JPS6049646B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition, and more specifically, the present invention relates to a resin composition, and more specifically, to a resin composition that can be applied to a resin composition, and more particularly, to
The present invention relates to a resin composition that is extremely useful as a molding material for sheet molding compound methods or as a material for FRP.

A resin obtained by dissolving an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid such as methacrylic acid in a polymerizable monomer such as styrene is generally called a vinyl ester resin, and has excellent chemical resistance. Due to its excellent properties, it is widely used in the field of corrosion-resistant equipment such as plating tanks and chemical tanks.

However, this vinyl ester resin has the disadvantage of poor storage stability. Conventionally, it has been known that the storage stability of unsaturated polyester resins can be improved by adding soluble copper and quinones, but even when this is applied to vinyl ester resins, the storage stability is still lower than that of unsaturated polyester resins. Because it is inferior, the less quinones, the less effective it is.
In addition, using a large amount of quinones improves storage stability, but the pot life becomes longer, resulting in poor workability. It is extremely difficult to strike a balance between stability and workability.

An object of the present invention is to eliminate the drawbacks of the prior art and provide a resin composition with excellent storage stability and workability.

As a result of intensive research by the present inventors to achieve this purpose,
It has been discovered that the storage stability of vinyl ester resins can be improved by using soluble copper and a compound having one or more nitro groups and phenolic hydroxyl groups in the aromatic ring, and that a resin composition with excellent workability can be obtained. We have arrived at the present invention.

The present invention is directed to an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid, a polymerizable monomer, soluble copper,
The present invention also relates to a resin composition containing a compound having one or more ditro groups and phenolic hydroxyl groups in an aromatic ring. The resin composition of the present invention preferably includes 10 to 90 parts by weight of the unsaturated ester, 90 to 1 part by weight of the polymerizable monomer, and 0.00001 parts by weight of soluble copper (metallic copper).
~0.005 parts by weight, and 0.005 parts by weight of the aromatic compound having a nitro group and a phenolic hydroxyl group as described above.
0005 to 0.5 parts by weight. In this case, the total amount of unsaturated polyester and polymerizable monomer is 100 parts by weight. The unsaturated ester used as a component of the resin composition of the present invention is obtained by reacting an epoxy resin with an unsaturated monobasic acid.

As the epoxy resin, for example, novolac epoxy resin, bisphenol epoxy resin, alicyclic epoxy resin, etc. are used, and these epoxy resins can be used alone or in combination of two or more kinds.

Commercially available novolac epoxy resins include, for example, Dow Chemical Company's D. E. N43l,D
．． E. N438, Epikote 152 and Epicoat 154 manufactured by Shell Chemical Co., Ltd., and EPNll38 manufactured by Ciba Corporation. The bisphenol epoxy resin is a commercially available low-molecular epoxy resin obtained using bisphenol as a reaction material, and examples of commercially available resins include Epikot 828, Epikot 1001, and Epicoat 1004 manufactured by Shell Chemical Co., Ltd., Arartite 6094 manufactured by Ciba Corporation, Examples include Araldite 6097. Examples of alicyclic epoxy resins include vinylcyclohexene dioxide (trade name Chitsonox 206), dicyclopentadiene dioxide (Titssonox 207X), 3,4-epoxy 6-methylcyclohexylmethyl-34-epoxy 6-methylcyclohexane Carbonate (Chitsonox 201) and the like. Note that halogen derivatives of epoxy resins can also be used, such as Tobu Kasei's manufactured boat YDB-3401 and manufactured boat YDB-400. Examples of unsaturated monobasic acids to be reacted with the epoxy resin include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo[5.2.1.02.6]-4-decene-8 (or 9) A partially esterified carbonic acid containing a residue and an unsaturated dibasic acid residue as constituent elements is used.

Examples of partially esterified carboxylic acids include 8- or 9-hydroxytricyclodecene-4-[5●2●1
・02.6] 1.00 to 1.20 mol and unsaturated dibasic acid such as maleic anhydride, itaconic acid, citraconic acid 1
There is an unsaturated dibasic acid monoester obtained by heating mol at 70 to 150°C under an inert gas stream.

Also, tricyclodecanediene-48-[5・2・1●0
2.6] 1.00 to 1.20 mol and 1 mol of an unsaturated dibasic acid such as maleic acid, fumaric acid, itaconic acid, etc. to sulfuric acid,
Unsaturated dibasic acid monoesters obtained by heating under a stream of inert gas in the presence of a catalyst such as a Lewis acid may also be used.

