JP2001048907A - Benzoyl peroxide composition and curing method using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safely handleable powdery benzoyl peroxide composition having excellent aging stability and weighing performance, a method for curing a thermosetting resin with the composition and a curing method of an acrylic unsaturated monomer composition. SOLUTION: The objective benzoyl peroxide composition is preferably composed of 20-50 wt.% benzoyl peroxide, 5-17 wt.% water and 33-75 wt.% non- hydraulic anhydrous gypsum. The curing method for thermosetting resin or acrylic unsaturated monomer composition is characterized by the use of the benzoyl peroxide composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a benzoyl peroxide composition and a curing method using the same. More specifically, a benzoyl peroxide composition that can be handled safely and is excellent in stability over time and meterability, a method of curing a thermosetting resin using the same, and a method of curing an acrylic unsaturated monomer composition It is about the method.

[0002]

2. Description of the Related Art Benzoyl peroxide has long been used as a polymerization initiator for radically polymerizable ethylenically unsaturated monomers and a curing agent for thermosetting resins. In particular,
The cured product obtained from benzoyl peroxide is excellent in various properties such as mechanical properties, adhesiveness, chemical resistance, heat resistance, etc., and is therefore a curing agent for thermosetting resins represented by unsaturated polyester resins and vinyl ester resins. Is widely used not only alone but also in combination with an aromatic tertiary amine such as N, N-dimethylaniline.

On the other hand, pure benzoyl peroxide is powdery, has high sensitivity to impacts, and has the property that it is explosively decomposed by relatively weak impacts and the detonation at that time is easily propagated. There are safety issues. Therefore,
In order to reduce the danger, it is commercialized as a safe benzoyl peroxide composition by diluting it with water or a plasticizer. Among these benzoyl peroxide compositions, 7
The 5% water-moisture product is widely used as a polymerization initiator for aqueous suspension polymerization because of its excellent handling safety. However, this benzoyl peroxide composition cannot be generally used as a curing agent for a non-aqueous unsaturated polyester resin or an acrylic unsaturated monomer composition. This is because the curability is reduced by the influence of a large amount of water that is inevitably mixed, or the physical properties of the obtained cured product are reduced. Also, a benzoyl peroxide composition diluted with di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) as a plasticizer is used as a curing agent for unsaturated polyester resins because of its excellent safety. However, there is a problem that workability at the time of measurement is extremely poor because the shape is a high-viscosity paste.

As a benzoyl peroxide composition which solves such problems, Japanese Patent Publication No. 48-42052 discloses benzoyl peroxide, water, an inert plasticizer such as dibutyl phthalate, and silica containing a hydrophobic alkyl group. A benzoyl peroxide composition containing is proposed. Although this composition has a lower viscosity than the above-mentioned benzoyl peroxide composition diluted with DOP, it has a new problem that it is still high to be handled as a liquid, and that phase separation occurs over time. . JP-A-11-49748 proposes a benzoyl peroxide composition containing benzoyl peroxide, water, chlorinated paraffin and, if necessary, a phthalate ester. Although this composition is a non-dangerous substance under the Fire Service Law depending on the embodiment, it is excellent in that it can be handled safely, but it is inferior in weighability due to high viscosity and the problem of phase separation over time is completely improved. Had not been.

[0005]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to such problems existing in the prior art.
The purpose is to handle it safely,
It is an object of the present invention to provide a powdery benzoyl peroxide composition excellent in stability over time and measuring property, a method for curing a thermosetting resin using the same, and a method for curing an acrylic unsaturated monomer composition.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that by adding water and an inorganic filler to benzoyl peroxide,
It has been found that a powdery benzoyl peroxide composition having high safety and excellent stability over time and weighability can be obtained,
The present invention has been completed.

That is, a first invention is a benzoyl peroxide composition containing benzoyl peroxide, water and an inorganic filler. A second invention is a benzoyl peroxide composition containing 20 to 50% by weight of benzoyl peroxide, 5 to 17% by weight of water and 33 to 75% by weight of an inorganic filler. A third invention is the benzoyl peroxide composition according to the first invention or the second invention, wherein the inorganic filler is non-hydraulic anhydrous gypsum. A fourth invention provides a method for curing a thermosetting resin using a curing agent, wherein the curing agent is the benzoyl peroxide composition of any one of the first to third inventions. Is the way. Fifth
The invention relates to a method for curing an acrylic unsaturated monomer composition using a curing agent, wherein the curing agent is the benzoyl peroxide composition of any one of the first to third inventions. This is a method for curing a saturated monomer composition.

