium, trimellitic acid, l-M, or 1.
2.3.4-7 Tracarboxybutanes: monomer maleate, monomer maleate) (2-hydroxy 1
semi-1 esters, etc. of polyhydric nonorboxylic acids such as sufur, or ebren glycol dimaleate, which is ring-opened and added with 2 moles of maleic anhydride to 1 mole of 1-dylene glycolyl, and alcoholic water M group-containing compounds. I can list many things.

[In the present invention] The usage ratio of boxy resin (A) and carboxylic acid component (B) is 1 pot group contained in epoxy resin (Δ) per unit of carboxylic acid component (13) The carboxyl group is 0. It is preferably 5 equivalents or more, more preferably 0.75 equivalents or more.

A ratio in which the carboxyl group is 0.5 molar mass is not preferred because the number of epoxy groups becomes relatively large and side reactions increase.

As the catalyst used for reacting the epoxy resin (Δ) and the carboxylic acid component (13), catalysts commonly used in the art can be used.

Such catalysts include, for example, metal hydroxides such as potassium hydroxide and lithium hydroxide; metal halogens such as ripuram chloride, potassium bromide, tin chloride, potassium chloride, lithium bromide, zinc chloride, and zirconium chloride. Chemicals; ethanolamine, laurylamine, aniline, dibupuramine, heptulfoline, piperidine, diphenylamine,
1 ~ Liedylamine, dimebrunaniline, trinibrenediamine, pyridine, dibupamine salt M salt, dimethylamine chu ML! 2. Amines such as trimethylamine salt M salt, 71-ramethylammonium bromide, trimylbenzylammonium chloride, etc. and their inorganic M
Salts, organic acid salts, and 4th grade salts; amides such as N,N-dimble small lumamide; acid-resistant alkali metals such as acid-resistant potassium and sodium phthalate
tp; small sulfone-resistant classes such as ben-phosphonic acid, triphenylmethylphosphonium iodite, and small sulfonium salts; Examples include Lewis acid type compounds such as wood, etc., and one or more of these compounds can be used.

Among them, compounds selected from the group consisting of amines, their Ta-free salts, t=i silicate salts, and quaternary ammonium salts cause fewer side reactions and can be used as particularly useful catalysts.

The amount of such a catalyst to be used is usually a ratio in the range of 0.001 to 5 parts, where 1 part of the resin (A) and the carboxylic acid component ([3) is 100 parts. This is what I heard.

-[For the reaction between the polycarbonate resin (A) and the carboxylic acid component ([3>, a radical reaction inhibitor is used together with the catalyst described above, which is used in the present invention) J carboxylic acid component (
Since a radical polymerization inhibitor is usually added to the (meth)acrylic acid included in B) to prevent it from polymerizing during storage, a radical polymerization inhibitor is added again when reacting with the epoxy resin (Δ). It is also possible to react without doing so.

However, it can be further added and used if necessary.

Such radical polymerization inhibitors include, for example, p-benzoquinone, naphthoquinone, baratorquinone, 2.5-
Quinones such as diphenyl-p-benzocon, 2,6-dichloroquinone; hydro-4-ninone, p-t-buf-
) Polyhydric phenols such as rehydro↑non, tolhitol, te]-raku-rohydroquinone, pyrogallol, hydro 4:non-7methyl 1-thyl, and their al-1-1-del derivatives, Phenol-10-phenols: Copper salts such as copper naphfonic acid and steel chloride; Picrylic acid, dinitrophenol, trinitrotoluene One or more of these compounds can be used. The use of such a radical inhibition agent 1N]M is,
If the (meth)acrylic acid contains a radical inhibition agent, the combination of the diboxy resin (A) and the carboxylic acid component (B), including the suspension in (a), should be combined for 100 grams. The ratio is usually in the range of 0.0001 to 0.5 parts by weight.

In order to obtain the resin according to the present invention, the above-mentioned boxy resin or compound and a polymerizable unsaturated carboxylic acid may be heated and mixed.

The amount of unreacted polymerizable unsaturated monocarboxylic acid is usually determined by measuring the acid value. By the way, when m of unreacted polymerizable unsaturated monocarboxylic acid is 0,0001 mol/9,
The acid value is 5.6 and 2.8 at 0,00005-t/9. However, as in the case where polyester resin is used as a raw material, salts other than polymerizable unsaturated nocarboxylic acids! If a substance containing 1 g is used, measurement by other means such as gas chromatography is required.

1. The resin that is removed is usually soubrene, α-media soubrene,
It is used by dissolving it in methacrylic viT esters such as vinyltoluene or spool methacrylate-1, acrylic esters such as methyl acrylate, and polymerizable heptamers such as vinyl acetate and diallyl phthalate. At this time, a divinyl monomer such as divinylbenzene may be mixed and used if necessary.

