JPH0366765A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition free from solvent, emitting little odor, exhibiting excellent permeability to a moisture-absorbing structural material, curable within a short time and having excellent water-proofing property and adhesivity to a top-coating material by using a specific compound, an unsaturated ester and a fatty acid amide at specific ratios. CONSTITUTION:The objective composition contains, as main components, (A) 100-70 pts.wt. of a compound of formula (R is H or methyl; R' is 2-13C alkylene or 4-6C oxaalkylene containing two or more segments of >=2C alkylene chain interposing oxygen atom therebetween; n is 0 or 1), (B) 0-30 pts.wt. of an unsaturated ester produced by reacting an epoxy resin with an unsaturated monobasic acid [e.g. (meth)acrylic acid] or the monobasic acid and a polybasic acid (e.g. maleic acid) and (C) 0.01-5 pts.wt. (based on 100 pts.wt. of A+B) of an aliphatic amide (preferably a fatty acid bisamide).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a coating composition that can be directly applied to hygroscopic structures such as wood, paper, pulp, cement, mortar, and concrete.

(Conventional technology) Structural materials such as lumber and cement products for architecture and civil engineering are painted with paint for the purpose of protection and beauty, but since the underlying structural materials are hygroscopic, oil-based Synthetic resin paints have poor adhesion and durability. In particular, in cement products, alkaline efflorescence occurs due to water absorption from the base and moisture absorption, causing discoloration and staining of the top coat. Therefore, the current method is to pre-treat the base with a sealer or primer, and then apply a top coat to prevent smudges. however,
These methods have problems such as poor adhesion between the topcoat material and the sealer or brimer, or no adhesion at all depending on the material of the topcoat material. Japanese Patent Publication No. 61-238861
Among the hygroscopic structures, the publication describes retinal-like capillary voids that are formed volumetrically due to free water left over in the process of water utilization by adding water to cement, gypsum, etc., and structural voids during the growth of wood. A solution paint made by dissolving a resin made by reacting lanolin oil and zinc naphthenate at a ratio of 2:1 with Kijirol, etc., is used to infiltrate and fill naturally occurring voids with water-insoluble substances. be done. However, since this paint uses a solvent, it cannot fill voids sufficiently.

There are problems such as odor caused by the solvent and long drying time.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks, and provides a coating composition that cures in a short time at room temperature without using a solvent and has excellent permeability.

(Means for solving problems) The present invention is.

(&) General formula (I); (However, R represents hydrogen or a methyl group, and R' is an alkylene group having 2 to 13 carbon atoms or two or more alkylene chains having at least 2 carbon atoms. represents an oxaalkylene group having a total number of carbon atoms of 4 to 6, in which the segment is bonded via an oxygen atom, where n is 0 or 1).

(b) 0 to 30 parts by weight of an unsaturated ester obtained by reacting an epoxy resin with an unsaturated basic acid or a polybasic acid.

and (c) a coating composition containing a mixture of fatty acid amide as a main component in an amount of 0.01 to 5 parts based on 100 parts of the total amount of component (a) and (bl component).

The compound represented by the general formula (1) which is the (al component) of the present invention is a known compound such as dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxypropyl acrylate, Examples include pentenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, acrylic ester or methacrylic ester of diethylene glycol monodicyclobentenyl ether, etc. These compounds are disclosed in 9% Publication No. 861-43337. As described in , dicyclopentadiene is subjected to an addition reaction with alkylene glycol or oxaalkylene glycol, and the resulting alkylene glycol monodicyclopentenyl ether or haoxaalkylene glycol monodicyclobentenyl ether is subjected to a condensation reaction with methacrylic acid. It can be produced by transesterification or transesterification with methyl methacrylate.It is also possible to replace methacrylic acid or methyl methacrylate with acrylic acid or methyl acrylate.
As described in Japanese Patent No. 200331, it can also be produced by addition-reacting alkylene glycol monoacrylate or alkylene glycol monomethacrylate to dicyclopentadiene.

(The bl component is used as necessary to impart toughness.

There are no particular restrictions on the epoxy resin used as a raw material for the unsaturated ester component (b). Aromatic epoxy resins such as bis-type epoxy resins, phenol novolak-type epoxy resins, and cresol-novolac-type epoxy resins are preferred because they impart good toughness.

These commercially available products include Epikoat 8281, Epicoat 1001°, Epicoat 1004, manufactured by Shell Chemical Co., Ltd. AER-664H, AER- manufactured by Asahi Kasei Kogyo ■
331, AER-337, manufactured by Dow Chemical Company, E, R
, 330, D, E, R, 660° D, E, R, 664, etc. E, N, 431. manufactured by Dow Chemical Company. D, B, N, 438° Epicoat 152, manufactured by Shell Chemical Co., Ltd. Epicote 154, EPNI 138 manufactured by Chipa. Union Carbide ERL42
11. CY2O3, CY221 manufactured by Ciba Geigy. C.Y.
350. XB2615, CY192. Examples include phenol novolak type epoxy resins such as CY184.