[0008]

Embodiments of the present invention will be described below in detail. The benzoyl peroxide composition of the present invention is a powdery benzoyl peroxide composition and contains benzoyl peroxide, water and an inorganic filler as essential components.

The benzoyl peroxide used for producing the benzoyl peroxide composition of the present invention is a known peroxide, and a commercially available product can be easily obtained. Pure products are often treated as wet products due to the high risk of water, and are usually marketed as 75% water wet products, but use 75-85% water wet products before purity adjustment in the manufacturing process. You can also. Therefore, the water contained in the benzoyl peroxide composition of the present invention is usually brought in from a water-wet product of benzoyl peroxide, but can be added separately.

Next, examples of the inorganic filler include non-hydraulic anhydrous gypsum, calcium carbonate, barium sulfate, clay, silica, talc, aluminum hydroxide and the like, and one or two kinds selected from these groups. The above is used. In the benzoyl peroxide composition of the present invention containing water as an essential component, a non-hydraulic anhydrous gypsum (chemical name refers to anhydrous calcium sulfate) which is excellent in water content is particularly preferable among the inorganic fillers described above. . Note that anhydrous gypsum is roughly classified into two types, that is, hydraulic and non-hydraulic, and non-hydraulic anhydrous gypsum is also called type II anhydrous gypsum and dead calcined gypsum.

In the benzoyl peroxide composition of the present invention, the content of benzoyl peroxide is preferably 20 to 50% by weight, the content of water is preferably 5 to 17% by weight, and the content of inorganic filler is The amount is preferably between 33 and 75% by weight. Further, by adjusting the amount of each component occupied in the benzoyl peroxide composition, it can be made a non-dangerous substance under the Fire Service Law. That is, the general tendency can be achieved by reducing the content of benzoyl peroxide, increasing the content of water, and increasing the content of the inorganic filler. Further, in the benzoyl peroxide composition of the present invention, a coloring agent such as a pigment or a dye, BHT (2,6-di-tert-butyl-P-cresol) is used as long as the performance is not impaired.
It is also possible to add an antioxidant such as

The benzoyl peroxide composition of the present invention can be produced, for example, as follows. A commercially available 75% water-containing benzoyl peroxide and an inorganic filler are mixed at a predetermined ratio using a mixer such as a planetary mixer, a pony mixer, a Nauter mixer or a tumbler, and if necessary, a suitable mesh sieve. By passing through a sieve, a uniform powdery benzoyl peroxide composition can be produced.

The benzoyl peroxide composition of the present invention can be used as a curing agent for a thermosetting resin or an acrylic unsaturated monomer composition. Among them, the thermosetting resin contains a component having two or more radically polymerizable unsaturated groups in one molecule as an essential component, and any one can be used as long as it can be made three-dimensional by polymerization. Specific examples include, for example, unsaturated polyester resins and vinyl ester resins. Of these, unsaturated polyester resins are obtained by subjecting unsaturated dibasic acids and polyhydric alcohols to a combination of saturated dibasic acids, if necessary, by heating and dehydration-condensation at a specific ratio, and then subjecting the unsaturated polyester obtained by esterification to radical polymerization. It is a liquid resin dissolved in an unsaturated monomer (hereinafter simply referred to as a monomer), and any known resin can be used.

The unsaturated dibasic acid includes, for example, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and one or more selected from these groups are used. Examples of the saturated dibasic acid include aromatic dibasic acids such as phthalic anhydride, orthophthalic acid, isophthalic acid, and terephthalic acid, adipic acid, succinic acid, and aliphatic dibasic acids such as sebacic acid. One or more selected from the group is used. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, and ethylene oxide of hydrogenated bisphenol A. Or propylene oxide adducts, and one or more selected from these groups are used. As the monomer, for example, styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene, styrene derivatives such as divinylbenzene,
Methyl methacrylate, 2-ethylhexyl methacrylate, alkyl esters of acrylic acid or methacrylic acid such as butyl acrylate, vinyl acetate, vinyl esters such as vinyl propionate, acrylic acid, methacrylic acid, diallyl phthalate, and the like, One or two or more selected from these groups are used.

