JPH08157544A - Method for cold curing of unsaturated polyester resin and/or vinyl ester resin and cold curing agent composition - Google Patents

Abstract

PURPOSE: To reduce the residual monomer content of the cured material and improve the odor by using a curing agent containing a specified peroxycarbonate for cold curing, an unsaturated polyester resin, a vinyl ester resin, etc. CONSTITUTION: A curing agent is produced which contains a metallic soap (e.g. cobalt naphthenate), acetylacetone peroxide, and a peroxycarbonate of formula I (wherein n is 1 or 2; R1 is 1-6C linear or branched alkyl or phenyl when n is 1, and it is ethylene, ethynylene, m-phenylene or p-phenylene when n is 2; and R2 is 3-8C branched alkyl, cyclohexyl or 4-t-butylcyclohexyl) or formula II (wherein m is 2; R3 is hexamethylene or 3-oxypentamethylene; and R4 is 1-6C linear or branched alkyl or phenyl). This curing agent is used for cold curing an unsaturated polyester resin and/or a vinyl ester resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a room temperature curing method for unsaturated polyester resin and / or vinyl ester resin and a curing agent composition.

[0002]

2. Description of the Related Art Reinforced plastics (hereinafter abbreviated as FRP) having glass fiber as a reinforcing material are used for housings such as bathtubs and septic tanks, ships such as fishing boats, yachts, and boats, pulp,
Plant-related products such as tanks and non-FRP,
It has been put to practical use in a wide range of areas such as paints, linings, casting, decorative boards, and laminated boards. Methyl ethyl ketone peroxide (hereinafter referred to as MEK) is used as a curing agent when the unsaturated polyester resin and / or the vinyl ester resin is cured at room temperature.
Abbreviated as P) and acetylacetone peroxide (hereinafter A)
A ketone peroxide such as AP) or a hydroperoxide such as cumene hydroperoxide (hereinafter abbreviated as CHP) and a redox type metal benzoyl peroxide such as cobalt naphthenate (hereinafter abbreviated as BPO). Aromatic tertiary amines such as N, N-dimethylaniline are commonly used in combination.

However, when the above-mentioned curing agent is used for room temperature curing, the amount of the monomer in the cured resin remains for a considerable period of time after curing, and remains in the FRP product depending on the product application. The problem of odor resulting from residual monomers was pointed out. In particular, in applications such as food tanks, water tanks, and water tank linings, odor pollution of food and water due to residual monomers is a problem, and post-heat treatment of products is performed to reduce residual monomers. There is a need. Further, in the case of a large open mold molded product by hand lay-up, lining treatment of a large tank, etc., post-heating treatment is difficult, and its application is practically limited.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the odor pollution caused by the residual monomer, which is brought from the FRP product molded by the conventional room temperature curing method, and eliminates the post-heat treatment of the room temperature cured product. An object of the present invention is to provide a room temperature curing method and a curing agent composition that can be used.

That is, the amount of residual styrene in the FRP product or the lining produced by the molding method at room temperature is reduced to the level achieved only by the heat molding or the post heat treatment at a high temperature for a long time.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that if a specific curing agent is used, the amount of residual monomer in the cured product is significantly increased even if the curing method is performed at room temperature. The present invention has been completed by finding that it can be reduced to

That is, the present invention provides (1) an unsaturated polyester resin and / or vinyl which is characterized by using a metal soap, acetylacetone peroxide and a peroxycarbonate represented by the formula (1) or (2). Room temperature curing method for ester resin

[0008]

Embedded image

(Where n is 1 or 2, when n = 1, R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, and when n = 2, R 1 ₁ represents an ethylene group, an ethynylene group or an m- or p-phenylene group, R ₂ represents a branched alkyl group having 3 to 8 carbon atoms,
It represents a cyclohexyl group or a 4-t-butylcyclohexyl group. )

[0010]

[Chemical 4]

(However, m is 2, R ₃ represents a hexamethylene group or a 3-oxypentanemethylene group, and R 3
₄ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group. (2) Acetylacetone peroxide and a curing agent for unsaturated polyester resin and / or vinyl ester resin, characterized by containing peroxycarbonate represented by the formula (1) and the formula (2) described in the above item 1. Agent composition.