These epoxy resins can be used alone or in combination of two or more, but they can also be used in combination with a low-viscosity epoxy resin to improve workability.

Examples of unsaturated basic acids to be reacted with the epoxy resin include acrylic acid, methacrylic acid, and crotonic acid.

Cinnamic acid, tricyclo(511,0)-4-decene-8
Alternatively, a partially esterified carboxylic acid containing 9 residues and an unsaturated dibasic acid residue as constituent elements can be used.

In addition to the above-mentioned -basic acid, a polybasic acid can be used in combination to further improve toughness and curability.

Polybasic acids that may be used as necessary include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and adipic acid.

Examples include azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and trimellitic anhydride.

As the polybasic acid, a dibasic acid having 12 or more carbon atoms can also be used.Specific examples include dodecanionic acid, commercially available product 5LB-12.
U is a mixture of isomers of an unsaturated dibasic acid having 16 carbon atoms.
LB-20 (also manufactured by Okamura Oil ■), and 5L-20 (also manufactured by Okamura Oil ■), which is a mixture mainly consisting of saturated dibasic acids having 20 carbon atoms.

Furthermore, there are dimerized fatty acids made from tall oil fatty acids, which have 36 carbon atoms and are commonly called dimer acids. A commercially available product of this dimer acid is Embol 1022. Emball 1024 (manufactured by Emery), Versaguim 2
16. Examples include Versadime 288 (manufactured by Dai-ichi General Co., Ltd.) and Haridimer◆200 (manufactured by Harima Kasei Kogyo ■).

The epoxy resin, the unsaturated basic acid and the polybasic acid used as necessary are heated at 60 to 150°C, preferably at 70 to 70°C.
The reaction is carried out at a temperature of 130°C to form an unsaturated ester.

The proportions of the unsaturated basic acid and the polybasic acid used as necessary are preferably such that the carboxyl groups of these acid components and the epoxy groups of the epoxy resin are approximately equivalent.

Here, the (a) component and (b) component are (a) component 1
00 to 70 parts by weight of component (b) and 0 to 30 parts by weight of component (b) are blended so that the total is 100 parts by weight. [b) component is 3
If it exceeds 0 parts by weight, the viscosity becomes high and the structural material to which it is applied is not sufficiently impregnated.

In the present invention, in order to further improve the impregnation strength (cl
Use fatty acid amide. There are two types of fatty acids: saturated fatty acid amides and unsaturated fatty acid amides, both of which can be used. Among these, fatty acid bisamides are preferred because they exhibit particularly good impregnation strength.

Specifically, (C+γH or C0NH)! (C toy), (C
12-Has CONM)! (CHt)t,
(Co Has C0MM)z (CHz)z
.

(C+tHssCONH)x(CHz)z, (
Examples include CtsHuNHCO)t(CHz)s.

These commercially available products include Bisamide, Slipax E, Slipax L, and Slipax O.

Slipax ZOS <1 Nippon Kasei ■Product name).

Tesbaron+ 6500. Desmelon+6900-1O
8, Death Baron◆6400 (all listed above, Kusumoto Kasei ■, product name), etc.

(The Cl component is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of components (a) and (b).

If it is less than 0.01 parts by weight, there is no effect on permeability, and if it exceeds 5 parts by weight, the viscosity increases, making coating work difficult and reducing permeability.

In the present invention, the above-mentioned components (al, (b), and (c)) are essential components, but various additives may be added.

Preferably, an organic peroxide is mixed in to cure the impregnated components.

Examples of organic peroxides include benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide,
Acetylacetone peroxide and the like can be used.

The amount used is preferably from 0.1 to 0.1 to the paint composition.
10 weight units, more preferably 0.5 to 3 weight units.

If it is less than 0.1 part by weight, the amount of radicals generated from the organic peroxide may be insufficient and the coating composition may not be sufficiently cured. It was a cabinet. When it exceeds 10% by weight, the organic peroxide acts as a plasticizer.

Cured resin tends to become soft.

Aniline, N,N-dimethylaniline, N,N-diethylaniline as aromatic amine accelerator.

Toluidine, N,N-di,methyl-p-toluidine.

One or more types of N,N-di(hydroxyethyl)toluidine and the like can be used.

The amount used is preferably in the range of 0.01 to 10 parts by weight, more preferably in the range of 0.1 to 1 parts by weight, based on the coating composition. If the amount used is less than 0.01'' iIL, the accelerating effect will not be sufficient and it will be undesirable. If it exceeds 10% by weight, a plasticizing effect will occur, leading to a decrease in the strength of the cured resin product, which is not preferable.

Furthermore, polyvalent metal salts and/or polyvalent metal complexes can also be added. These are generally desiccants (dryers)
Metal salts of higher fatty acids are well known. For example, polyvalent gold true salts of naphthenic acid and octenoic acid, polyvalent metals and calcium, copper, zirconium, and manganese.

Indicates cobalt, lead, iron, vanadium, etc. Particularly preferred examples include cobalt octenoate and cobalt octenoate.