The preferred constitutional ratio between the unsaturated polyester, which is a constituent component of the unsaturated polyester resin, and the monomer is 30 to 80% by weight of the unsaturated polyester and 70 to 20% by weight of the monomer. When the content of the unsaturated polyester is less than 30% by weight and the content of the monomer exceeds 70% by weight, the mechanical properties of the cured product of the unsaturated polyester resin obtained therefrom tend to decrease. On the other hand, when the amount of the unsaturated polyester exceeds 80% by weight and the amount of the monomer is less than 20% by weight, the viscosity of the unsaturated polyester resin obtained therefrom tends to increase, and the workability tends to deteriorate.

On the other hand, a vinyl ester resin is also called an unsaturated epoxy resin or an epoxy acrylate resin. The epoxy group of an epoxy resin having two or more epoxy groups in one molecule has an epoxy group such as acrylic acid or methacrylic acid. A liquid resin in which a reaction product (hereinafter abbreviated as epoxy acrylate) obtained by ring-opening addition of a monoester of a saturated monobasic acid or an unsaturated dibasic acid such as maleic acid or fumaric acid is dissolved in a monomer. Yes, any known one can be used.

As the epoxy resin having two or more epoxy groups in one molecule, any of known epoxy resins can be used. Specifically, for example, bisphenol A, bisphenol F or bisphenol S and epichlorohydrin are synthesized from epichlorohydrin. Bisphenol A epoxy resin, bisphenol F epoxy resin or bisphenol S epoxy resin, or a phenol synthesized from epichlorohydrin and a so-called phenol novolak resin obtained by reacting phenol with formaldehyde in the presence of an acidic catalyst. Cresol novol synthesized from epichlorohydrin and so-called cresol novolak resin obtained by reacting novolak epoxy resin and cresol with formaldehyde in the presence of an acidic catalyst Novolak epoxy resins such as click-type epoxy resins.

As the monomer, any of the above-mentioned monomers in the unsaturated polyester resin can be used, and one or two or more selected from these groups are used. A preferred composition ratio of the epoxy acrylate, which is a component of the vinyl ester resin, and the monomer is such that the epoxy acrylate is 30 to 90% by weight and the monomer is 70 to 10% by weight.
It is. If the epoxy acrylate content is less than 30% by weight and the monomer content exceeds 70% by weight, the cured product of the vinyl ester resin obtained therefrom tends to have poor corrosion resistance and heat resistance. On the other hand, when the amount of the epoxy acrylate is more than 90% by weight and the amount of the monomer is less than 10% by weight, the viscosity of the vinyl ester resin obtained therefrom tends to be high, and the workability tends to deteriorate.

As the acrylic unsaturated monomer composition, any one containing an acrylic unsaturated monomer as an essential component can be used. Examples of the acrylic unsaturated monomer include (meth) acrylic acid or an ester thereof. Specific examples of (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid Alkyl esters of (meth) acrylic acid such as lauryl; cycloalkyl esters of (meth) acrylic acid such as cyclohexyl (meth) acrylate; glycidyl (meth) acrylate; and the like. More than one species is used. The acrylic unsaturated monomer composition contains a polyfunctional unsaturated monomer having two or more radically polymerizable unsaturated groups in one molecule in an amount of 30% by weight or less. be able to. Specifically, as a polyfunctional acrylic unsaturated monomer,
For example, ethylene glycol di (meth) acrylate,
Alkylene glycol di (meth) acrylates such as 1,3-propylene glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) Examples thereof include acrylate and vinyl (meth) acrylate, and one or two or more selected from these groups are used.

The acrylic unsaturated monomer composition further includes unsaturated monobasic acids such as crotonic acid, unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid, and unsaturated dibasic acids such as these. Monoesters of acid, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, t-butylstyrene and chlorostyrene, and vinyl esters such as vinyl acetate and vinyl propionate in an amount of 30% by weight or less. it can.