The acetylacetone peroxide referred to in the present invention is generally prepared by charging equimolar amounts of acetylacetone (2,4-pentanedione) and hydrogen peroxide, and adding a diluent such as DMP or N-methylpyrrolidone thereto under an acid catalyst. It is obtained by addition reaction.

As specific examples of the compound represented by the formula (1) or (2), first, as the compound of the formula (1), t-butylperoxyisopropyl carbonate (hereinafter referred to as BIC) is used.
Abbreviated), t-amyl peroxy isopropyl carbonate, t-hexyl peroxy isopropyl carbonate, t-octyl peroxy isopropyl carbonate, α-cumyl peroxy isopropyl carbonate,
2,5-Dimethyl-2,5-di (isopropyloxycarbonylperoxy) hexane, 2,5-dimethyl-
2,5-Di (isopropyloxycarbonylperoxy) hexyne-3, α, α ^/ -di (isopropyloxycarbonylperoxy) -m-diisopropylbenzene, α, α ^/ -di (isopropyloxycarbonylperoxy) -p -Isopropylbenzene, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxy-sec-butyl carbonate, t-butylperoxy-sec-octyl carbonate, t-butylperoxycyclohexyl carbonate, t-butylperoxy -4-t-butylcyclohexyl carbonate or the like, or as the compound of the formula (2), 1,6-bis (t
-Butylperoxycarbonyloxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate) and the like, respectively.

The unsaturated polyester resin referred to in the present invention always contains an unsaturated dibasic acid as one component, and if necessary, a saturated dibasic acid is used in combination with a glycol to heat-dehydrate and condense the reaction product to obtain styrene. It is obtained by diluting with a vinyl monomer such as. Examples of unsaturated dibasic acids that can be used include maleic anhydride, fumaric acid, citraconic acid, chloromaleic acid and the like. Examples of the saturated dibasic acid that can be used include phthalic anhydride, isophthalic acid,
Examples thereof include terephthalic acid, succinic acid, adipic acid and sebacic acid. Examples of glycols that can be used are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and hexanediol.
And bisphenol A, propylene oxide adducts and the like.

The vinyl ester resin referred to in the present invention means
It refers to a product obtained by diluting an equivalent reaction product of a polyepoxide and an α, β-unsaturated monobasic acid with a vinyl monomer. Examples of polyepoxides that can be used are bisphenol A,
Epi-bis type glycidyl ethers such as bisphenol F, novolac type glycidyl ethers, brominated glycidyl ethers, nitrogen-containing polyepoxides such as triglycidyl isocyanurate, phthalic acid, glycidyl esters such as hexahydrophthalic acid, Examples thereof include glycol type glycidyl ether and the like. Examples of unsaturated monobasic acids that can be used include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and sorbic acid. In addition to styrene, examples of vinyl-based monomers that can be used in the above include methyl methacrylate, vinyltoluene, α-methylstyrene, and chlorostyrene.

In the curing of unsaturated polyester resins and vinyl ester resins to which the curing method and curing agent composition of the present invention are applied, reinforcing materials such as glass fibers, fillers such as calcium carbonate, titanium oxide and the like are used. A coloring agent, a release agent such as wax, a polymer such as polystyrene as a low-shrinking agent, etc. can be used in combination, if necessary. The specific method for carrying out is at room temperature, gel coating method, hand lay-up method. It is possible to use a molding method known per se, such as a spray-up method, an RTM method, a casting method, a film method, or a coating by a flow coater method.