When reacting an unsaturated monobasic acid with an epoxy resin, both compounds should be 60 to 1500 C1, preferably 70 to 13
The mixture is heated to 0°C and reacted to form an unsaturated ester.

Approximately 1 equivalent of unsaturated monobasic acid is used per equivalent of epoxy resin. The acid value of the unsaturated ester produced is 50 or less, preferably 20 or less. In order to prevent gelation due to polymerization during the reaction, for example, hydroquinone di-t
- It is preferable to use a polymerization inhibitor such as butylcatechol or hydroquinone monomethyl ether. In addition, in this esterification reaction, for example, ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, and tin chloride are used. Esterification catalysts can also be used to shorten the reaction time. As the polymerizable monomer, for example, styrene, divinylbenzene, methylstyrene, vinyl acetate, methyl methacrylate, ethyl acrylate, ethylene glycol dimethacrylate, etc. are used, but styrene is mainly used, and p-methylstyrene is heat-resistant. It is preferable because it improves the properties.

The ratio of the polymerizable monomer to the unsaturated ester is not particularly limited, but from the viewpoint of strength, corrosion resistance, etc., it is preferably 90 to 1 part by weight of the polymerizable monomer to 10 to 9 parts by weight of the unsaturated ester; Particularly preferred is 60 to 1 part by weight of the polymerizable monomer per 40 to 9 parts by weight of the unsaturated ester.

Examples of soluble copper include copper naphthenate, copper 3-phenylsalicylate, copper 8-hydroxyquinoate, copper acetate, copper laurate, copper stearate, copper ethylenediamine triacetate, copper citrate, copper benzoate, copper salicylate, and benzene. Copper sulfonate and the like are used, and copper naphthenate is particularly preferred because it improves storage stability.

From the viewpoint of storage stability and coloring, the amount of soluble copper to be blended is 0.00001 parts of metallic copper per 10 parts of vinyl ester resin made by blending the unsaturated ester and polymerizable monomer.
~0.005 part by weight is preferred.

Examples of compounds having one or more nitro groups and phenolic hydroxyl groups in the aromatic ring (hereinafter referred to as nitrophenols) include 2-nitro p-cresol, 4-nitrocatechol, 0-nitrophenol,
m-nitrophenol, p-nitrophenol, 2●3
-dinitrophenol, 4●6-dinitro 0-cresol, 2-nitro 1-naphthol, etc. are used, and 0-nitrophenol is particularly preferred because it has improved storage stability and has less delay in pot life. The amount of nitrophenol compounded is preferably 0.0005 to 0.5 parts by weight based on 10 parts by weight of the vinyl ester resin in terms of storage stability and pot life.

In cases where it is necessary to improve storage stability even if the pot life is long, more than 0.5 part by weight may be used. The resin composition of the present invention may contain a curing organic peroxide, a curing accelerator, a filler, a reinforcing material, a mold release agent, a coloring agent, a thickener, etc., as necessary. Further, polymerization inhibitors other than nitrophenols may be combined. As the organic peroxide for curing, for example, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, etc. are used. As the curing accelerator, for example, metal compounds such as cobalt octenoate, cobalt naphthenate, potassium octenoate, and manganese naphthenate, and tertiary amines such as dimethylaniline and diethylaniline are used. As the filler, for example, calcium carbonate, clay, barium sulfate, aluminum hydroxide, etc. are used. As the reinforcing material, various processed materials such as roping-like materials made of fibers such as glass fibers, vinylon fibers, and carbon fibers, short fibers, woven materials, knitted materials, threads, and plaited materials may be used. As the mold release agent, for example, zinc stearate, calcium stearate, etc. are used. As the colorant, an inorganic or organic colorant used for coloring unsaturated polyester resins is used. Examples of the thickener include metal oxides such as magnesium oxide and calcium oxide, metal hydroxides such as magnesium hydroxide, and organic thickeners based on diisocyanates such as diphenylmethane diisocyanate. These compounds can also be used in combination. Examples of polymerization inhibitors other than nitrophenols include hydroquinone, parabenzoquinone, catechol, 2●5-diphenylparabenzoquinone, and the like. The resin composition of the present invention may also contain thermoplastic polymers such as polystyrene, polyacetic acid, vinyl, polymethyl methacrylate, and saturated polyester, thermosetting polymers such as phenol resin, epoxy resin, and melamine resin, etc., as necessary. It may also contain flame retardants such as antimony trioxide, hexabromobenzene, and chlorinated paraffin.

