JP2000063412A - Composition of curing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain and to develop a curing agent composition of unsaturated polyester putty and FRP, excellent in storage stability. SOLUTION: A curing agent composition remarkably improved in storage stability and the like can be obtained by combination of an ester compound represented by the following formula I or phosphonic acid represented by the following formula II alone or together with the curing agent, respectively. Formula I:R1-CO-O-R2 Formula II:H2O3P-X(-PO3H2)n (In formula I, R1 is a 1-6C alkyl, and R2 is a 2-20C alkyl in the total carbon number containing at least one ether bond. In formula II, X is a crosslinking group which means a 1-20C crosslinking group not containing different atoms or containing 1-5 different atoms in the crosslinking chain, and (n) is an integer of 1-10.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curing agent composition. More specifically, unsaturated polyester putty and FRP
The present invention relates to a curing agent composition comprising specific components used for curing (fiber reinforced plastic).

[0002]

2. Description of the Related Art Unsaturated polyester putty and FRP are composed of unsaturated polyester resin (hereinafter abbreviated as UP resin), and the curing speed of the UP resin gives workability when molding the polyester putty and FRP. The choice of curing agent is important in these operations because of the large impact.

In order to cure the UP resin at room temperature, it is necessary to use an accelerator together with a curing agent (organic peroxide), and there are many combinations, but they are roughly classified into the following two.

One of them is benzoyl peroxide, ortho-methylbenzoyl peroxide as a curing agent,
A system using benzoyl peroxides (hereinafter abbreviated as BPOs) such as meta-methylbenzoyl peroxide and a tertiary amine such as dimethylaniline or dimethylparatoluidine as an accelerator. It has advantages such as fast curing at low temperature and good adhesion of the cured resin to the substrate. On the other hand, however, this system has the drawback that the surface dryness is poor and the amount of styrene monomer remaining in the cured product is large.

The other is to use ketone peroxides (abbreviated as KPOs) such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, and metal soap such as cobalt naphthenate and manganese naphthenate as an accelerator. This curing system has the advantages that the surface dryness of the molded product of polyester putty or FRP is good and the amount of residual styrene monomer is small. However, on the other hand, there is a drawback that the curing at a low temperature is slow and the adhesion of the cured resin to the substrate is relatively poor.

[0006]

Attempts have been made to use these two types of curing systems in combination in order to retain the advantages of these two types of curing systems and to make up for the drawbacks. That is, BPOs and K as curing agents
Attempts were made to use POs at the same time as the tertiary amine and metal soap as accelerators, and the expected results were obtained, but the process of adding the curing agent to the polyester putty or UP resin becomes complicated. , Has not been put to practical use. That is, since tertiary amines and metal soaps can be mixed in advance with polyester putty and UP resin, there is no particular problem in molding work even if there are many types, but the curing agent has a problem of pot life and polyester putty. Since it is necessary to add and mix immediately before molding of FRP or FRP, when two kinds of curing agents are used, it is necessary to add the curing agent in two steps, which complicates the work. In addition, since it is easy to cause troubles such as forgetting to add the curing agent or putting it in twice, it has not been put to practical use.

In order to simplify the process of adding a curing agent and prevent troubles, the combination of BPOs and KPOs with a composition has been tried by various combinations, but with BPOs that are generally commercially available, When a simple composition of KPOs is stored at room temperature, the reduction rate of the active ingredient (represented by the amount of active oxygen) and the amount of gas generated by decomposition are much higher than those of BPOs and KPOs alone. Is very large.

As a method for improving it, a method of using alcohol in combination with commercially available BPOs and KPOs (JP-A-57-57)
No. 40507), but alcohols have an adverse effect on the physical properties and surface dryness of polyester putty and FRP, but they have not been put to practical use in this method.

Another improvement method is commercially available BPO.
There has been proposed a mixed composition (KOKAI No. 61-281140) in which KPOs which are solid (crystalline) at room temperature are used and integrated. This method is a blend of BPOs and KPOs improved from JP-A-57-40507, which is not adversely affected by alcohols. The mixed composition is prepared from dimethyl phthalate (DMP) or dioctyl phthalate (DOP). However, the paste-like product obtained by adding a plasticizer such as) and a thixotropic agent such as silica has a drawback that crystals of KPOs grow due to repeated cold and warm storage at room temperature for a long time.

