JPH1143618A - Curing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored curing agent composition having excellent storage stability and used for curable resins such as unsaturated polyesters by including an organic peroxide and a dye having a specified chemical structure. SOLUTION: It is desirable that 0.1-10 wt.%, based on the composition, dye represented by the formula is added to an organic peroxide as a curing agent. It is desirable that this composition is used to cure unsaturated polyesters or vinyl ester resins. The uniform mixing of the mixture can be easily confirmed visually. The organic peroxides are exemplified by room temperature decomposable curing agents such as ketone peroxides (e.g. methyl ethyl ketone peroxide) and thermally decomposable curing agents such as cumene hydroperoxide, benzoyl peroxide and alkyl peresters. The dye represented by the formula is an ink dye known as Color Index Constitution No. 21230.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curing agent composition. More specifically, the present invention relates to a colored curing agent composition containing a specific component used for curing a curable resin such as an unsaturated polyester resin and a vinyl ester resin.

[0002]

2. Description of the Related Art Curable resins, particularly unsaturated polyester resins and vinyl ester resins, are inexpensive and have many excellent properties, and are therefore used in automobile parts, electric parts, housing equipment, housing material septic tanks and the like. It is widely used to produce molded articles.

[0003] Unsaturated polyester resins and vinyl ester resins are usually viscous liquids that cannot be molded as they are, and are hardened by using an organic peroxide as a curing agent. Characteristics are obtained.

[0004] Organic peroxides are generally in the form of liquid, powder or paste, and are frequently used as a curing agent for curing unsaturated polyester resins and vinyl ester resins.

[0005] Curing processes of curable resins such as unsaturated polyester resins and vinyl ester resins are generally classified into two types depending on the curing temperature. Curing agents are also broadly divided into room-temperature curing agents and heat-curing curing agents, depending on the type of organic peroxide that is usually used for them.

In the case of molding at room temperature, a room temperature curing type curing agent is used, the temperature is not controlled, and the curing speed is adjusted by the addition of cobalt naphthenate, cobalt octenoate, dimethyl dimethylate or the like which is usually added as a curing accelerator. This is performed by adjusting the amount of aniline or the like added. When curing by heating, a thermosetting curing agent is used, and the unsaturated polyester resin or vinyl ester resin injected into the mold and the thermosetting curing agent are mixed and heat-treated in an electric furnace. Molded.

[0007]

When an unsaturated polyester resin or a vinyl ester resin is mixed with a curing agent, it is difficult to confirm whether or not they are uniformly mixed because they are a colorless to pale yellow transparent liquid. If curing starts without uniformly mixing the resin and curing agent, uneven curing will occur,
It causes poor appearance such as cracks and whitening. As a method for easily confirming whether or not these resins and the curing agent are uniformly mixed, for example, Japanese Patent Publication No. 32-3387
There is a method described. That is, it is a proposal to add a coloring agent to the curing agent to color the curing agent and visually check whether the resin and the curing agent are uniformly mixed. In this method, the coloring power when the curing agent composition obtained by adding the coloring agent to the resin is sufficient, but since the inorganic pigment is used as the coloring agent, the curing agent composition has storage stability. Poorly, particularly at the time of high temperature in summer, there is a drawback that the amount of active oxygen is remarkably reduced and the curing ability is lowered. Japanese Patent Publication No. 47-1112 proposes coloring a curing agent by adding an oil-soluble dye. In this case, problems such as a decrease in the curing ability in summer and fading of the dye have been improved, but the oil-soluble dyes described in the publication have weak coloring power and are insufficient to color the resin. Therefore, visually confirming the uniform mixing does not sufficiently achieve its purpose.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the colorant of a curing agent used for curing a curable resin such as an unsaturated polyester resin and a vinyl ester resin. As a result, the following formula (1) was obtained. By coloring the curing agent with the dye shown, it can be easily confirmed whether the curing agent is uniformly dispersed in the resin, and it has been found that a colored curing agent composition having excellent storage stability can be obtained. Invented the invention.