The acrylic unsaturated monomer composition may be an acrylic syrup obtained by dissolving the above-mentioned prepolymer of the acrylic unsaturated monomer in the acrylic unsaturated monomer. Any known acrylic syrup can be used.

When the benzoyl peroxide composition of the present invention is used as a curing agent for a thermosetting resin or an acrylic unsaturated monomer composition, for example, t-butyl peroxybenzoate or t-butyl peroxy-2 A known organic peroxide such as -ethylhexanoate may be used in combination. In general, at a temperature of 60 ° C. or higher, the benzoyl peroxide composition of the present invention can be used alone or in combination with the above-mentioned known organic peroxide to cure a thermosetting resin or an acrylic unsaturated monomer composition. On the other hand, 60 ° C
With less than curing, for example, N, N-dimethylaniline,
Generally, an aromatic tertiary amine such as N, N-dimethyl-p-toluidine is used in combination as a promoter.

When the benzoyl peroxide composition of the present invention is used as a curing agent for a thermosetting resin or an acrylic unsaturated monomer composition, the amount added depends on the curing temperature and the desired curing time. As a pure component of the peroxide, preferably 0.1 to 100 parts by weight of the thermosetting resin or the acrylic unsaturated monomer composition.
It is 5 parts by weight, more preferably 0.3 to 4 parts by weight. If the amount of pure benzoyl peroxide added is less than 0.1 part by weight, the curing time will be extremely long and the curing will not be completed. On the other hand, when the pure addition amount is 5
When the amount exceeds the weight part, the effect of the increased amount is not seen, and it is not practical.

In the case of curing at a temperature lower than 60 ° C., N, N
The amount of addition when an aromatic tertiary amine such as -dimethylaniline or N, N-dimethyl-p-toluidine is used as an accelerator varies depending on the amount of the benzoyl peroxide composition added and the curing temperature. It is preferably 0.05 to 2 parts by weight based on 100 parts by weight of the curable resin or the acrylic unsaturated monomer composition.

In the curing of a thermosetting resin or an acrylic unsaturated monomer composition using the benzoyl peroxide composition of the present invention, for example, glass fiber, carbon fiber and the like are used for the purpose of improving the mechanical strength of the cured product. And inorganic fibers such as aramid fibers and polyester fibers can be used as the reinforcing material. Examples of the form of the reinforcing material include chopped strands, chopped strand mats, roving cloths, surface mats, and nonwoven fabrics.

Further, if necessary, a polymerization inhibitor, a filler, a coloring agent, a low-shrinking agent and the like can be added. Examples of the polymerization inhibitor include t-butylcatechol and hydroquinone. Examples of the filler include calcium carbonate, barium sulfate, clay, silica, talc, silica sand, aluminum hydroxide, and glass frit. Examples of the colorant include various organic dyes or inorganic pigments, and examples of the low shrinkage agent include a thermoplastic homopolymer or copolymer.

Curing of a thermosetting resin using the benzoyl peroxide composition of the present invention can be performed, for example, as follows. At room temperature of -5 to 35 ° C, 0.05 to 2 parts by weight of an accelerator such as N, N-dimethylaniline is added to 100 parts by weight of the unsaturated polyester resin and mixed, and the benzoyl peroxide composition of the present invention is further treated with benzoyl peroxide. By adding and mixing so as to be 0.1 to 5 parts by weight as a pure content of the peroxide, it can be cured in several minutes to several hours. Also, the benzoyl peroxide composition of the present invention is added and mixed with 100 parts by weight of the unsaturated polyester resin so as to be 0.1 to 5 parts by weight as a pure component of benzoyl peroxide, and is mixed at 60 ° C. or more, preferably 80 ° C.
By heating as described above, curing can be completed in several minutes to several tens of minutes.

