JP2840121B2 - Curable urethane vinyl ester resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a curable vinyl ester resin composition having excellent heat resistance, chemical resistance and boiling resistance. More specifically, it has excellent heat deformation resistance, hot water resistance and alkali resistance,
In addition, the present invention relates to a curable urethane vinyl ester resin composition which has excellent performance of improving mechanical strength such as tensile strength, and has excellent workability.

[Conventional technology]

Conventionally, an unsaturated acid such as an unsaturated dibasic acid, or an unsaturated polyester resin solution obtained by dissolving a reaction condensate of such an unsaturated acid and a polyhydric alcohol in a vinyl monomer, as a curable resin composition, In order to obtain a cured resin that requires mechanical strength for reinforced plastics (so-called FRP) in combination with glass fiber, and to obtain a cured resin that requires water resistance and alkali resistance at room temperature Although it is known that each is used, however, the performance of each of the mechanical strengths such as heat deformation resistance at high temperatures as described above, hot water resistance, alkali resistance and tensile strength is not yet practically satisfactory. .

Especially when using the above unsaturated polyester resin liquid,
(1) In order to improve the heat-resistant deformation temperature, the resin liquid using the reaction condensate having a large number of unsaturated bonds is better, but the more the resin liquid becomes, the lower the mechanical strength such as tensile strength is. (2) In order to improve the water resistance and the alkali resistance at the time of the high temperature, it is better to use the reaction condensate having a high molecular weight. However, it is unsatisfactory in practical use as a curable resin composition which exhibits excellent performances as described in the present invention. Further, even in the urethane unsaturated polyester resin in which the terminal hydroxyl group present in the unsaturated polyester resin is treated with various diisocyanate compounds under a vinyl monomer or an organic solvent, according to the study of the present inventors, the hot water resistance at the high temperature, Practically unsatisfactory in terms of alkali resistance,
Further, in the case of the above-mentioned unsaturated polyester resin liquid, the performance as a resin cured product as described in the above (1), that is, if the heat-resistant deformation temperature at the high temperature is to be improved, the tensile strength is lowered. Mechanical strength decreases,
Further, when the performance as a resin cured product as described in the above (2), that is, the water resistance and the alkali resistance at the time of the high temperature are to be improved, the workability is reduced, and in any case, as described in the present invention, It is practically unsatisfactory as a curable resin composition that exhibits excellent various performances.

Next, a curable vinyl ester resin solution composed of a vinyl ester compound and a vinyl monomer obtained by reacting an epoxy compound containing one or more epoxy groups in a molecule with an unsaturated monobasic acid is a component of the curable vinyl ester resin solution. Any of the above-mentioned properties are practically unsatisfactory as a curable resin composition including the novolak-type epoxy compound, which is said to have good hot water resistance and alkali resistance at high temperatures.

[Problems to be solved by the invention]

The above-mentioned curable resin composition has no performance defect as a cured resin, and has a heat deformation resistance, a hot water resistance and an alkali resistance at a high temperature of 100 ° C. or higher as compared with the curable resin composition described above. As described above, in addition to providing excellent performance as well as mechanical strength such as tensile strength, which is generally considered to be reduced when the heat deformation resistance is improved as described above, and excellent workability. An object of the present invention is to provide a curable urethane vinyl ester resin composition.

[Means for Solving the Invention]

As a result of intensive studies, the present inventors have found that urethanization obtained by reacting a specific vinyl ester compound containing a free OH group with 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane is obtained. The present inventors have found that a curable urethanized vinyl ester resin composition comprising a vinyl ester compound and a vinyl monomer is suitable for the above object, and have completed the present invention.

That is, the present invention relates to (A) a vinyl ester compound containing a free OH group obtained by reacting an epoxy compound containing at least one epoxy group in a molecule with an unsaturated monobasic acid, and (B) 2,5 (6) a urethane-modified vinyl ester compound obtained by reacting with -diisocyanatomethyl-bicyclo [2,2,1] heptane;
(C) A curable urethanized vinyl ester resin composition comprising a vinyl monomer.

As the epoxy compound in the present invention, for example, an epoxy resin `` Epicoat 828 '' manufactured by Ciel of the United States represented by the following formula, Diglycidyl ether such as, and further polyglycidyl ether such as novolak epoxy resin "DEN438" (shown by the following general formula) manufactured by Dow Chemical Company, USA, Of course, an epoxy compound obtained by epoxidizing an intramolecular double bond with peracetic acid can also be used.

