JP3307036B2 - Colored unsaturated polyester resin composition, paint or gel coat agent, molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a colored unsaturated polyester resin composition and a paint having excellent weather resistance and hot water resistance.
The present invention relates to a gel coating agent and other FRP molding materials.

[0002]

2. Description of the Related Art Conventionally, gel coat paints obtained by adding pigments to unsaturated polyester resins have been used in various applications because of their excellent design properties, moldability, chemical, physical, mechanical, and electrical properties. ing. Its main uses are for FRP for bathtubs, unit baths, boats, fishing boats, tanks, vehicles, housings, etc., and non-FRP for casting, paints, resin concretes, etc. On the other hand, weather resistance,
Hot water.

[0003] Unsaturated polyester resins for gel coat paints which have been used in the past, in most cases, use an aromatic polybasic acid such as phthalic acid as a saturated acid in consideration of the balance between mechanical properties and hot water resistance. When exposed to the outdoors, discoloration such as yellowing and a remarkable decrease in surface gloss occur, resulting in poor weather resistance. These performance improvements are addressed by studying the pigment composition, adding an ultraviolet absorber, and other methods. However, it is not a fundamental solution.

Therefore, as an attempt, a combined use of in-mold coating with a normally dry non-crosslinked fluororesin has been proposed. (See JP-A-4-12829) However, such a fluorine coating has extremely excellent weather resistance, but is inferior in hot water resistance. In addition, it is very expensive and increases the number of molding steps, and is not economically easily accepted.

[0005]

An object of the present invention is to improve the light resistance and weather resistance without impairing the hot water resistance of a cured product obtained from a colored unsaturated polyester resin composition.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the composition of the unsaturated polyester resin. As a result, when the pigment was added, the specific unsaturated polyester resin became light- and weather-resistant. It has been found that they have excellent heat resistance and good hot water resistance, and have completed the present invention.

That is, the present invention relates to an alicyclic saturated acid (however,
Those having an aliphatic polycyclic skeleton more than tricyclodecane
Excluding) , aliphatic unsaturated acids (A-1) and aliphatic
Alcohol, alcohol (A-
Consisting 2) unsaturated polyester (A), to the polymerizable vinyl monomer and (B), comprising the pigment (C) to be
The present invention provides a colored unsaturated polyester resin composition for a covering . Further, a paint or gel coat agent containing a resin composition as a main component. Further, the present invention provides an unsaturated polyester resin composition for coating comprising a reinforcing material (D) and / or a filler (E) and a molded article using the same.

(Constitution) The alicyclic saturated acid and the aliphatic unsaturated acid (A-1) are, specifically, an alicyclic saturated mono- or dibasic acid and an aliphatic unsaturated dibasic acid. Basic acids and the like.

The essential components of the alicyclic saturated monobasic acid include:
For example, cyclohexane carboxylic acid, alicyclic saturated dibasic acid (provided that an aliphatic polycyclic skeleton of tricyclodecane or higher is
[For example, dicarboxytricyclodecane, etc.]
Excluding) include, for example, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
Examples thereof include 1,4 cyclohexanedicarboxylic acid and esters thereof. These may be used alone or in combination of two or more.

Further, it is possible to use an aliphatic saturated dibasic acid in combination within a range that does not lower the weather resistance and hot water resistance depending on the use. For example, oxalic acid, malonic acid, succinic acid,
Adipic acid, sebacic acid, azelaic acid, glutaric acid,
Examples include pimelic acid, suberic acid and esters thereof. These may be used in combination with an essential component as a modifier.

Examples of the aliphatic unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and esters thereof. Preferred are maleic acid, maleic anhydride and fumaric acid. These may be used alone or in combination of two or more.