[Means for Solving the Problems]

The present inventor has conducted extensive studies to reduce the rate of reduction of the active ingredient and the amount of gas generated during storage. As a result, when formulating BPOs and KPOs, the composition of the following general formula (1) ) Or a phosphonic acid represented by the general formula (2), for example, a phosphonic acid compound such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetra (methylenephosphonic acid) It was found that the storage stability of the mixed curing agent composition of BPOs and KPOs is remarkably improved by coexisting with, and the present invention has been completed. That is, the present invention provides the following 1. ~ 7. It is about.

1. A curing agent composition comprising an organic peroxide and at least one of an ester compound represented by the following general formula (1) or a phosphonic acid represented by the following general formula (2).

[0012]

[Chemical 3]

(In the formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents an alkyl group having at least one ether bond and having 2 to 20 carbon atoms in the whole group. In the formula (2), X represents a bridging group, and the bridging group means a bridging group having 1 to 20 carbon atoms, which does not contain a heteroatom or contains 1 to 5 heteroatoms in the bridging chain. Then n
Represents an integer of 1 to 7. )

2. The phosphonic acid represented by the general formula (2) is one or more selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetra (methylenephosphonic acid). The curing agent composition as described in 1 above, which is a phosphonic acid compound.

3. The curing agent composition according to 1 or 2, wherein the compound of the general formula (1) is an ester compound represented by the following general formula (3).

[Chemical 4] (In the formula, R ₁ has the same meaning as described above, and R ₃ and R ₄ each independently represent an alkyl group having 1 to 6 carbon atoms.)

4. The curing agent composition according to any one of claims 1 to 3, wherein each of the ester compound of the general formula (1) and the phosphonic acid of the general formula (2) is contained in at least one kind or more. 5. The curing agent composition according to any one of 1 to 4 above, wherein the content of the ester compound represented by the general formula (1) is 1 to 50% by weight based on the entire curing agent composition. 6. The curing agent composition according to any one of 1 to 5 above, wherein the content of the phosphonic acid of the general formula (2) is 0.001% by weight to 1.0% by weight based on the entire curing agent composition. 7. The content of the ester compound represented by the general formula (1) is 1 to 50% by weight based on the entire curing agent composition, and 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or The content of one or more phosphonic acid compounds selected from the group consisting of ethylenediaminetetra (methylenephosphonic acid) is 0.0
The curing agent composition according to any one of 1 to 6 above, which is from 01% by weight to 1.0% by weight. 8. 8. The curing agent composition according to any one of 1 to 7 above, wherein the organic peroxide is a mixed organic peroxide containing both benzoyl peroxides and ketone peroxides. 9. Any one of 1 to 8 above, wherein the ester compound of the general formula (1) is methoxy-alkyl acetate having 1 to 6 carbon atoms, and the phosphonic acid of the general formula (2) is 1-hydroxyethylidene-1,1-diphosphonic acid. A curing agent composition as described in 1.

As is clear from the above, the present invention provides (A) an organic peroxide such as a mixed curing agent of BPOs and KPOs as a curing agent for unsaturated polyester putty, FRP and the like.
A curing agent composition containing an ester compound represented by the general formula (1), (B) an organic peroxide such as BPOs and KP
The mixed curing agent of O's is selected from the group consisting of phosphonic acids represented by the general formula (2), for example, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetra (methylenephosphonic acid). A curing agent composition containing at least one or more kinds of phosphonic acid compounds and the like, and (C) an organic peroxide such as a mixed curing agent of BPOs and KPOs,
There is provided a curing agent composition or the like containing at least one phosphonic acid represented by the general formula (1) or the phosphonic acid represented by the general formula (2), such as the above-mentioned phosphonic acid compound.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The organic peroxide in the present invention is not particularly limited as long as it is an organic peroxide used as a curing agent, but mixed organic peroxides of benzoyl peroxides and ketone peroxides. The thing is preferable. In the present invention, the term “alkyl” is used to include any of linear, branched, unbranched, cyclic and the like. Specific examples thereof include a chain alkyl group,
Methyl group, ethyl group, n- or i-propyl group, n-,
i- or t-butyl group, pentyl, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, eicodecyl group and the like. Examples of the cyclic group include a cyclopropyl group and a cyclohexyl group.