Further, as the unsaturated monobasic acid in the present invention,
For example, acrylic acid, methacrylic acid, crotonic acid, methyl malate, propyl malate, butyl malate, 2
Examples include ethylhexyl fumarate, methyl fumarate, propyl fumarate, butyl fumarate, and 2-ethylhexyl fumarate.

In order to obtain the above-mentioned vinyl ester compound (A) used in the present invention, the epoxy group 1
The molar ratio of unsaturated monobasic acid to mol is usually 0.1 mol to
Although 1.9 mol is used, it is particularly preferable to use 0.3 to 1.2 mol.

In the present invention, together with the above unsaturated monobasic acid, a part of this acid may be replaced with a saturated monobasic acid such as acetic acid, propionic acid or benzoic acid, or a saturated polybasic acid such as phthalic anhydride, isophthalic acid or hetonic acid. Basic acid, maleic anhydride,
Substitution with at least one of unsaturated polybasic acids such as fumaric acid and cytocholanic acid may be used in combination.

In the present invention, the vinyl ester compound (A) described above can also be produced and used as follows.

For example, in the reaction of an epoxy compound containing one or more epoxy groups in the molecule with an unsaturated monobasic acid, in the presence of the above-mentioned (C) vinyl monomer used in the present invention, for example, secondary, tertiary or tertiary A reaction catalyst such as a quaternary ammonium salt and a polymerization inhibitor such as, for example, parapenzoquinone or hydroquinone are added, and the reaction is carried out usually at a temperature of 100 to 120 ° C. It is preferable to obtain a mixed solution of the vinyl ester and the vinyl monomer (C) used above. In this case, of course, the vinyl monomer (C) only plays a role of a diluent, and is thus obtained. 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane of (B) used in the present invention as a process for producing the curable resin composition according to the present invention. With It is advisable to add and mix (hereinafter, this compound is abbreviated as liquid A).

The vinyl monomer of (C) in the above method is not present during the above-mentioned reaction, and the 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane of (B) in the above method is used. May be added and blended in the mixed solution in the above method.

Also, 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane is, for example, 2,5 (6) -diaminomethyl-bicyclo [2,2,1] heptane obtained by isoamyl acetate and O- In a mixed solvent of dichlorobenzene, hydrogen chloride gas is blown to cause a salt formation reaction, then phosgene is blown to cause a phosgenation reaction, and then rectification is performed.

Next, as the vinyl monomer of the above-mentioned (C) used in the present invention, for example, styrene, divinylbenzene, vinyltoluene, acrylate, methacrylate, vinyl acetate, diallyl phthalate, glycidyl methacrylate, diallyl fumarate, triaryl Lucyanurate and the like, and at least one of these various vinyl monomers can be used in the present invention.

The above-mentioned vinyl monomer (C) used in the present invention is preferably present in the curable urethanized vinyl ester resin composition of the present invention in an amount of usually 20 to 60% by weight.

Thus, in the curable urethanized vinyl ester resin composition of the present invention, 2,5 (6) of (B) relative to the free hydroxyl group (OH group) in the vinyl ester compound of (A) as a constituent component ) -Diisocyanatomethyl-
Bicyclo [2,2,1] heptane isocyanate group (NCO
Molar ratio (NCO / OH) is usually 0.01 to 0.85 or 1.15 to 1.
In the range of 80, 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane of (B) is preferably used as a component, and particularly preferably 0.30 to 0.80. The curable urethane vinyl ester resin composition of the present invention is obtained as follows.

(1) Solution A obtained by the method described above, or (2) an epoxy compound containing at least one epoxy group in a molecule and an unsaturated monobasic acid are usually added in the presence of the vinyl monomer (C). , Trimethylammonium chloride, a catalyst such as diethylamine hydrochloride, tertiary butyl catechol,
The reaction is carried out in the presence of a polymerization inhibitor such as hydroquinone to obtain the vinyl ester compound of the above (A), and this compound is added to the vinyl monomer of the above (C) and 2,5 of the above (B).
(6) -diisocyanatomethyl-bicyclo [2,2,1]
Each of the liquids (hereinafter abbreviated as liquid B) obtained by blending heptane, that is, the liquid A or the liquid B is usually added in the presence of a catalyst such as cobalt naphthenate or calcium naphthenate for 50 hours.
By maintaining the temperature at 〜100 ° C., the vinyl ester compound of (A) and the diisocyanate of (B) undergo a urethanization reaction in the presence of the vinyl monomer of (C),
The liquid material of the urethane resin containing the vinyl monomer (C), that is, the curable urethane vinyl resin composition of the present invention is obtained.