The alcohols (A-2) which are the raw materials of the unsaturated polyester in the present invention include aliphatic alcohols and alicyclic alcohols such as ethylene glycol and propylene glycol. , Diethylene glycol,
Dipropylene glycol, 1,3-butanediol, 1,4-
Butanediol, 2-methylpropane-1,3-diol, neopentylglycol, triethyleneglycol, tetraethyleneglycol, 1,5-pentaneddiol, 1,6-hexanediol 1,1,4-cyclohexanedimethanol,
Hydrogenated bisphenol A, ethylene glycol alcohol
And other alcohols, etc., and are used alone or in combination.

The vinyl polymerizable monomer (B) used in the present invention has one or more polymerizable double bonds in the molecule, and is not particularly limited. For example, styrene, α used for resins
-Methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diallyl phthalate, triallyl cyanurate, acrylate methacrylate, and the like. , Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol
Rudimethacrylate, neopentylglycol-luji (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate
-G, dipentaerythritol penta (meth) acryle-
And dipentaerythritol hexa (meth) acrylate.

These vinyl polymerizable monomers (B) may be used in combination of two or more.

The pigment (C) used in the present invention includes:
Preferably used for coloring, for example, titanium white, red iron, condensed azo red, titanium yellow, cobalt blue, quinacridone red, carbon black, iron black, ultramarine green, blue, perinone, dark blue, isoindolinone, chrome green , Cyanine blue, green and the like. A material which has excellent ultraviolet stability and does not hinder the curing of the polyester resin is selected, and is blended according to the color tone. These coloring pigments
It can be directly mixed and dispersed in the polyester resin, or added as a color toner previously kneaded with a saturated or unsaturated polyester resin solid within a range that does not reduce weather resistance and hot water resistance.

The resin composition of the present invention is preferably prepared by dissolving 20 to 90 parts by weight of the unsaturated polyester (A) and 80 to 10 parts by weight of the polymerizable monomer (B), and dissolving 100 parts by weight of the pigment. 1 to 50 parts by weight of (C) is dispersed to form a composition.

The alicyclic unsaturated polyester resin of the present invention comprises an alicyclic saturated dibasic acid and an unsaturated dibasic acid, glycol or / and, if necessary, an aliphatic dibasic acid. The reaction product thus obtained is dissolved in a polymerizable monomer, and a pigment is further dispersed to obtain a composition.

It is preferable to add a polymerization inhibitor to the resin composition of the present invention. Examples of the polymerization inhibitor include toluhydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, trihydroquinone, and p-te.
rt-butylcatechol, 2,6-tert-butyl-4-methylphenol and the like. It is 30-1
000 ppm can be added.

Further, a curing accelerator is usually used in the composition of the present invention. As a curing accelerator, a metal compound is added as necessary, and as such a metal compound,
For example, cobalt naphthonate, cobalt octonate,
Divalent acetylacetone cobalt, trivalent acetylacetone cobalt, potassium hexoate, zirconium naphthonate, zirconium acetylacetonate, vanadium naphthonate, vanadium octonate, vanadium acetylacetonate, vanadyl acetyl Acetonate,
Metal compound accelerators generally used for unsaturated polyester resins such as lithium acetylacetonate may be used and used in combination. In addition, other accelerators such as amines, phosphorus-containing compounds, β-diketones And other known accelerators.

The resin composition of the present invention is usually cured by adding a curing agent. The curing agent that can be added is an electron beam curing agent,
One or more types selected from thermosetting agents and the like.

Examples of the electron beam curing agent include halogenated alkylbenzene, disulfide, acetophenone, benzoin ether, benzophenone, and thioxanthone compounds.

The thermosetting agent includes an organic peroxide,
For example, diacyl peroxide-based, peroxyester-based, hydroperoxide-based, dialkyl peroxide-based, ketone peroxide-based, peroxyketal-based,
Known substances such as alkyl peresters and parka-carbonates are used, and specific examples include methyl ethyl ketone peroxide, benzoyl peroxide and the like. These curing agents are appropriately selected depending on kneading conditions, curing temperature and the like.