The metal soap used in the present invention acts as an accelerator, and examples of the metal soap which can be used include cobalt naphthenate, potassium naphthenate, calcium naphthenate, copper naphthenate, manganese naphthenate, cobalt octenoate, Potassium octenoate, calcium octenoate,
Copper octenoate, manganese octenoate and the like,
Of these, cobalt soaps such as cobalt naphthenate and cobalt octenoate are preferred. Further, β-diketones such as acetylacetone and ethyl acetoacetate, and aromatic tertiary amines such as N, N-dimethylaniline can be used in combination as a promoter (co-promoter), if necessary.

The amount of metallic soap added is 0.1 to 2 parts by weight, preferably 0.3 to 1.5, relative to 100 parts by weight of the resin.
Parts by weight. If necessary, various promoters are used in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the resin.

The acetylacetone peroxide used in the present invention and the compounds of the formulas (1) and (2) act as a curing agent, but the amount of the curing agent added is 0.5 to 100 parts by weight of acetylacetone peroxide. 5 parts by weight, preferably 1 to 3 parts by weight, and 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, of the peroxymonocarbonate of formula (1) and formula (2). is there. Acetylacetone peroxide and peroxycarbonate may be added to the resin separately or may be added to the resin as a premixed curing agent composition.

If necessary, methyl ethyl ketone peroxide and t-butyl hydroperoxide (TB) which are used for room temperature curing of unsaturated polyester resins are also used.
H) and cumene hydroperoxide can be used together.

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of ortho unsaturated polyester resin (Resin 1) Propylene glycol 1 was placed in a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a gas introduction tube and a thermometer.
61 g, maleic anhydride 196 g, phthalic anhydride 296
g was charged and esterified in a nitrogen gas stream at 180 to 205 ° C. to obtain an unsaturated alkyd resin having an acid value of 36.1. Hydroquinone 0.1g, styrene 385g
Was added to obtain an ortho polyester resin (Resin 1).

Synthesis Example 2 Synthesis of Iso-Unsaturated Polyester Resin (Resin 2) Propylene glycol 7 was placed in a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a gas introduction tube and a thermometer.
6 g, neopentyl glycol 104 g, maleic acid 4
Charged 2 g and 90 g of isophthalic acid in a nitrogen gas stream,
The temperature was raised to 200 ° C. over 10 hours with stirring, and stirring was continued at this temperature for 3 hours to complete the reaction.
To obtain unsaturated alkyd resin. Hydroquinone (0.1 g) and styrene (184 g) were added thereto to obtain an iso type unsaturated polyester resin (Resin 2).

Synthesis Example 3 Synthesis of bis type unsaturated polyester resin (Resin 3) In a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a gas introduction tube and a thermometer, propylene glycol 7 was added.
6 g, bisphenol A 224 g, maleic acid 42 g,
90 g of isophthalic acid was charged, the temperature was raised to 200 ° C. in a nitrogen gas stream for 10 hours with stirring, and the stirring was continued at this temperature for 3 hours to complete the reaction, and an unsaturated alkyd resin having an acid value of 30 was obtained. It was Hydroquinone 0.1
g and 184 g of styrene were added to obtain a bis type unsaturated polyester resin (Resin 3).

Synthesis Example 4 Vinyl ester resin (Resin 4)
In a 1 l separable flask equipped with a stirrer, a fractionating condenser, and a thermometer, 550 g of Ebicoat # 1001 (trade name, epoxy resin, Yuka Shell Co., Ltd.), 86 g of methacrylic acid, 0.5 g of hydroquinone, trimethyl Charge benzyl ammonium chloride 2g, 130 ~ 13
The reaction was carried out at 5 ° C. for 3 hours with vigorous stirring. Acid value 9.
The reaction product of No. 4 was initially charged with 300 g of styrene, then 2 l
The content was poured into a beaker and 250 g was added to obtain a vinyl ester resin (Resin 4).