[0009]

Embedded image

That is, the present invention provides (1) a colored curing agent composition comprising an organic peroxide and a dye represented by the following formula (1):

[0011]

Embedded image (2) The content of the dye is 0.1 to 10% by weight.
(3) A method for curing an unsaturated polyester resin or a vinyl ester resin, comprising using the colored curing agent composition according to (1) or (2). And a cured product of an unsaturated polyester resin or a vinyl ester resin obtained by the curing method described above.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The dye represented by the formula (1) used in the present invention is commercially available mainly as an ink dye, and has a color index composition number of 2123.
What is known as zero. When this dye is added to the curing agent, it can be used as it is as a powder, but it can also be used as a solution that is dissolved and diluted in a solvent such as an aromatic solvent such as xylene or toluene.

Examples of the organic peroxide usable in the colored curing agent composition of the present invention include, as specific examples of room temperature curing type curing agents, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide and the like. In addition to ketone peroxides, cumene hydroperoxide and the like can be mentioned. Specific examples of the heat-curable curing agent include hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, benzoyl peroxide, and lauroyl peroxide. Oxide, bis-3,
Diacyl peroxides such as 3,5-trimethylhexanoyl peroxide, t-butylperoxy 2-
Alkyl peresters such as ethylhexanoate and t-butylperoxybenzoate, bis (4-t-butylcyclohexyl) peroxydicarbonate and t-
In addition to percarbonates such as butylperoxyisopropyl carbonate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and 1,1-
Peroxy ketals such as di-t-butyl peroxycyclohexane are exemplified. These organic peroxides can be used alone or in combination of two or more in the coloring curing agent composition of the present invention. The colored curing agent composition of the present invention contains 90 to 99.1% by weight of an organic peroxide and 0.1% of a dye.
Each contains 1 to 10% by weight.

The coloring curing agent composition of the present invention may contain, if necessary, phthalic acid esters such as dimethyl phthalate and dioctyl phthalate, adipates such as dioctyl adipate and diisodecyl adipate, and aromatic solvents such as xylene and toluene. And the like can be blended in any ratio as long as the stability and curing performance of the composition are not impaired. Usually, the amount of the solvent used is in the range of 1 to 900 parts by weight based on 100 parts by weight of the curing agent.

In the curing agent composition of the present invention, inorganic fillers such as fine silica powder, talc and calcium carbonate can be used as long as the storage stability and curing performance are not impaired. The filler may be surface-treated with a fatty acid, a silane coupling agent, or the like. Usually, the amount of the inorganic filler used is in the range of 1 to 100 parts by weight based on 100 parts by weight of the curing agent. These inorganic fillers
One or more kinds can be added to and mixed with the curing agent composition of the present invention. By mixing these with the coloring curing agent composition of the invention, a viscous liquid or a paste-like composition can be obtained. Can be provided.

The colored curing agent composition of the present invention is produced by mixing the above-mentioned components. That is, the dye may be added to the organic peroxide and stirred, but in the case of using an inorganic filler and manufacturing in the form of a viscous liquid or paste, kneading with a high-speed disperser such as a dissolver or a planetary mixer is performed. The use of a machine is preferred. Usually, each component is mixed
It is carried out by stirring at 40 ° C. for 5 to 60 minutes. An internal mixer such as a Banbury mixer or a kneader is not preferred in terms of safety.

The colored curing agent composition of the present invention can be used for curing various curable resins. Preferred curable resins are unsaturated polyester resins and vinyl resins. Of these, unsaturated polyester resins use an unsaturated dibasic acid as one component, and if necessary, use a saturated dibasic acid in combination with a glycol to thermally dehydrate and condense the reaction product. It was diluted with a monomer.

The vinyl ester resin is obtained by diluting an equivalent reaction product of a polyepoxide and an α, β-unsaturated monobasic acid with a vinyl monomer such as styrene.

The resin to be cured may be a mixture of an unsaturated polyester resin and a vinyl ester resin.

Next, a method for curing an unsaturated polyester resin or a vinyl ester resin using the colored curing agent composition of the present invention will be described.

First, the room temperature curing method will be described. In this case, the unsaturated polyester resin or vinyl ester resin 10
0.5 to 3 parts by weight of the coloring curing agent composition of the present invention is added to 0 parts by weight, and the mixture is stirred until a uniform colored mixture is obtained. If necessary, a filler used for ordinary resin curing, for example, glass fiber or the like can be added thereto.
When glass fiber is used, the usual amount is 10
It is 1 to 100 parts by weight with respect to 0 parts by weight. Other fillers commonly used for curing resins can be used in a usual manner and in an amount used. The mixture thus obtained is cast into a mold or molded by a method such as spraying, and the curing agent containing a room temperature-curable organic peroxide is allowed to stand still for about 30 minutes to 3 hours, depending on the outside air temperature. . After confirming that the hardness of the resin is developed, the resin is taken out of the mold, and the molded product is further left for about 24 hours to obtain a final product.