Examples of polyvalent metal complexes include well-known complexes of acetylacetone, eg, cobalt acetylacetonate, manganese acetylacetonate, and the like.

These are preferably used in a range of 0.01 to 5% by weight in the coating composition, but they act to promote the action of organic peroxides, and if less than 0.01% by weight, The effect is not sufficient, and even if 5-fold fcs is exceeded, no further effect is shown.

The coating composition of the present invention also includes pigments and dyes.

It is also possible to add antioxidants, ultraviolet absorbers, flow control agents, chirotroping agents, and plasticizers as necessary.

The coating composition of the present invention obtained as described above can be used both as a primer and as a top coat.

(Function) The compound (a) Fi represented by the general formula (I) has a low viscosity.

Highly impregnable to adherends without containing any solvent.

It also has a high flash point. Furthermore, the unsaturated ester [b) is well compatible with the fal component and improves adhesion to adherends.

Fatty acid amide te) is partially compatible with component (a) and improves impregnation into the adherend.

The coating composition of the present invention can be applied without using solvents or diluents.
It is possible to eliminate odor and cure in a short time while sufficiently maintaining impregnating properties to adherends.

(Example) The present invention will be explained with reference to Examples, and "parts" in the Examples are parts by weight.

Examples 1 to 4 (1) Synthesis of dicyclopentenyloxyethyl methacrylate 660 parts of dicyclopentadiene, 1 part of ethylene glyfur
60 Part 1 784 parts of halatoluenesulfo + After reacting at 120°C for 4 hours, the temperature was lowered to 80°C, 430 parts of methacrylic acid and 4 parts of para-toluenesulfonic acid were added, and water was distilled off at 100°C. The reaction was allowed to proceed for 5 hours, and the resulting reaction products were neutralized with magnesium oxide. After washing the reactant with water.

It was purified by vacuum distillation.

(2) Synthesis of unsaturated esters 411 parts of methacrylic acid, 453 parts of Ebisu type epoxy resin Epicoat 828 and Epicoat 1001
．． 1136 copies (product name: Shell).

0.4 part of hydroquinone and 4 parts of trimethylbenzylammonium chloride were heated at 100°C for 10 hours to obtain an unsaturated ester with an acid value of 15.

Unsaturated ester, the above dicyclopentenyloxyethyl methacrylate, and Slipax E (ethylene bisstearamide, manufactured by Nippon Kasei ■).

(trade name) or Slipax 0 (ethylene bisoleic acid amide, manufactured by Nippon Kasei ■, trade name) were mixed in the proportions shown in Table 1 to obtain a mixed solution [11 to □□□. For this mixture,
Additionally, 2 parts of 6% cobalt naphthenate (xylene solution),
A coating composition was obtained by mixing 4 parts of cumene hydroperoxide (80%).

This paint composition was applied with a brush to a pavement board (JIS A 5304, moisture 2.5%) at a weight of 0.5 kg/m''.Then, the solvent odor, drying time (dry to the touch), and penetration depth (with the naked eye using a magnifying glass) were measured. Judgment) and water permeability (JIS A6910
) was measured.

The penetration depth and water permeability were tested after being left for 7 days after application.

<Adhesion strength with top coat material> Acrylic lacquer Acrylic Lacquer 60 as top coat material
(manufactured by Atom Kagaku ■) at 0.5 ka/m",
Dry for 7 days at room temperature. Furthermore, the foundation test is JIS
Measured according to K5400. The results are shown in Table 1.

Comparative Example 1 Comparative Example 1 was prepared in the same manner as in Example 1 using only dicyclopentenyloxyethyl methacrylate synthesized in Example 1.

A coating composition was prepared by adding cumene hydroperoxide, and was applied and evaluated in the same manner.

Comparative Example 2 The coating compositions of Examples 1 to 4 were applied to a pavement board in the same manner as in Example 1 using Pulbar (manufactured by Osseo), a commercially available penetrant, as a comparative product. Excellent, and even more odor compared to Comparative Example 2.

Excellent drying and water permeability.

(Effects of the Invention) The coating composition of the present invention does not contain a solvent and has little odor.
It has excellent permeability to hygroscopic structural materials, cures in a short time, has good waterproof properties, and has excellent adhesion to top coat materials. Therefore,
It is also effective as a sealer and brusher and as a regular paint.

Claims (1)

[Claims] 1. (a) General formula (I); ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R represents hydrogen or a methyl group, and R' has 2 to 2 carbon atoms. 13 alkylene group or an oxaalkylene group having a total number of carbon atoms of 4 to 6, in which two or more segments of an alkylene chain having at least 2 carbon atoms are bonded via an oxygen atom, and n is 0 or 1. (b) 0 to 30 parts by weight of an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid or a polybasic acid, and (c) a fatty acid. A coating composition containing as a main component a mixture of amide in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of components (a) and (b). 2. The coating composition according to claim 1, further comprising an organic peroxide. 3. The coating composition according to claim 2, further comprising a polyvalent metal salt and/or a polyvalent metal complex.