Examples 1 to 12, Comparative Examples 1 to 17 Resin 1 obtained in Synthesis Example 1, metal soaps and a curing agent were blended in a mixing ratio shown in Table 2 to obtain a liquid composition. 10 cm x 1 obtained by impregnating 450 glass mats
A 0 cm, 2-ply FRP (20% by weight of glass content) was prepared at a temperature of 25 ° C. on a glass plate of 30 cm × 30 cm, and allowed to stand at 25 ° C. for 24 hours.

The obtained FRP was cut into small pieces with a diamond cutter, about 3 g thereof was placed in a test tube, 18 ml of dichloromethane and 0.045 g of toluene were added thereto, and the mixture was placed in a cool and dark place for 24 hours, and then the solution was added. The amount of residual styrene was determined by subjecting to gas chromatography. In each table, the residual styrene content (%) is a weight ratio with respect to 100 parts by weight of the cured resin.

In the comparative example, the mixing ratio of each component was based on Table 1, and the treatment was carried out in the same manner as in Examples 1 to 12 except that 6% cobalt naphthenate was used as the accelerator except for BPO.
In the comparative example, dimethylaniline (DMA) is used for BPO. Also, in each table, phr is resin 1
This is parts by weight relative to 00 parts by weight.

In each table, the following curing agents were used. Methyl ethyl ketone peroxide (MEK
Abbreviated as P, Kayamek M is used, acetylacetone peroxide (abbreviated as AAP, trigonox 40 is used), dibenzoyl peroxide (abbreviated as BPO, lucidol 50P is used), t-butyl peroxybenzoate (abbreviated as TBPB, Kayabutyl B is used), t-
Butyl peroxy octoate (abbreviated as TBPO, Kayaester O is used), t-butyl peroxy isopropyl carbonate (abbreviated as BIC, Kaya carvone BIC-)
75), t-butylperoxy-2-ethylhexyl carbonate (abbreviated as BOC, trigonox 11)
7) 1,6-bis (t-butylperoxycarbonyloxy) hexane (abbreviated as BCH, Kayalen 6-70)
), Diethylene glycol-bis (t-butylperoxycarbonate) (DEBC, Kayalen O)
-50). The above is a product of Kayaku Akzo Co., Ltd.

T-Butylperoxycyclohexyl carbonate (abbreviated as BCC), t-amyl peroxyisopropyl carbonate (abbreviated as AIC), t-hexyl peroxyisopropyl carbonate (abbreviated as HIC), t-octyl peroxyisopropyl carbonate (abbreviated as Abbreviated as OIC), 2,5-dimethyl 2,5-di (isopropyloxycarbonylperoxy) hexane (2,5BIC). The above is synthesized and used.

[0031]

[Table 1] Table 1 Residual styrene content in the case of Resin 1 (Comparative Example) Comparative Example 1st curing agent 2nd curing agent Naphthenic acid Residual Sty No. Species addition amount Species addition amount Cobalt addition amount Ren amount 1 MEKP 2phr --0.5 phr 8.5% 2 MEKP 3 phr --0.5 phr 7.8% 3 MEKP 3 phr --1.0 phr 7.5% 4 BPO 5 phr --DMA 0.3 phr 8.2% 5 MEKP 2 phr TBPB 1 phr 0.5 phr 5.2% 6 MEKP 2 phr TBPO 1 phr 0.5 phr 6.3% 7 MEKP 2 phr BPO 2 phr 0.5 phr 7.9% 8 MEKP 2 phr TBH 1 phr 0.5 phr 7.2% 9 MEKP 2 phr AAP 1 phr 0 0.5 phr 5.8% 10 AAP 2 phr − − 0.5 phr 6.3% 11 AAP 3 phr − − 0.5 phr 6.1% 12 AAP 3 phr − − 1.0 phr 5.7% 13 AAP 2 phr TB B 1 phr 0.5 phr 3.2% 14 AAP 2 phr TBPO 1 phr 0.5 phr 4.1% 15 AAP 2 phr BPO 1 phr 0.5 phr 6.1% 16 AAP 2 phr TBH 1 phr 0.5 phr 5.3% 17 AAP 2 phr MEKP 1 phr 0.5phr 5.3%