In this curing method, a curing accelerator can be used in addition to the colored curing agent composition of the present invention. Specific examples of the curing accelerator that can be used include metal soaps represented by cobalt naphthenate and cobalt octenoate, and tertiary amines such as dimethylaniline. The addition amount is usually in the range of 0.05 to 2 parts by weight in terms of 6% cobalt metal content per 100 parts by weight of the resin.

Next, the heat curing method will be described. In this case, the unsaturated polyester resin or vinyl ester resin 10
0.5 to 3 parts by weight of the coloring curing agent composition of the present invention and, if necessary, a filler are added to 0 parts by weight, and 0 to 40 ° C.
, And the mixture is poured into a molding die at 60 ° C to 1 ° C.
Heat to 50 ° C. to completely cure the resin. Molding temperature is 6
If the temperature is lower than 0 ° C., it takes a long time to cure, and thus the productivity is deteriorated. If the molding temperature exceeds 150 ° C., the molded product may have poor appearance such as burning or blistering. In such a heat curing method, a curing accelerator can be used in combination, as in the case of room temperature curing. It is also possible to adjust the curing speed by using a curing inhibitor as needed.
Specific examples of the curing accelerator that can be used include metal soaps represented by cobalt naphthenate and cobalt octenoate, and tertiary amines such as dimethylaniline.
The addition amount is usually in the range of 0.05 to 2 parts by weight in terms of 6% cobalt metal content per 100 parts by weight of the resin. Specific examples of curing inhibitors that can be used include:
Hydroquinone, 1,4-benzoquinone, 4-t-butylcatechol and the like are used, and the amount of the resin used is 100
It is in the range of 0.05 to 2 parts by weight based on parts by weight.

[0024]

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.

Examples 1 to 4 Using a ribbon mixer at 20 ° C. at a ratio shown in Table 1 until each component (the numerical values indicate parts by weight in the table) is uniform.
After mixing for 30 minutes, a colored curing agent composition of the present invention was obtained. However, in Example 2, a paste-like composition was obtained by mixing using a planetary mixer in the same manner as described above. Here, methyl ethyl ketone peroxide (hereinafter abbreviated as MEKPO; active oxygen content of this product is 10.25%), cyclohexanone peroxide (hereinafter abbreviated as CYHPO; active oxygen content of this product is 8.25%), and acetylacetone peroxide (hereinafter abbreviated as AAPO) The amount of active oxygen was 4.00%.)
As for cumene hydroperoxide (hereinafter abbreviated as CHPO; active oxygen content of 8.40%), Kayamec A, Cyclonox, Trigonox 40 and Kayakumen H manufactured by Kayaku Akzo Co., Ltd. were used. Here, the amount of active oxygen means a value defined by the following equation. Active oxygen content (%) = {(number of peroxide bonds × 16) ÷ molecular weight} × purity (%) In Table 1, O-129 is a compound represented by the formula (1). The product name is Oil Yellow 129. Aerosil 2 used as inorganic filler
00 is silicic anhydride of Nippon Aerosil Co., Ltd., and DOP is an abbreviation for dioctyl phthalate, which is a commercially available plasticizer. Also O
The -129 solution is obtained by adding oil yellow 129 to xylene for 10 times.
It is a dye solution in which the weight% is dissolved.

[0026]

Table 1 ○ Composition and composition ratio Example 1 Example 2 Example 3 Example 4 MEKPO 99.5 CYHPO 85 AAPO 70 CHPO 85 O-129 0.5 2 O-129 solution 10 15 Aerosil 200 13 DOP 20 ○ Properties of the obtained colored curing agent composition Shape Liquid Liquid Paste Liquid Liquid Active oxygen content (%) 10.20 6.97 2.80 7.14

Examples 5 to 8 The test results of the storage stability of the colored curing agent compositions of the present invention obtained in Examples 1 to 4 are shown in Table 2. The test method is described below. That is, 100 g of each of the obtained compositions was weighed into a polyethylene container and stored in a 50 ° C. constant temperature water bath and a 20 ° C. constant temperature bath for 7 days and 1 year, respectively, and the purity retention rate and appearance abnormality (fading, blistering, scumming, The presence or absence of insoluble components) was measured. Even after the elapse of a predetermined period, there is no discoloration, no smudge and no insoluble matter (precipitate), and it is preferable that the blister of this size container is 5 cc or less.