The resin composition of the present invention has excellent storage stability and workability, and can be used not only in normal temperature and normal pressure molding methods such as hand lay-up and spray-up, but also in resin injection molding methods and preform matted metal die molding methods. It can be used as a molding material in molding methods, sheet molding compound methods, bulk molding compound methods, etc., and its application range is extremely wide.

Examples of the present invention are shown below.

Parts in the examples below mean parts by weight. Pot life is JIS
In accordance with K69Ol4, 10 parts of resin composition, 0.01 part of dimethylaniline, and 0.5 part of 6% cobalt naphthenate were thoroughly mixed, and then 1 part of methyl ethyl ketone peroxide was added until gelation occurred. It was the time of

Accelerated storage stability: inner diameter 18wrIn, height 150TI
Put the sample into an Un test tube to a height of 701T0fL, and seal it tightly to leave a space of 50mm at the top.
The mixture was placed in an oil bath at ℃ and turned over at regular intervals to determine the time until gelatinization occurred. Example 1 Methacrylic acid 172.0y (2.0 mol) Epicote 8
28 (bisphenol epoxy resin manufactured by Shell Chemical Co., epoxy equivalent weight 189) 151.2 g (0.40 mol), Epicoat 1001 (manufactured by Shell Chemical Co., Ltd., epoxy equivalent weight 47)
5) 570.0y (0.60 mol), hydroquinone 0
．． A resin composition (hereinafter referred to as VE-1) was obtained.

The pot life of the obtained VE-1 was 1 gin, and the accelerated storage stability was 12 gin. ■ Add 0.0005 parts of copper naphthenate (metallic copper content) and 0.001 parts, 0.01 parts, and 0.05 parts of O-nitrophenol to part E-11 (1), and make it usable. Time and accelerated storage stability were measured.

The results are shown in Table 1. Accelerates storage stability and improves
It can also be seen that there is little delay in pot life.

Example 2 0.0005 parts of copper acetate (metallic copper content) and 0-nitrophenol were added to (4) parts of VE-11 obtained in Example 1.
．． 01 parts were added to determine pot life and accelerated storage stability.

The results are shown in Table 1. Similar to Example 1, it can be seen that the accelerated storage stability is improved and the pot life is less delayed. Example 3 In the VE-11 hammered part obtained in Example 1,
Copper naphthenate (metallic copper content) 0.0005 parts and 2.3 parts
Pot life and accelerated storage stability were determined by adding 0.01 part of dinitrophenol.

The results are shown in Table 1. Similar to Example 1, it can be seen that the accelerated storage stability is improved and the pot life is less delayed.

Comparative Example 1 0.0005 parts of copper naphthenate (metallic copper content) was added to (6) parts of E-11 obtained in Example 1, and pot life and accelerated storage stability were measured.

The results are shown in Table 1. It can be seen that the accelerated storage stability has not been improved much.

Comparative Example 2 To (1) part of E-11 obtained in Example 1, 0
- 0.01 part of nitrophenol was added to determine pot life and accelerated storage stability.

The results are shown in Table 1. It can be seen that the accelerated storage stability has not been improved much.

Comparative Example 3 To the VE-110 suspension obtained in Example 1, 0.0005 parts of copper naphthenate (metallic copper content) and 0.001 parts, 0.01 parts, and 0.05 parts of hydroquinone were added, respectively. , pot life and accelerated storage stability were determined.

The results are shown in Table 1. It can be seen that increasing the amount of hydroquinone improves the accelerated storage stability but delays the pot life.

Comparative Example 4 0.0005 parts of copper naphthenate (metallic copper content) and 0.001 parts, 0.01 parts, and 0.0 parts of parabenzoquinone were added to (1) part of E-11 obtained in Example 1, respectively. The pot life and accelerated storage stability were measured by adding 0.05 parts.

The results are shown in Table 1. It is found that increasing the amount of parabenzoquinone improves the accelerated storage stability but delays the pot life.