[0032]

[Table 2] Table 2 Residual Styrene Amount for Resin 1 (Example) Example 1st Curing Agent 2nd Curing Agent Naphthenic Acid Residual Sty No. Species Addition Species Addition Cobalt Addition Ren Quantities 1 AAP 2phr BIC 1phr 0.5phr 0.06% 2 AAP 1phr BIC 1phr 0.5phr 0.09% 3 AAP 1phr BOC 1phr 0.5phr 0.12% 4 AAP 1phr BCH 1phr 0.5phr 0.07% 5 AAP 1phr DEBC 1phr 0.5phr 0.14% 6A AIC 1phr 0.5phr 0.04% 7 AAP 1phr BCC 1phr 0.5phr 0.06% 8 AAP 1phr HIC 1phr 0.5phr 0.08% 9 AAP 1phr OIC 1phr 0.5phr 0.05% 10 AAP 1phr 2.5 BIC 1phr 0.5phr 0.08% 11 AAP 1 phr BIC 1 phr 0.5 phr 0.07% − − TBH 0.5 phr − 12 AAP 0.5 phr BIC 0.5 phr 0.5 phr 0.11% MEKP 0.5 phr TBH 0.5 phr − ( Note) TBH and MEKP were added in Examples 11 and 12 to control heat generation. (Same below)

Examples 13 to 24, Comparative Examples 18 to 34 Examples 1 to 12 and Comparative Examples 1 to 17 except that Resin 2 was used.
The same experiment as above was carried out to measure the amount of residual styrene in the obtained FRP.

[0034]

[Table 3] Table 3 Amount of residual styrene in the case of resin 2 (Comparative example) Comparative example 1st curing agent 2nd curing agent Naphthenic acid Residual sty No. Type addition amount Type addition amount Cobalt addition amount Ren amount 18 MEKP 2phr --0.5 phr 8.3% 19 MEKP 3 phr --0.5 phr 7.9% 20 MEKP 3 phr --1.0 phr 7.8% 21 BPO 5 phr --DMA 0.3 phr 7.4% 22 MEKP 2 phr TBPB 1 phr 0.5 phr 7.1% 23 MEKP 2 phr TBPO 1 phr 0.5 phr 7.4% 24 MEKP 2 phr BPO 2 phr 0.5 phr 8.1% 25 MEKP 2 phr TBH 1 phr 0.5 phr 7.5% 26 MEKP 2 phr AAP 1 phr 0 0.5 phr 6.2% 27 AAP 2 phr − − 0.5 phr 6.4% 28 AAP 3 phr − − 0.5 phr 5.8% 29 AAP 3 phr − − 1.0 phr 5.5% 3 AAP 2 phr TBPB 1 phr 0.5 phr 3.7% 31 AAP 2 phr TBPO 1 phr 0.5 phr 3.9% 32 AAP 2 phr BPO 1 phr 0.5 phr 5.7% 33 AAP 2 phr TBH 1 phr 0.5 phr 5.5% 34 AAP 2 phr MEKP 1phr 0.5phr 5.7%

[0035]