On the other hand, the curing of the acrylic unsaturated monomer composition (acryl syrup) using the benzoyl peroxide composition of the present invention can be carried out, for example, as follows. Acrylic syrup 10 at room temperature of -5 to 35 ° C
An accelerator such as N, N-dimethylaniline is added in an amount of 0 part by weight.
By adding and mixing the benzoyl peroxide composition of the present invention in an amount of 0.1 to 5 parts by weight as a pure component of the benzoyl peroxide, the composition is cured in several minutes to several hours. be able to.
Further, the benzoyl peroxide composition of the present invention is added to and mixed with 100 parts by weight of acrylic syrup so as to be 0.1 to 5 parts by weight as a pure component of benzoyl peroxide, and heated to 60 ° C. or higher, preferably 80 ° C. or higher. By doing so, the curing can be completed in several minutes to several tens of minutes.

[0029]

EXAMPLES The present invention will be described more specifically with reference to Examples, Reference Examples and Comparative Examples. In these examples,% and parts represent% by weight and parts by weight, respectively.

Example 1 In a kneader having a capacity of 1 liter, 400 g of a 75% water-wet product of benzoyl peroxide (hereinafter abbreviated as BPO) (manufactured by NOF CORPORATION, trade name: Niper BW) was used as an inorganic filler. 350 g of type II anhydrous gypsum (trade name: D-101A, manufactured by Noritake Company Limited) was weighed and mixed for 15 minutes. Next, after passing through a 20-mesh sieve, the mixture is further mixed by a kneader for 10 minutes to obtain a powdery BPO composition (composition ratio: BPO / water / II type anhydrous gypsum = 40% / 13.3%). /46.7%) 740 g
I got When three points were arbitrarily sampled from this and the amount of active oxygen was measured by the iodometry method,
The average value is 2.65%, the standard deviation value is 0.01%,
It was confirmed that the composition was uniform. The amount of active oxygen in this sample was calculated as the theoretical amount of active oxygen of BPO (6.61%).
The calculated purity was 40.1%.

Example 2 A powdery BPO composition (composition ratio: BPO / BPO) was prepared in the same manner as in Example 1 except that the amounts of the 75% water-moistened BPO and the type II anhydrous gypsum were changed to 300 g and 450 g, respectively. Water / II
(Anhydrous gypsum = 30% / 10% / 60%) 745 g was obtained. The average value of the amount of active oxygen of this BPO composition was 1.9.
8% and a standard deviation value of 0.00% were uniform.
The BPO purity was 30.0%.

Example 3 A powdery BPO composition (composition ratio: BPO / BPO) was prepared in the same manner as in Example 1 except that the amounts of the 75% water-moistened BPO and the type II anhydrous gypsum were changed to 500 g and 250 g, respectively. Water / II
Type anhydrous gypsum = 50% / 16.7% / 33.3%) 740
g was obtained. The active oxygen content of this BPO composition was uniform, with an average value of 3.29% and a standard deviation value of 0.01%. The BPO purity was 49.8%.

Reference Example 1 Niper BW manufactured by NOF Corporation, which is a 75% water-wet BPO product, was used as it was.

Reference Example 2 Nipper BO manufactured by NOF Corporation, a 50% DOP diluted product of BPO, was used as it was. The shape of the BPO composition is a high-viscosity paste.

Reference Example 3 According to the method described in JP-B-48-42052,
PO 40%, water 10%, dibutyl phthalate 48% and hydrophobic alkyl group-containing silica (Nippon Aerosil Co., Ltd.)
BPO composition (BPO purity: 40.1%) which is a viscous liquid composed of 2% (trade name: Aerosil R972). The viscosity of this BPO composition was measured using a BM type viscometer (Rotor No. 3, rotational speed: 60 rpm, manufactured by Tokimec Co., Ltd.).
m) was 1200 mPa · s.

Reference Example 4 According to the method described in JP-A-11-49748,
BPO composition (BPO purity: 39.8) which is a viscous liquid composed of 40% PO, 10% water, 12% chlorinated paraffin (manufactured by Ajinomoto Co., Inc., trade name: Empara K-43), and 38% dibutyl phthalate. %). This BP
When the viscosity of the O composition was measured with a BM viscometer in the same manner as in Reference Example 3, it was 800 mPa · s.

Performance Evaluation 1 Each of the BPO compositions of the present invention obtained in Examples 1 to 3 was put in a polyethylene bag laminated with nylon in an amount of 100%.
g and stored in a thermostat at 40 ° C. On the other hand, Reference Example 2
Each of the conventional BPO compositions described in Nos. 1 to 4 was placed in a 200 ml glass container in an amount of 100 g, and similarly stored in a 40 ° C. thermostat. Then, the presence or absence of phase separation and the change in purity over time were examined, and the results are shown in Tables 1 and 2.