As the alkyl group having 1 to 6 carbon atoms for R ₁ , among those exemplified above, those having 1 to 6 carbon atoms can be mentioned, and those having 1 to 3 carbon atoms are preferable. R
_The alkyl group containing at least one ether bond in 2 and having a total number of carbon atoms of 2 to 20 is not particularly limited as long as it contains an ether bond in a chain alkyl group or a cyclic alkyl group. There is no. The number of ether bonds is, for example, about 1 to 3, and usually one. Examples of the alkyl group containing one ether bond include a group represented by —R ₃ —O—R ₄ (R ₃ and R ₄ have the same meanings as described above). Examples thereof include methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxyethyl group, propoxypropyl group and the like. A preferred group for R ₃ is an alkyl group having 1 to 6 carbon atoms. A preferred group for R ₄ is an alkyl group having 1 to 3 carbon atoms.

Specific examples of the ester compound represented by the general formula (1) include ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether propionate, 3-methyl-3-methoxybutyl acetate, 2 −
Methyl-2-methoxybutyl propionate, 2,2-
Examples thereof include dimethyl-4-methyl-4-methoxypropyl acetate.

The bridging group represented by X in the general formula (2) is not particularly limited as long as it is a bridging group which binds two or more phosphonic acid groups, but it is generally a hydrocarbon chain, in which It may contain heteroatoms. Examples of the foreign atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like, and a nitrogen atom is usually preferable. Further, this cross-linking group may contain a substituent such as a hydroxy group. Typical examples of those bridging groups include a carbon number of 1 which may be substituted with a hydroxy group.
~ 3 alkylene group, a group represented by the following general formula (4)

[Chemical 5]

Or the following general formula (5)

[Chemical 6] And the like.

Preferred compounds as the phosphonic acids represented by the general formula (2) include, for example, the following structural formula (a):
Examples thereof include 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and the like represented by (b) or (c). 1-Hydroxyethylidene-1,1-diphosphonic acid is the most preferable from the viewpoint of effect and economical efficiency.

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

The KPOs used in the present invention include methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBKP), cyclohexanone peroxide (CYHP), methyl cyclohexanone peroxide (MCYHP), acetylacetone peroxide (AAP). Liquid ketone peroxides such as

In preparing the mixed composition of these liquid KPOs and BPOs, the ester compound of the general formula (1) or the phosphonic acid represented by the general formula (2), for example, 1
1 selected from the group consisting of: hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetra (methylenephosphonic acid)
By coexisting one or more phosphonic acid compounds or by using the ester compound of the general formula (1) or the phosphonic acid represented by the general formula (2) in combination, adversely affects the curing of the polyester putty and FRP. For the first time, it was possible to obtain stable compositions of BPOs and KPOs without the use of the alcohols provided and without the use of solid ketone peroxides which lead to crystal growth during storage.

The BPOs to be blended with the ketone peroxide include benzoyl peroxide (BPO) and ortho-methylbenzoyl peroxide (O-MBP).
O), meta-methylbenzoyl peroxide (MM
BPO), para-methylbenzoyl peroxide (P
-MBPO) and the like can be used. For safety reasons, it is usually preferable to use water or a plasticizer diluted product having a purity of 75% or less for safety reasons, but the purity is 75%.
The above BPOs can also be used.

The mixing ratio of BPOs and KPOs can be arbitrarily selected, but from the viewpoint of curing characteristics, it is usually a weight ratio of BP.
O / KPO = 10/90 to 90/10,
It is preferably 25/75 to 75/25. According to the blending of BPOs and KPOs, BPOs are separated and precipitation of the mixture occurs at the bottom, and powders can be obtained due to the small amount of liquid formulation, but the BPOs are separated and precipitated. In the case of using silica, a thixotropic agent such as Aerosil (trade name, manufactured by Nippon Aerosil Co., Ltd.) is used to form a uniform paste, and in the case of powder, it is diluted with a plasticizer. It is possible to obtain a uniform formulation by forming a paste. Further, the obtained paste composition can be colored with a pigment, a dye or the like, if necessary.