[Table 4] Table 4 Amount of residual styrene in the case of resin 2 (Example) Example 1st curing agent 2nd curing agent Naphthenic acid Residual sty No. Type addition amount Type addition amount Cobalt addition amount Ren amount 13 AAP 2phr BIC 1phr 0.5phr 0.01% 14 AAP 1phr BIC 1phr 0.5phr 0.02% 15 AAP 1phr BOC 1phr 0.5phr 0.01% 16 AAP 1phr BCH 1phr 0.5phr 0.02% 17 AAP 1phr DEBC 1phr 0.5phr 0.03% 1 APR AIC 1phr 0.5phr 0.01% 19 AAP 1phr BCC 1phr 0.5phr 0.03% 20 AAP 1phr HIC 1phr 0.5phr 0.01% 21 AAP 1phr OIC 1phr 0.5phr 0.01% 22 AAP 1phr 2.5 BIC 1phr 0.5phr 0.02% 23 AAP 1 phr BIC 1 phr 0.5 phr 0.03% --- TBH 0.5 phr-24 AAP 0.5 phr BIC 0.5 phr 0.5 phr 0.05% MEKP 0.5 p hr TBH 0.5phr −

Examples 25 to 36, Comparative Examples 35 to 51 Examples 1 to 12 and Comparative Examples 1 to 17 except that Resin 3 was used.
The same experiment as above was carried out to measure the amount of residual styrene in the obtained FRP.

[0037]

[Table 5] Table 5 Remaining Styrene Amount for Resin 3 (Comparative Example) Comparative Example First Curing Agent Second Curing Agent Naphthenic Acid Residual Sty No. Species Addition Species Addition Cobalt Addition Ren Amount 35 MEKP 2phr --0.5 phr 7.2% 36 MEKP 3 phr --0.5 phr 6.9% 37 MEKP 3 phr --1.0 phr 7.0% 38 BPO 5 phr --DMA 0.3 phr 8.5% 39 MEKP 2 phr TBPB 1 phr 0.5 phr 6.8% 40 MEKP 2 phr TBPO 1 phr 0.5 phr 6.7% 41 MEKP 2 phr BPO 2 phr 0.5 phr 7.3% 42 MEKP 2 phr TBH 1 phr 0.5 phr 6.5% 43 MEKP 2 phr AAP 1 phr 0 0.5 phr 6.3% 44 AAP 2 phr − − 0.5 phr 5.3% 45 AAP 3 phr − − 0.5 phr 5.1% 46 AAP 3 phr − − 1.0 phr 5.0% 4 AAP 2 phr TBPB 1 phr 0.5 phr 3.8% 48 AAP 2 phr TBPO 1 phr 0.5 phr 3.9% 49 AAP 2 phr BPO 1 phr 0.5 phr 5.5% 50 AAP 2 phr TBH 1 phr 0.5 phr 4.8% 51 AAP 2 phr MEKP 1phr 0.5phr 5.1%

[0038]

[Table 6] Table 6 Amount of residual styrene in the case of resin 3 (Example) Example 1st curing agent 2nd curing agent Naphthenic acid Residual sty No. Type addition amount Type addition amount Cobalt addition amount Ren amount 25 AAP 2phr BIC 1phr 0.5phr 0.05% 26 AAP 1phr BIC 1phr 0.5phr 0.07% 27 AAP 1phr BOC 1phr 0.5phr 0.09% 28 AAP 1phr BCH 1phr 0.5phr 0.11% 29 AAP 1phr DEBC 1phr 0.5phr 0.12% 30A AIC 1phr 0.5phr 0.06% 31 AAP 1phr BCC 1phr 0.5phr 0.05% 32 AAP 1phr HIC 1phr 0.5phr 0.07% 33 AAP 1phr OIC 1phr 0.5phr 0.09% 34 AAP 1phr 2.5 BIC 1phr 0.5phr 0.12% 35 AAP 1 phr BIC 1 phr 0.5 phr 0.15% --- TBH 0.5 phr -36 AAP 0.5 phr BIC 0.5 phr 0.5 phr 0.17% MEKP 0.5p hr TBH 0.5phr −

Examples 37 to 48, Comparative Examples 52 to 68 Examples 1 to 12 and Comparative Examples 1 to 17 except that Resin 4 was used.
The same experiment as above was carried out to measure the amount of residual styrene in the obtained FRP.