[0038]

[Table 1]

[0039]

[Table 2]

From Tables 1 and 2, it can be seen that the conventional BPO composition shows a phase separation and a decrease in purity over time, whereas the BPO composition of the present invention shows no change in purity and shows a stability with time. It turned out to be excellent.

Performance evaluation 2 The BPO of the present invention obtained in Examples 1 to 3 according to the Fire Defense Law
The composition and the conventional BPO composition described in Reference Examples 1 to 4 were subjected to a pressure vessel test and a thermal analysis with a differential scanning calorimeter, and the flash point and the heat of combustion were measured. Tables 3 and 4 show the results.
It was shown to.

[0042]

[Table 3]

[0043]

[Table 4]

As shown in Tables 3 and 4, the BPO compositions of the present invention (Examples 1 to 3) and the BPO compositions described in Reference Examples 3 and 4 were classified into Class 5 self-reactive substances and Class 2 flashes according to the Fire Service Law. Solid, 4th
It did not correspond to any of the flammable liquids and was determined to be non-dangerous. Therefore, it can be handled safely. On the other hand, the BPO compositions described in Reference Examples 1 and 2 both corresponded to Class 5 self-reactive substances (described as Class 5 Class 2 in the table) under the Fire Service Law. Therefore, care must be taken in handling. In addition, in the judgment by the Fire Service Law of organic peroxides, 1 m
In a pressure vessel test with an orifice diameter of m, if the number of bursts is 4 or less out of 10 tests, and if it is determined to be non-explosive by thermal analysis, it falls under Class 5 self-reactive substance do not do. Further, if it is not liquid at 40 ° C. and has a flash point of 40 ° C. or higher, it does not correspond to the second class flammable solid. Furthermore, the flash point is 100 ° C or more and 200
If the temperature is less than ° C and the heat of combustion is less than 34 kJ / g, it is determined to be non-dangerous.

Examples 4 to 6 The BPO compositions obtained in Examples 1 to 3 as the curing agent and N, N-dimethylaniline as the curing accelerator were mixed in the amounts shown in Table 5 to obtain orthophthalic acid. Acid-based unsaturated polyester resin (manufactured by Takeda Pharmaceutical Co., Ltd., trade name:
JI conducted a curing test at 25 ° C for
The gelation time (hereinafter abbreviated as GT) is determined according to the test method of the room temperature curing property specified in SK-6901.
The minimum curing time (hereinafter abbreviated as CT) and the maximum heat generation temperature (hereinafter abbreviated as PET) were determined. And the Barcol hardness of the obtained hardened | cured material was measured according to JIS-K-6911 using the Barber hardness meter (type GYZJ934-1) made by Barber Coleman. The criteria for determining the measurability at the time of adding the curing agent to the unsaturated polyester resin were as follows. When the BPO composition is added to 100 g of the unsaturated polyester resin, if the time required to accurately measure the required amount of the BPO composition is less than 30 seconds, it is determined that the measurement property is good, When the time was 30 seconds or more and less than 1 minute, the weighing property was determined to be slightly poor, and when it was 1 minute or more, the weighing property was determined to be poor.

[0046]

[Table 5]

Comparative Examples 1 to 4 A curing test of an orthophthalic unsaturated polyester resin at 25 ° C. was carried out in the same manner as in Example 4 except that the BPO compositions described in Reference Examples 1 to 4 were used as curing agents. The Barcol hardness of the obtained cured product was measured. Also,
The weighability at the time of adding the curing agent to the unsaturated polyester resin was examined. Table 6 shows the results.

[0048]

[Table 6]

Examples 7 to 9 The BPO compositions obtained in Examples 1 to 3 were added and mixed as curing agents in the amounts shown in Table 7 to obtain a mixture of the orthophthalic unsaturated polyester resin used in Example 4. A curing test at a temperature of ° C. was performed in accordance with a test method for high-temperature curing properties specified in JIS-K-6901, and GT, CT and PET were determined. Then, the Barcol hardness of the obtained cured product was measured in the same manner as in Example 4. Table 7 shows the results.