Further, as the reinforcing material (D) used in the composition of the present invention, for example, glass fiber (chopped strand mat, glass roving cloth, etc.), carbon fiber,
Organic fibers (vinylon, polyester, phenol, etc.),
Metal fiber, etc., and 10 to 70% by weight of FRP
It can be.

The filler (E) used in the composition of the present invention includes, for example, calcium carbonate, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, Alumina powder, silica powder, glass beads, crushed sand and the like can be mentioned, and these can be blended and used as a putty, a sealing agent or a coating material. It is also effective as a material for impregnating and reinforcing cloth, kraft paper and the like.

The resin composition of the present invention can be used for coating, for example,
Paints, Geruko - DOO agent, used as a lining material or the like. In such a case, if necessary, additives such as a flame retardant and an ultraviolet stabilizer may be added. In particular, as additives for further improving weather resistance, ultraviolet absorbers include benzophenone-based, benzotriazole-based, and cyanoacrylate-based compounds, and ultraviolet stabilizers include hindered amine-based compounds, and are appropriately selected and used. .

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Further, “parts” in the text indicates parts by weight.

Production Example 1 Production of Alicyclic Unsaturated Polyester (H-1) 208 parts of neopentyl glycol in a 1 L four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. , 88 parts of propylene glycol, 192 parts of hexahydrophthalic anhydride, and 171 parts of maleic anhydride, and the mixture was heated to 210 ° C. to carry out an esterification reaction.
After the reaction for 400 hours, 400 parts of styrene monomer and 0.1 part of hydroquinone were added, the non-volatile content was 60%, the acid value was 10, and the viscosity was 4.5.
A poise unsaturated polyester resin composition was obtained.

Production Example 2 Production of Alicyclic Unsaturated Polyester (H-2) In the same manner as in Production Example 1, 215 parts of 1,3 cyclohexanedicarboxylic acid was charged into a 1-L flask in place of hexahydrophthalic anhydride and reacted in the same manner. Was. Nonvolatile content 60
%, An acid value of 8, and a viscosity of 4.6 poise.

Production Example 3 Production of Alicyclic Unsaturated Polyester (H-3) In the same manner as in Production Example 1, 215 parts of 1,4-cyclohexanedicarboxylic acid was charged into a 1 L flask in place of hexahydrophthalic anhydride and reacted in the same manner. Was. Nonvolatile content 60
%, An acid value of 7, and a viscosity of 4.6 poise.

Production Example 4 Production of Aromatic Unsaturated Polyester (P-1) In the same manner as in Production Example 1, 185 parts of phthalic anhydride was charged into a 1-L flask in place of hexahydrophthalic anhydride, and reacted similarly. Nonvolatile content 60%, acid value 12, viscosity 5.
A 0 poise resin composition was obtained.

Production Example 5 Production of Aromatic Unsaturated Polyester (P-2) As in Production Example 1, a 1 L flask was charged with 208 parts of neopentyl glycol, 88 parts of propylene glycol and 207 parts of isophthalic acid, and heated at 210 ° C. The reaction was performed up to an acid value of 10. The mixture was cooled to 150 ° C., charged with 171 parts of maleic anhydride, heated to 210 ° C., and subjected to an esterification reaction.
After reacting for 15 hours, 400 parts of styrene monomer and 0.1 part of hydroquinone were added to obtain an unsaturated polyester resin composition having a nonvolatile content of 60%, an acid value of 7, and a viscosity of 5.5 poise.

Production Example 6 Production of Aromatic Unsaturated Polyester (P-3) In the same manner as in Production Example 1, 208 parts of neopentyl glycol, 88 parts of propylene glycol, 207 parts of terephthalic acid, 0.2 part of dibutyltin oxide were placed in a 1 L flask. Five parts were charged and reacted at 210 ° C. to an acid value of 5. After cooling to 150 ° C., 171 parts of maleic anhydride was charged, the temperature was raised to 210 ° C., an esterification reaction was performed, and after 15 hours of reaction, 400 parts of styrene monomer and 0.1 part of hydroquinone were added. An unsaturated polyester resin having an acid value of 7 and a viscosity of 5.8 poise was obtained.