[0040]

Table 7 Table 7. Residual styrene content in the case of Resin 4 (Comparative Example) Comparative Example 1st curing agent 2nd curing agent Naphthenic acid Residual Sty No. Species addition amount Species addition amount Cobalt addition amount len amount 52 MEKP 2phr − − 0.5phr 6 2% 53 MEKP 3 phr − − 0.5 phr 6.1% 54 MEKP 3 phr − − 1.0 phr 6.5% 55 BPO 5 phr − − DMA 0.3 phr 7.4% 56 MEKP 2 phr TBPB 1 phr 0.5 phr 3. 2% 57 MEKP 2 phr TBPO 1 phr 0.5 phr 3.6% 58 MEKP 2 phr BPO 2 phr 0.5 phr 6.0% 59 MEKP 2 phr TBH 1 phr 0.5 phr 6.5% 60 MEKP 2 phr AAP 1 phr 0.5 phr 5.3% 61 AAP 2 phr − − 0.5 phr 4.8% 62 AAP 3 phr − − 0.5 phr 4.5% 63 AAP 3 phr − − 1.0 phr 4.3% 64 AAP 2 phr TBPB 1 phr 0.5 phr 3.1% 65 AAP 2 phr TBPO 1 phr 0.5 phr 3.5% 66 AAP 2 phr BPO 1 phr 0.5 phr 4.6% 67 AAP 2 phr TBH 1 phr 0.5 phr 4.7% 68 AAP 2 phr MEKP 1 phr 0.5phr 4.8%

[0041]

[Table 8] Table 8 Residual Styrene Amount for Resin 4 (Example) Example 1st Curing Agent 2nd Curing Agent Naphthenic Acid Residual Sty No. Species Addition Species Addition Cobalt Addition Ren Amount 37 AAP 2phr BIC 1 phr 0.5 phr 0.15% 38 AAP 1 phr BIC 1 phr 0.5 phr 0.20% 39 AAP 1 phr BOC 1 phr 0.5 phr 0.23% 40 AAP 1 phr BCH 1 phr 0.5 phr 0.21% 41 AAP 1 phr DEBC 1 phr 0.5 phr 0.5 A 0.25% 1 42 phr AIC 1phr 0.5phr 0.11% 43 AAP 1phr BCC 1phr 0.5phr 0.14% 44 AAP 1phr HIC 1phr 0.5phr 0.10% 45 AAP 1phr OIC 1phr 0.5phr 0.18% 46 AAP 1phr 2.5 BIC 1phr 0.5phr 0.19% 47 AAP 1 phr BIC 1 phr 0.5 phr 0.23% --- TBH 0.5 phr -48 AAP 0.5 phr BIC 0.5 phr 0.5 phr 0.25% MEKP 0.5p hr TBH 0.5phr −

Examples 49 to 53, Comparative Examples 69 to 73 The same experiments as in Examples 1 to 12 and Comparative Examples 1 to 17 were carried out, except that an equal mixture of resins 1 to 4 was used as the resin. The amount of residual styrene in the FRP was measured.

[0043]

[Table 9] Table 9 Residual Styrene Amount in Equal Mixture of Resins 1 to 4 (Comparative Example) Comparative Example First Curing Agent Second Curing Agent Naphthenic Acid Residual Sty No. Quantity Ren quantity 69 Resin 1/4 MEKP 3phr − − 0.5 phr 7.5% Equivalent mixture 70 Resin 2/4 MEKP 3phr − − 0.5 phr 7.7% Equivalent mixture 71 Resin 3/4 MEKP 3phr − − 0.5 phr 7.8 % Equivalent mixture 72 Resin 1/2 MEKP 3phr − − 0.5 phr 7.5% Equivalent mixture 73 Resin 1/3 MEKP 3phr − − 0.5 phr 7.6% Equivalent mixture

[0044]