[0028]

Table 2 State of the colored curing agent composition after 50 ° C. for 7 days Example 5 Example 6 Example 7 Example 8 Type of composition Example 1 Example 2 Example 3 Example 4 Active oxygen Amount retention rate (%) 98.7 99.0 98.5 99.1 Appearance of abnormal appearance Fading No None None None Blistering (cc) 000 0 0 No smear None None None None Insoluble content None None None ○ State of colored curing agent composition at 20 ° C./one year Retention rate of active oxygen content (%) 98.0 98.5 97.0 98.4 Abnormal appearance Discoloration None None None None Blistering (cc) 32 10 Dirty None None None None Undissolved None None None None

Examples 9 to 16 Using the colored curing agent compositions of the present invention obtained in Examples 1 to 4, unsaturated polyester resins or vinyl ester resins were cured. That is, first, commercially available 6 parts were added to 100 parts by weight of resin.
% Of cobalt naphthenate was added in an amount of 0.5 part by weight, and then 1 part by weight of the coloring curing agent composition of the present invention obtained in Examples 1 to 4 was added and mixed until uniformly dispersed in the resin. The curing temperatures were 20 ° C and 80 ° C. Curing characteristics are JIS-K
Gelation time (hereinafter abbreviated as GT) according to -6901,
Curing time (hereinafter abbreviated as CT), maximum heat generation temperature (hereinafter PE)
T). An iso resin was used as the unsaturated polyester resin. As a 6% cobalt naphthenate as a curing accelerator, first-class reagent manufactured by Wako Pure Chemical Industries, Ltd. was used. Also, chopped strand # 450, 8 plies,
A laminate was prepared with a glass content of 50%, and the presence or absence of cracking and whitening of the molded product one day after curing was visually confirmed. Examples 9 to 12 use an unsaturated polyester resin, Examples 13 to 16 use a vinyl ester resin, and Examples 9 to 11 and Examples 13 to 15 mix a resin and a curing agent at 20C. The time immediately after performing for 1 minute was measured to obtain GT and CT. The curing temperature was kept at 20 ° C. In Example 12 and Example 16, the mixing of the resin and the curing agent was performed at 20 ° C. for 1 minute, and the mixture was poured into a mold.
The time immediately after putting in the oil bath kept at 80 ° C. was measured to obtain GT and CT. In addition, the mixed state of the resin and the colored curing agent composition was visually confirmed, and the following curing test was performed in a completely uniform state.

[0030]

Table 3 Example 9 Example 10 Example 11 Example 12 Example 12 Composition Type Example 1 Example 2 Example 3 Example 4 GT (min) 16 35 405 CT (min) 45 75 120 12 PET (℃) 120 83 60 155 Presence or absence of cracks None None None None Whitening presence None None None None

[0031]

Table 4 Example 13 Example 14 Example 14 Example 15 Example 16 Kind of composition Example 1 Example 2 Example 3 Example 4 GT (min) 40 17 120 3 CT (min) 85 30 300 8 PET (℃) 120 100 60 162 Presence or absence of cracks None None None None Whitening presence None None None None

From the results in Tables 2, 3, and 4, the colored curing agent composition of the present invention has very good storage stability and excellent curing characteristics, and is caused by uneven mixing of the resin and the curing agent. Gives cured moldings free of cracks and whitening.

[0033]

By using the colored curing agent composition of the present invention, the state of dispersion of the curing agent in the unsaturated polyester resin or vinyl ester resin can be easily visually confirmed. As a result, an excellent cured molded article can be obtained without causing cracks or whitening of the cured molded article due to uneven dispersion of the resin and the curing agent, which often become a problem at room temperature and heat curing.

Claims (4)

[Claims] 1. A colored curing agent composition comprising an organic peroxide and a dye represented by the following formula (1). Embedded image 2. The colored curing agent composition according to claim 1, wherein the content of the dye is 0.1 to 10% by weight. 3. A method for curing an unsaturated polyester resin or a vinyl ester resin, comprising using the colored curing agent composition according to claim 1 or 2. 4. A cured product of an unsaturated polyester resin or vinyl ester resin obtained by the curing method according to claim 3.