[0050]

[Table 7]

Comparative Example 5 A curing test of an orthophthalic unsaturated polyester resin at 80 ° C. was performed in the same manner as in Example 7 except that the BPO composition described in Reference Example 1 was used as a curing agent.
Barcol hardness of the obtained cured product was measured. Table 7 shows the results.

Examples 10 to 12 The BPO compositions obtained in Examples 1 to 3 were added as curing agents, and N, N-dimethyl-p-toluidine was added and mixed as curing accelerators in the amounts shown in Table 8 to obtain acrylic. A syrup (manufactured by Mitsubishi Rayon Co., Ltd., trade name: DR-415) was subjected to a curing test at 25 ° C. in accordance with the normal temperature curing property test method specified in JIS-K-6901, and GT, CT and PE
T was determined. Table 8 shows the results.

[0053]

[Table 8]

As is clear from Examples 4 to 6 in Table 5, the unsaturated polyester resin could be rapidly cured at room temperature by combining the BPO composition of the present invention with N, N-dimethylaniline. . Further, the Barcol hardness of the obtained cured product was high and had good physical properties, and the BPO composition of the present invention was excellent in weighability because it was granular. Further, as is apparent from Examples 7 to 9 in Table 7, under the heating atmosphere, the BPO of the present invention was used.
It was found that the unsaturated polyester resin could be rapidly cured by using the composition alone, and that the cured product obtained had a high Barcol hardness and good physical properties. Furthermore, as is clear from Examples 10 to 12 in Table 8, by combining the BPO composition of the present invention with N, N-dimethyl-p-toluidine, acrylic syrup could be rapidly cured at room temperature. .

On the other hand, as shown in Comparative Examples 1 and 5, when a 75% water wet product of BPO was used as a curing agent, the BPO composition of the present invention was used in terms of curing speed. Although the same as the case, turbidity was observed in the obtained cured product, and the Barcol hardness was slightly lowered. This was presumed to be an adverse effect of the water mixed in at the same time. In addition, as shown in Comparative Examples 2 to 4, the shape of the BPO composition was a high-viscosity paste (Reference Example 2) or a viscous liquid (Reference Examples 3 and 4).
In the case of, the meterability at the time of addition to the unsaturated polyester resin was poor.

[0056]

As described in detail above, according to the present invention, the following excellent effects can be obtained. That is, the BPO compositions of the first to third inventions have high safety, and are excellent in stability over time and weighability. At this time, depending on the embodiment, it can be a non-dangerous item under the Fire Service Law. In the method for curing a thermosetting resin according to the fourth aspect, the thermosetting resin can be rapidly cured at room temperature or in a heated atmosphere, and a cured product having good physical properties can be obtained. Furthermore, in the method for curing an acrylic unsaturated monomer composition of the fifth invention, the acrylic unsaturated monomer composition can be rapidly cured at room temperature or under a heated atmosphere, and has good physical properties. A cured product is obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4H006 AA03 AB49 4J015 BA06 BA13 4J027 AB05 AB06 AB07 AB08 AB14 AB15 AB16 AB17 AB18 AB22 AB23 AB24 AB25 AE01 AE02 AE03 BA04 BA05 BA06 BA07 BA22 CA06 CA07 CA12 CA19 CA38 CB01 CB03 CB04 CC02

Claims (5)

[Claims] 1. A benzoyl peroxide composition comprising benzoyl peroxide, water and an inorganic filler. 2. A benzoyl peroxide composition containing 20 to 50% by weight of benzoyl peroxide, 5 to 17% by weight of water and 33 to 75% by weight of an inorganic filler. 3. The benzoyl peroxide composition according to claim 1, wherein the inorganic filler is a non-hydraulic anhydrous gypsum. 4. A method for curing a thermosetting resin using a curing agent, wherein the curing agent is the benzoyl peroxide composition according to claim 1. Method. 5. A method for curing an acrylic unsaturated monomer composition using a curing agent, wherein the curing agent is the benzoyl peroxide composition according to any one of claims 1 to 3. A method for curing a system unsaturated monomer composition.