The preferred composition ratio (% by weight to the total composition) of the curing agent composition of the present invention is as follows. Organic peroxide: 20 to 80%, preferably 30 to 70% (Ratio of KPOs and BPO: BPOs / KPOs = 10/90 to 90/10, preferably 25/75 to 75/25 weight ratio) General Ester compound of formula (1): 0 to 40%, preferably 15 to 35% Phosphonic acid of general formula (2): 0 to 3%, preferably 0.001 to 1% Other components: balance (however, generally (The total of the ester compound of formula (1) and the phosphonic acid of formula (2) is not zero.)

[0032]

EXAMPLES Next, the present invention will be described in more detail with reference to Comparative Examples and Examples, but these are merely examples and do not limit the present invention.

Comparative Examples 1 to 5 Each component was precisely weighed so that 220 g of the test sample could be prepared in a 500 ml beaker with the composition ratio shown in Table 1, and after mixing well, two polyethylene tubes having an internal volume of 130 cc were prepared. 100 g of the mixture is sampled, and the air in the mixture is pushed out as much as possible, and then the container is sealed. Each tube was placed in an oven at 40 ° C. for 1 year at room temperature for 28 days, and the amount of active oxygen (abbreviated as AO), gas generation amount and shape change (crystal growth) of the mixture were measured. The amount of active oxygen was quantified by the iodine titration method, and the amount of gas generated was shown in cc of the blister of the tube per 100 g of the mixture. The results are shown in Table 2. In addition, no change in shape was observed.

The BPOs used were pastes obtained by diluting a pure product to 50%. BPOs BPO: 50% DOP diluted product (AO: 3.32%) O-MBPO: 50% DOP diluted product (AO: 3.10%) M-MBPO: 50% DOP diluted product (A. O: 3.15%)

KPOs are commercially available products (manufactured by Kayaku Akzo Co., Ltd.)
Was used. KPOs MEKP: Kayamek A (AO: 10.21%) MIBKP: Kayamek B (AO: 10.15%) CYHP: Cyclonox (AO: 8.20%)

[0036]

[Table 1]

[0037]

[Table 2]

Examples 1 to 5 In a 500 ml beaker, each component was precisely weighed so that 220 g of the test sample could be obtained with the composition ratio shown in Table 3, and after mixing well, it was placed in two polyethylene tubes having an internal volume of 130 cc. 100 g of the mixture is sampled, and the air in the mixture is pushed out as much as possible, and then the container is sealed. Each tube was placed in an oven at 40 ° C. for 1 year at room temperature for 28 days, and the amount of active oxygen (abbreviated as AO), gas generation amount and shape change (crystal growth) of the mixture were measured. The amount of active oxygen was quantified by the iodine titration method, and the amount of gas generated was shown in cc of the blister of the tube per 100 g of the mixture. The results are shown in Table 4.
Described in. Moreover, no change in shape was observed. The same BPOs and KPOs as in Table 1 were used. The ethylene glycol methyl ether acetate (trade name Arcosolv PMA) and 3-methyl-3-methoxybutyl acetate (trade name Solfit AC) in the table used as the ester compound of the general formula (1) are both Kuraray Co., Ltd. Used. Further, 1-hydroxyethylidene-used as the phosphonic acid of the general formula (2)
1,1-diphosphonic acid (trade name Dequest 201
0) ,, aminotri (methylenephosphonic acid) (trade name Dequest 2000), ethylenediaminetetra (methylenephosphonic acid) (trade name Dequest 2041)
Both were manufactured by Nippon Monsanto Co., Ltd. Silica (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) was used as a thixotropic agent. An organic pigment Chromophtal Brown 5R (trade name, manufactured by Ciba Geigy) was used as a colorant.

[0039]

[Table 3]

[0040]

[Table 4]

Application Example Practical tests of the curing agent compositions of Examples 3 and 4 were carried out using commercially available putty. At the same time, two commercially available curing agents (BP
O type and CYHP type) were comparatively tested. There are two types of commercially available putty, polyester putty (compounded with metallic soap as a promoter) and sheet metal putty (compounded with tertiary amine as a promoter).
A CYHP-based curing agent is used for polyester putty, and a BPO-based curing agent is used for sheet metal putty. For the evaluation of the curing agent composition of the present invention, the above two types of putty were mixed and used in a ratio of 1: 1. The amount of the curing agent added was all 2 parts, and the results are summarized in Table 5.