Examples 1-3 and Comparative Examples 1-3 The alicyclic unsaturated polyesters (H
-1 to 3) and aromatic unsaturated polyester (P-1 to
Using 3), a colored resin composition was obtained with the composition shown below.

(Coloring gel coat test formulation) 15 parts of an unsaturated polyester resin 10 parts of titanium white (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) are kneaded with a three-roll mill and dispersed well. Further, 65 parts of an unsaturated polyester resin, 2 parts of finely divided silica (# 200, manufactured by Nippon Aerosil Co., Ltd.) 2 parts, 0.5 part of a naphthenic acid Co solution (Co concentration: 6% by weight), 5 parts of styrene monomer (for adjusting viscosity) And kneaded well with a roll.

The viscosity was adjusted to 20 to 24 ps and the thixotropic degree to 5 to 6. The following tests were carried out using the colored gel coat thus obtained, and the results are shown in Table 1.

Examples 4 to 6 and Comparative Examples 4 to 6 The alicyclic unsaturated polyester (H
-1 to 3) and aromatic unsaturated polyester (P-1 to
Using 3), a colored resin composition was obtained with the composition shown below.

(Coloring gel coat test formulation) 15 parts of an unsaturated polyester resin 5 parts of a quinacridone let pigment (manufactured by Dainippon Ink and Chemicals, Inc.) are kneaded with a three-roll mill and dispersed well. Further, 70 parts of unsaturated polyester resin, 2 parts of finely divided silica (# 200, manufactured by Nippon Aegiril Co., Ltd.) 2 parts of 0.5% naphthenic acid solution (Co concentration: 6% by weight) 5 to 8 parts of styrene monomer (for adjusting viscosity) The mixture was kneaded well with a roll. 20 ~ 24p viscosity
s, the degree of rocking fluctuation was adjusted to 5-6. Using the colored gel coat thus obtained, the following tests were conducted, and the results are shown in Table 2.

Examples 7 to 9 and Comparative Examples 7 to 9 In the same manner as in the above Examples and Comparative Examples, the resin and pigment produced in the above Production Example were titanium yellow (TY-55, Ishihara Sangyo
(Manufactured by Co., Ltd.) was used to obtain a colored resin composition. The following tests were performed using the obtained colored gel coat, and the results are shown in Table 3.

Examples 10 to 12 and Comparative Examples 10 to 12 In the same manner as in the above Examples and Comparative Examples, the resin and pigment produced in the above Production Examples were cyanine blue pigments (Dainippon Ink Chemicals, Ltd.).
(Manufactured by Co., Ltd.) was used to obtain a colored resin composition. The following tests were performed using the obtained colored gel coat, and the results are shown in Table 4.

Comparative Examples 13 to 18 The alicyclic unsaturated polyesters (H
-1 to 3) and aromatic unsaturated polyester (P-1 to
Using 3), a transparent resin composition was obtained with the following composition.

(Transparent gel coat test formulation) 85 parts of an unsaturated polyester resin, 2 parts of fine powder silica (# 200, manufactured by Nippon Aerosil Co., Ltd.) are kneaded with a three-roll mill and dispersed well. Further, 0.5 part of a naphthenic acid Co solution (Co concentration: 6% by weight) and 10 to 13 parts of a styrene monomer (for adjusting viscosity) were mixed and kneaded well with a roll. 20 ~ 24p viscosity
s, the degree of rocking fluctuation was adjusted to 5-6. The following test was conducted using the transparent gel coat thus obtained, and the results are shown in Table 5.