The mixing ratio of the unsaturated epoxy ester resin and the polymerizable monomer is preferably 40 to 70 parts of the unsaturated epoxy ester resin to 60 to 30 parts of the bamboo monomer.

Mixing may be carried out by ordinary stirring. Further, the mixing may be carried out in a pot during or after the reaction of the unsaturated epoxy ester 84 resin.

Pigments include titanium oxide, benzidine yellow, cadmium yellow, butanium yellow, yellow lead, Hanzai yellow, nickel azo yellow, molybdate orange, pembudine orange, cadmium orange, cadmium sulfoserepid orange, cadmium red,
Red Garla, Watching Red, Cardin [8, Bordeaux, Maroon, Quinagritone Red, Cobalt Violet, Quinagliton Violet, Phthalocyanine Green, Chrome Green, Rium Oxide Green, Cobalt Blue, Phthalocyanine Blue, Ultramarine, Iron Blue -Excellence can be mentioned.

The usage m of the pigment varies depending on its use.

For example, when used as a gel coat, unsaturated epoxy ester resin and polymerizable heptamine 100 fflff1
It is sufficient to use about 1 to 5 parts per part, but when used for coating the surface of a decorative board, it is preferably about 15 to 25 parts per part.

Further, the pigments may be mixed by ordinary stirring, or if necessary, they may be mixed by dispersion using a 3-wheel or paint sieve.

The method for using the entrance surface coating composition obtained by the above method is the same as that for ordinary unsaturated polyester 6 (fat).

That is, benzoyl peroxide: (J ide, cumene hydroperoxide, methyl ethyl ketone peroxide
A hand initiator such as Said may be used.

Furthermore, if necessary, a Φ promoting agent such as cobalt naphthenate or dimedylaniline may be added.

[Actual fI+! i example]

The present invention will be specifically explained below with reference to Examples.
The invention is not equally limited by this example.

(Example 1) 1000 g of U.S. Shell Petroleum Epicote #1001, methacrylic'f! t160g, diethylamine salt M salt 0
．． 4 g of hydroquinone and 0.5 g of hydroquinone were reacted at 110°C to form an unsaturated 1-bo-4 diester with an unreacted product of polymerizable unsaturated heptanocarboxylic acid (methacrylic acid) of 0.00009 mol/9. Resin (A) was synthesized.

(Example 2) In the same manner as in Example 1, an unsaturated epoxy with an unreacted product of polymerizable methacrylic acid of 0.00003 E/g and stell resin (B) were synthesized by changing the polymerization time (n). did.

(Big Catch rI43) An unsaturated epoxy Nisderian resin (C) containing 0.000009 mol/g of unreacted polymerizable methacrylic acid was synthesized in the same manner as in Example 1 by changing the polymerization time.

(Comparative Example 1) An unsaturated epoxy ester resin (D) having an unreacted product of polymerizable methacrylic acid of 0.00018 mol/9 was synthesized in the same manner as in Example 1 by changing the polymerization time.

Using unsaturated epoxy ester resins (A) to (D),
Gelcoats (A) to (D>) were prototyped using the following formulations. (The symbols on the gelcoat correspond to the symbols on the raw material unsaturated epoxy ester resin.) (Composition) Unsaturated Evo-t diester resin 60 parts by weight Styrene 40 parts 1 part cadmium yellow 2 parts methyl ethyl ketone peroxide 1,000 parts cobalt naphthenate
0.5ffiffi part (Comparative Example 2) Unsaturated polyester resin XE-155 manufactured by Mitsui Tsukuka Kagaku ■
Using the same formulation as above, a gel coat (E) was experimentally produced.

(Comparative Example 3) The XE-155 and unsaturated epoxy ester resin (A>
A gel coat (F) was experimentally produced using the same mixture as described above.

(Comparative Example 4) The XE-155 and unsaturated 1-boxyester resin (A>
A gel coat (G) was prepared using the same formulation as above.

After gel coats (A) to (G) were cured to a thickness of 2ffll11, color unevenness was observed. Furthermore, using an autoclave, the sample was kept in water at 140° C. for 72 hours, and the water absorption rate was measured. The results are shown in Table 1. As is clear from the table, the composition for several surfaces according to the present invention has no uneven color and has poor water resistance.

(Effects of the Invention) The surface coating composition according to the present invention is an unsaturated epoxy ester resin with improved pigment dispersibility. Since the unevenness was 41, this resin was used in Dokushikawa. There is no need to blend unsaturated polyester resin as in the past, so we use unsaturated polyester resin with excellent water resistance and crack resistance. The right product is 1r, I.

This is a proud invention that provides a composition that is extremely useful as a surface coating composition for glucoat reinforced plastics and decorative laminates.

Claims (1)

[Claims] Unreacted component of polymerizable unsaturated monocarboxylic acid is 0.000
an unsaturated epoxy ester resin having a content of 1 mol/g or less;
A surface coating composition comprising a polymerizable monomer and a pigment.