The curable urethane-containing vinyl ester resin composition of the present invention obtained as described above is usually used as a curing catalyst such as, for example, methyl ethyl ketone peroxide and isobutyl ketone peroxide, or a curing accelerator such as cobalt naphthenate. Alternatively, if appropriate, a curing accelerator such as dimethylaniline or diethylaniline may be used in combination to cure at a low temperature such as 0 to 40 ° C. to obtain a cured product.

The cured product of the curable urethane-vinyl ester resin composition according to the present invention thus obtained has not only the excellent properties described above but also the solvent resistance at high temperatures as described above. As compared with the cured product of the curable resin composition of a saturated polyester resin or a urethanized unsaturated polyester resin, the resin composition of the present invention is excellent in various parts used in a high temperature part, for example, a transportation conduit. It has a very high practical value as a hardening resin composition for the production of reaction towers, storage tanks, etc. In this case, glass fiber is blended to form a hardened molded product in the form of glass fiber reinforced plastic, or hardening for corrosion resistant lining. The curable urethanized vinyl ester resin composition of the present invention has very high useful value.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,
1] Production of heptane (BCHI) Isoamyl acetate (687 g) and O-dichlorobenzene (2189 g) were mixed as solvents, and prepared as a solvent for salt formation and phosgenation (hereinafter referred to as a mixed solvent). The mixture was placed in a flask and cooled to 5 ° C. with ice water while stirring. Hydrogen chloride gas was blown into this at a rate of 1.6 Nl / min for 30 minutes, and then about 60% of the 2,5-isomer and about 2,6-isomer
A 40% mixture of diaminomethyl-bicyclo [2,2,
1] Heptane (BHCA) 250.0 g (1.62 mol) mixed solvent 1750
The solution (concentration: 12.5% by weight) dissolved in g was dropped into the liquid in the flask over 2 hours. Continue cooling during the dropping, keep the temperature inside the flask at 10 to 15 ° C, and blow hydrogen chloride gas at 1N.
Continued at l / min.

After completion of the dropwise addition of the starting diamine solution, blowing of hydrogen chloride gas was continued at a rate of 0.4 Nl / min for 2 hours while maintaining the temperature inside the flask at 25 ° C. or lower, to complete the salt formation reaction. In the salt-forming reaction, agglomeration of hydrochloride particles did not occur, and the transition was extremely smooth, and a slurry of white uniform fine particles was obtained.

After completion of the salt-forming reaction, the temperature inside the flask is increased from 25 ° C to 160 ° C
The phosgene reaction was started by gradually blowing phosgene from 100 ° C. while the temperature was raised in 0 minutes. Blowing of phosgene was continued at a rate of 100 g / h to 120 g / h while adjusting the internal temperature to 160 ± 1 ° C. with a mantle heater. After about 6 hours from the start of phosgene blowing, the property of the reaction solution changed from a slurry (white) to clear (red), and then phosgene gas was blown at a rate of 50 g / h for 30 minutes, and the phosgenation reaction was terminated. did.

Thereafter, into the flask the reaction solution, subjected to 80 minutes blown degassed with N ₂ gas at a rate of 1.3Nl / min, while this liquid temperature is 160
± 1 ° C. After cooling and filtration, the filtrate was desolvated and then rectified under vacuum to obtain a main fraction of 110-116 ° C / 0.4-0.6 torr.
06.5 g was obtained.

The main fraction obtained from the results of elemental analysis, IR spectrum, NMR spectrum and the like was confirmed to be the target product.

Example 1 and Comparative Example 1 Comparative Example 1 A mixture comprising, as an epoxy compound, 1140 g of an epoxy resin “Epicoat 828” manufactured by Ciel Corporation, 516 g of methacrylic acid, 1.6 g of hydroquinone as a polymerization inhibitor, and 4 g of trimethylbenzylammonium chloride as a reaction catalyst. Was heated and maintained at 120 ° C. for 3 hours, whereby the acid value became almost zero. 60 parts by weight of the product obtained by this reaction was dissolved in 40 parts by weight of styrene to obtain a liquid vinyl ester resin (resin composition A). The viscosity of the obtained vinyl ester resin liquid at 25 ° C. was 0.5 poise, and the hue was Gardner 3-4.