The following terms in the table have the following meanings. Cup gel time: Take 50g of putty in a polyethylene cup, add 1g of curing agent to it, mix well for 1 minute,
It represents the time from the start of mixing until gelation (until the fluidity of putty disappears). Touch dry time: Take 50g of putty in a polyethylene cup, add 1g of curing agent to it, and mix well for 1 minute.
It represents the time from the start of mixing after coating the iron plate to a thickness of 0.6 mm until the putty surface is dry to the touch. Polishable time: This is the time from the start of mixing to the time when polishing can be performed with # 80 sandpaper, following the measurement of the dry-to-touch time. Heat-resistant adhesion: Putty and a curing agent are mixed in the same manner, coated on an iron plate to a thickness of 3 mm, left in an oven at 20 ° C for one day, heated to 80 ° C, held for 2 hours, and then heated to 20 ° C. return. The putty is bent together with the iron plate at an angle of 90 °, and the presence or absence of interface peeling is observed.

[0043]

[Table 5]

[0044]

EFFECT OF THE INVENTION By using the peroxide composition obtained by the present invention, polyester putty and FRP can be obtained.
It is possible to realize a curing system which is fast in low temperature and excellent in surface dryness.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/5317 C08K 5/5317 C08L 67/06 C08L 67/06 C09D 5/34 C09D 5/34 // C08J 5/10 CFE C08J 5/10 CFE

Claims (9)

[Claims] 1. A curing agent containing an organic peroxide and at least one of an ester compound represented by the following general formula (1) and a phosphonic acid represented by the following general formula (2). Composition. [Chemical 1] (In the formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents an alkyl group having at least one ether bond and having 2 to 20 carbon atoms in the whole group. ), X represents a bridging group, the bridging group means a bridging group having 1 to 20 carbon atoms, which does not contain a heteroatom in the bridging chain or contains 1 to 5 heteroatoms, and n is Indicates an integer of 1 to 10.) 2. The phosphonic acid represented by the general formula (2) is 1-hydroxyethylidene-1,1-diphosphonic acid,
The curing agent composition according to claim 1, which is one or more phosphonic acid compounds selected from the group consisting of aminotri (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid). 3. The compound of the general formula (1) is an ester compound represented by the following general formula (3).
The curing agent composition according to. [Chemical 2] (In the formula, R ₁ has the same meaning as described above, and R ₃ and R ₄ each independently represent an alkyl group having 1 to 6 carbon atoms.) 4. The ester compound of the general formula (1) and the phosphonic acid of the general formula (2) are each contained in at least one kind or more, respectively, and the method according to claim 1. Hardener composition. 5. The content of the ester compound represented by the general formula (1) is from 1 to 50% by weight based on the whole curing agent composition.
The curing agent composition according to any one of claims 1 to 4. 6. The content of the phosphonic acid represented by the general formula (2) is 0.001% by weight to 1.0% by weight based on the whole curing agent composition.
The curing agent composition according to any one of claims 1 to 5, which is contained in a weight percentage. 7. The content of the ester compound represented by the general formula (1) is 1 to 50% by weight based on the entire curing agent composition, and 1-hydroxyethylidene-1,1-diphosphonic acid and aminotri ( The content of one or more phosphonic acid compounds selected from the group consisting of methylenephosphonic acid) or ethylenediaminetetra (methylenephosphonic acid) is 0.001% by weight to 1.0% by weight.
The hardening | curing agent composition in any one of-6. 8. The curing agent composition according to claim 1, wherein the organic peroxide is a mixed organic peroxide containing both benzoyl peroxides and ketone peroxides. 9. The ester compound of the general formula (1) is methoxy-alkyl acetate having 1 to 6 carbon atoms, and the phosphonic acid of the general formula (2) is 1-hydroxyethylidene-
The curing agent composition according to claim 1, which is 1,1-diphosphonic acid.