[0042]

[Table 1] Titanium white gel coat

[0043]

[Table 2] Quinacridone red gel coat

[0044]

[Table 3] Titanium yellow gel coat

[0045]

[Table 4] Cyanine blue gel coat

[0046]

[Table 5] Transparent gel coat

1) Method of preparing FRP board for weather resistance and water resistance test 55% methyl ethyl ketone peroxide (1.0%) was added to the gel coats obtained in Examples and Comparative Examples, and the mixture was stirred and uniformly dispersed. (Fricoat FRP, FREKOTE) is applied by spraying onto a glass plate and then at room temperature.
After leaving it for a period of time, it is further cured at 60 ° C. for 30 minutes to obtain a film thickness of about 0.1 mm.
A 5 mm gel coat layer was obtained. After cooling, the resulting coating film, surface mats (S), 450g / m ² glass chopped strand mat (M), 570g / m ² Garasuro - Bing laminating resin to cross (R) (trade name POLYLITE FH-286 , Manufactured by Dainippon Ink and Chemicals, Inc.), and an L-shaped core having a configuration of (S) + (M) + (R) + (M).
They were molded at once so that they overlap at the corner. At this time, 0.2 part of 6% cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide were used. Then, after being left at room temperature for 2 hours, it was further post-cured at 50 ° C. for 3 hours. After cooling, the FRP molded product was peeled off from the glass plate to obtain a test piece.

2) Weather Resistance Test Method A test piece of 50 mm × 50 mm was cut out from the test plate obtained in 1) to prepare a weather resistance test piece. As the weather resistance test method,
Sunshine Weatherometer (WE manufactured by Suga Test Instruments Co., Ltd.)
(L-SUN-HCH-B type).

Test conditions: Temperature 63 ± 3 ° C. Cycle 18 minutes in 120 minutes Rain time 1500 h 3) Evaluation of weather resistance • The color difference of the test specimen after the test was measured. A color difference meter (# 80 manufactured by Nippon Denshoku Industries Co., Ltd.) was used as a measuring instrument. Note that the numerical value of the color difference indicates that the smaller the number, the smaller the degree of discoloration. -The gloss of the test piece after the test was measured, and a three-step evaluation was performed. The measuring instrument used was a gloss meter (Model GM-5 manufactured by Murakami Color Research Laboratory). The measurement angle was 60 degrees. Judgment was evaluated in three steps based on the following criteria.

The test was stopped after 1000 hours if the gloss was visually confirmed and the gloss significantly decreased.

[0051]

4) Heat-resistant water test A 100 mm × 100 mm test piece was cut out from the test plate obtained in 1), and the test piece was attached to a single-sided boiling apparatus having a round window with a diameter of 70 mm and subjected to a heat-resistant water test.

Test conditions: temperature 80 ± 3 ° C. time 1
00h

5) Evaluation of hot water resistance The surface condition of the test piece after the test was visually judged. Little change ○ Blistering has occurred. △ Blistering occurred and there was no gloss ×

[0055]

The resin composition of the present invention has a light resistance of a cured product,
Since it has excellent weather resistance and has hot water resistance, it can be used as an FRP molded product for various applications or a resin for coating.

Since the composition of the present invention has poor weather resistance when no pigment is added, when the pigment is added, the unsaturated polyester resin and the pigment component have a very low sensitizing effect in the photochemical reaction, and It is considered that since the decomposition of the resin that occurs is small, the resin has excellent light resistance and weather resistance, and also has good hot water resistance.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 67/06-67/07 C09D 167/06-167/07

Claims (4)

(57) [Claims] 1. An alicyclic saturated acid (provided that tricyclodeca
, An aliphatic unsaturated acid (A-1), an aliphatic alcohol, and an alicyclic ring.
A colored unsaturated polyester resin for coating comprising an unsaturated polyester (A) comprising an alcohol (A-2) which is an aromatic alcohol, and a polymerizable vinyl monomer (B) and a pigment (C) Composition. 2. A paint or gel coat agent comprising the resin composition of claim 1 as a main component. 3. Unsaturated polyester resin composition according to claim 1, consisting of reinforcing material (D) and / or filler (E) This
And an unsaturated polyester resin composition for coating . 4. A molded article using the unsaturated polyester resin composition for coating according to claim 1.