Example 4 Methacrylic acid 86q (1.0 mol), DEN438 (
Novolak epoxy resin manufactured by Da2 Chemical Co., Ltd., epoxy equivalent weight 179) 179q (1 epoxy equivalent), hydroquinone 0.054V, and trimethylbenzylammonium chloride 2.7q were heated at 90°C for 7 hours to obtain an acid value of 14. m parts of unsaturated ester and styrene. N3?
A resin composition (hereinafter referred to as VE-2) was obtained by mixing the following.

The pot life of the obtained VE-2 was 8 minutes, and the accelerated storage stability was 10 powders. To part VE-21 (1), add 0.0005 part of copper naphthenate (metallic copper content) and 0.001 part, 0.01 part, and 0.05 part of O-nitrophenol, respectively.
pot life and accelerated storage stability were determined. The results are shown in Table 2. It can be seen that the accelerated storage stability is improved and the pot life is less delayed.

Example 5 0.0005 part of copper acetate (metallic copper content) and 0.0 part of O-nitrophenol were added to VE-210@ obtained in Example 4.
1 part was added to determine pot life and accelerated storage stability.

The results are shown in Table 2. Similar to Example 4, it can be seen that the accelerated storage stability is improved and the pot life is less delayed. Example 6 ■ E-21 Urabe obtained in Example 4,
Copper naphthenate (metallic copper content) 0.0005 parts and 2.3 parts
Pot life and accelerated storage stability were determined by adding 0.01 part of dinitrophenol.

The results are shown in Table 2. Similar to Example 4, it can be seen that the accelerated storage stability is improved and the pot life is less delayed.

Comparative Example 5 0.0005 part of copper naphthenate (metallic copper content) was added to (1) part of E-21 obtained in Example 4, and the pot life and accelerated storage stability were measured.

The results are shown in Table 2. It can be seen that the accelerated storage stability has not been improved much.

Comparative Example 6 To (4) parts of ■E-21 obtained in Example 4, 0
- Pot life and accelerated storage stability were determined by adding 0.01 part of nitrophenol.

The results are shown in Table 2. It can be seen that the accelerated storage stability has not been improved much.

Comparative Example 7 0.0005 parts of copper naphthenate (metallic copper content) and 0.001 parts, 0.01 parts, and 0.05 parts of hydroquinone were added to the E-21 beaten part obtained in Example 4, respectively. The pot life and accelerated storage stability were determined.

The results are shown in Table 2. It can be seen that increasing the amount of hydroquinone improves the accelerated storage stability, but delays the pot life.

Comparative Example 8 To (1) part of VE-21 obtained in Example 4, 0.0005 part of copper naphthenate (metallic copper content) and 0.001 part, 0.01 part, and 0.05 part of parabenzoquinone were added, respectively. pot life and accelerated storage stability were determined.

The results are shown in Table 2. It can be seen that increasing the amount of parabenzoquinone improves the accelerated storage stability, but delays the pot life.

Example 7 Acrylic acid 144.0y (2.0 mol), Epicote 8
28 (bisphenol epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent: 189) 151.2y (a). 40 moles),
Epicoat 1001 (manufactured by Shell Chemical Co., Ltd., epoxy equivalent: 4
75) m parts of an unsaturated ester with an acid value of 7 obtained by heating 570.0y (0.60 mol), 0.40y of hydroquinone, and 0.5v of trimethylbenzylammonium chloride at 120'C for 8 hours, and styrene. A resin composition (hereinafter referred to as ①E-3) was obtained by mixing the following parts.

The pot life of the obtained E-3 was 9 minutes, and the accelerated storage stability was 14 powders. (2) 0.0005 part of copper naphthenate (metallic copper content) and 0.01 part of O-nitrophenol were added to (1) part of E-31, and the pot life and accelerated storage stability were measured.

As a result, the pot life was 22 minutes, and the accelerated storage stability was 38 gin. It can be seen that the accelerated storage stability is improved and the pot life is less delayed.

As is clear from the above results, the resin composition of the present invention has excellent storage stability and workability.

Claims (1)

[Claims] 1. An unsaturated ester obtained by reacting an epoxy resin with an unsaturated basic acid, a polymerizable monomer, soluble copper, and one or more nitro groups and phenolic hydroxyl in an aromatic ring. A resin composition containing an aromatic compound having a group. 2 10 to 90 parts by weight of the unsaturated ester, 90 to 10 parts by weight of the polymerizable monomer, and 0.2 parts by weight of the soluble copper (metallic copper content).
00001 to 0.005 parts by weight, and 0.0005 to 0.5 parts by weight of the aromatic compound.