[Table 10] Table 10 Residual Styrene Amount in Equivalent Mixture of Resins 1 to 4 (Example) Example First Curing Agent Second Curing Agent Naphthenic Acid Residual Sty No. Resin Type Addition Type Addition Quantity Ren quantity 49 Resin 1/4 AAP 2phr BIC 1phr 0.5phr 0.05% Equivalent mixture 50 Resin 2/4 AAP 2phr BIC 1phr 0.5phr 0.06% Equivalent mixture 51 Resin 3/4 AAP 2phr BIC 1phr 0.5phr 0.05 % Equivalent mixture 52 Resin 1/2 AAP 2phr BIC 1phr 0.5phr 0.05% Equivalent mixture 53 Resin 1/3 AAP 2phr BIC 1phr 0.5phr 0.06% Equivalent mixture

Examples 54 to 61, Comparative Examples 74 to 79 Residuals in FRP obtained by conducting the same experiments as in Examples 1 to 12 and Comparative Examples 1 to 17 except that cobalt octenoate was used as the accelerator. The amount of styrene was measured.

[0046]

[Table 11] Table 11 Residual Styrene Amount Using Cobalt Octenoate (Comparative Example) Comparative Example First Curing Agent Second Curing Agent Octenic Acid Residual Sty No. Resin Type Addition Type Addition Quantity Cobalt Addition Quantity 74 Resin 1 MEKP 3phr − − 0.5phr 7.8% 75 Resin 2 MEKP 3phr − − 0.5phr 7.9% 76 Resin 3 MEKP 3phr − − 0.5phr 6.9% 77 Resin 4 MEKP 3phr − − 0.5phr 6.1% 78 Resin 1/4 MEKP 3phr − − 0.5phr 7.5% Equivalent mixture 79 Resin 1 AAP 2phr TBPO 1phr 0.5phr 4.1%

[0047]

[Table 12] Table 12 Residual Styrene Amount Using Cobalt Octenoate (Example) Example First Curing Agent Second Curing Agent Octenic Acid Residual Sty No. Resin Type Addition Type Addition Cobalt Addition Ren 54 Resin 1 AAP 2phr BIC 1phr 0.5phr 0.06% 55 Resin 1 AAP 2phr BOC 1phr 0.5phr 0.12% 56 Resin 1 AAP 2phr BCH 1phr 0.5phr 0.07% 57 Resin 1 AAP 2phr DEBC 1phr 0.5phr 0.14% 58 Resin 2 AAP 2phr BIC 1phr 0.5phr 0.01% 59 Resin 3 AAP 2phr BIC 1phr 0.5phr 0.05% 60 Resin 4 AAP 2phr BIC 1phr 0.5phr 0.15% 61 Resin 1/4 AAP 2phr BIC 1phr 0.5phr 0.05% Equivalent blend

[0048]

By using the curing method of the present invention,
An FRP product having a significantly lower residual styrene content can be prepared as compared with the case where a conventional curing system is used for room temperature curing of various unsaturated polyester resins and / or vinyl ester resins.

Claims (2)

[Claims] 1. A room temperature curing method for unsaturated polyester resin and / or vinyl ester resin, which comprises using metal soap, acetylacetone peroxide and peroxycarbonate represented by the formula (1) or (2). [Chemical 1] (However, n is 1 or 2, and when n = 1, R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, and when n = 2, R ₁ is ethylene. Represents a group, an ethynylene group, or an m- or p-phenylene group.
R ₂ represents a branched alkyl group having 3 to 8 carbon atoms, a cyclohexyl group or a 4-t-butylcyclohexyl group. ) (However, m is 2, R ₃ represents a hexamethylene group or a 3-oxypentamethylene group, and R ₄ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group. ) 2. An unsaturated polyester resin and / or a vinyl ester resin, characterized by containing acetylacetone peroxide and the peroxycarbonate represented by the formula (1) and the formula (2) according to claim 1. Hardener composition