Example 1 With respect to 2760 g of the resin composition A obtained in Comparative Example 1, 276 g of 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane obtained in Reference Example, 541 g of styrene, 541 g of cobalt naphthenate By adding 18 g and maintaining at 75 ° C. for 2 hours to carry out a urethanization reaction, free isocyanate groups became almost zero. The liquid material (resin composition B) of the urethane resin thus obtained had a viscosity of 4 poise at 25 ° C. and a hue of reddish brown.

Example 2 and Comparative Example 2 Comparative Example 2 Novolac epoxy resin “DE manufactured by Dow Chemical Co., USA”
N438 "(epoxy equivalent 176-181, viscosity at 52 ° C 300
A mixture consisting of 370 g of g900 poise), 172 g of methacrylic acid, 3 g of trimethylbenzylammonium chloride as a reaction catalyst and 0.5 g of hydroquinone as a polymerization inhibitor was heated and maintained at 110 to 120 ° C. for 3 hours to obtain an acid value of 8. became. At this point, add 1177 g of styrene and add
The mixture was reacted for 30 minutes and cooled. The acid value was almost zero. The liquid (resin composition C) of the vinyl ester resin thus obtained had a viscosity at 25 ° C. of about 1.0 poise and a hue of reddish brown and transparent.

Example 2 139 g of 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane obtained in Reference Example, 411 g of styrene and cobalt naphthenate were added to C719 g of the resin composition obtained in Comparative Example 2 above. By adding 6.5 g and maintaining at 75 ° C. for 2 hours, free isocyanate groups became almost zero. The liquid material (resin composition D) of the urethane resin thus obtained had a viscosity of 3.5 poise at 25 ° C. and a hue of reddish brown and transparent.

Comparative Example 4 As a commercially available bisphenol A type unsaturated polyester resin (resin composition E), “Ester” manufactured by Mitsui Toatsu Chemicals, Inc.
R2110 "was used.

Comparative Example 3 The resin composition E1000 g of Comparative Example 4
5 (6) -diisocyanatomethyl-bicyclo [2,2,1]
Heptane (10 g) and cobalt naphthenate (5 g) were added to carry out a urethanization reaction at 75 ° C. for 2 hours. The obtained urethane-containing unsaturated polyester resin (resin composition F) had a viscosity of 20 poise at 25 ° C. and a light yellow transparent color.

For each 100 parts by weight of the vinyl ester resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 4 described above, 1.0 part by weight of methyl ethyl ketone peroxide, 0.5 part by weight of dimethylaniline and 0.5 part by weight of cobalt naphthenate were used. The parts to which parts by weight were added were each cured at 25 ° C. Tensile strength, heat deformation temperature,
Table 1 shows the results of measurement of hot water resistance, alkali resistance, and solvent resistance.

(Note 1) A cast plate as a cured resin was immersed in an autoclave containing pure water at 140 ° C. for 15 days, taken out, and the appearance was measured.

(Note 2) A cast plate as a cured resin was immersed in an autoclave containing a 30% aqueous solution of NaOH at 140 ° C. for 15 days, taken out, and measured in the same manner as (Note 1).

(Note 3) The cast plate as the cured resin was immersed in an autoclave containing 100% xylene for 5 days at 130 ° C., taken out, and measured in the same manner as in the above (Note 1). In addition, ○, Δ, and × shown in Table 1 mean the following facts.

In the case of ○, no abnormality such as a crack was observed on the casting plate surface.

Δ indicates that slight cracks are slightly generated on the casting plate surface.

× indicates that many fine cracks are generated on the surface of the casting plate.

〔The invention's effect〕

The present invention relates to a useful curable urethane vinyl ester resin composition having increased crosslink density by increasing the number of vinyl groups in one molecule from two to four, and having improved heat resistance, chemical resistance and boiling resistance. is there.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-290420 (JP, A) JP-A-4-33969 (JP, A) JP-A-4-226965 (JP, A) JP-A-4- 91112 (JP, A) US Patent 3,595,917 (US, A) US Patent 3,492,330 (US, A) US Patent 3,646,132 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 290/00 -290/14 C08G 18/00-18/87

Claims (1)

(57) [Claims] (1) A vinyl ester compound containing a free OH group obtained by reacting (A) an epoxy compound containing at least one epoxy group in a molecule with an unsaturated monobasic acid is used as a component (B)
(6) -diisocyanatomethyl-bicyclo [2,2,1]
A curable urethane vinyl ester resin composition comprising a urethane vinyl ester compound obtained by reacting with heptane and (C) a vinyl monomer.