JP2613330B2 - Multi-component thermosetting resin composition and method for producing cured resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a molded article having excellent heat resistance, chemical resistance and mechanical properties (especially impact resistance) and excellent cutting workability, storage stability, handleability and moldability. The present invention relates to a liquid type thermosetting resin composition and a method for producing a cured resin molded product using the same.

[0002]

2. Description of the Related Art In recent years, with the progress of technology, resins having excellent heat resistance, mechanical properties, and excellent moldability have been demanded. Among these resins, in particular, a reaction molding type resin using a reactive monomer or oligomer, that is, a curable resin that simultaneously performs molding and polymerization using a relatively low-viscosity (preferably liquid at room temperature) raw material, Is attracting attention.

[0003] Such resins include polyurethane resins,
Epoxy resins, unsaturated polyester resins, vinyl ester resins and the like are known, and some of them are commercialized. However, each of these resins has advantages and disadvantages. For example, polyurethane resins have low heat resistance, and unsaturated polyester resins and epoxy resins are harder and more brittle than heat resistant polyurethane resins.

As a method for improving the heat resistance of a polyurethane resin, introduction of an isocyanurate ring by trimerization of an isocyanate has been known from, for example, Japanese Patent Publication No. 44-16669 for a long time and has been put to practical use. However, the heat resistance is improved by about 20 to 30 ° C. compared with the conventional one, and the heat deformation temperature is at most 150 to 16
Stops at 0 ° C.

[0005] As a thermosetting resin using this polyisocyanate as one raw material, a thermosetting resin utilizing oxazolidone ring formation, which is a ring-forming reaction between an isocyanate group and an epoxy group, has been known for a long time. Kaisho 6
As described in 2-62879, a combination of an isocyanurate ring obtained by trimerizing an isocyanate and the formation of an oxazolidone ring has been proposed.

However, this resin has high heat resistance, but is brittle and has low impact resistance. Such brittleness and low impact resistance are the general characteristics of thermosetting resins. As an improvement, the addition of an elastic material such as rubber is generally performed, but the improvement effect is not remarkable, and other characteristics such as a large decrease in the heat deformation temperature of the molded product when the amount of addition is increased. Causes a decrease.

Therefore, the present inventors have considered a thermosetting resin composition comprising a polyisocyanate compound, a polyepoxy compound, a polyol compound and a curing catalyst. However, this composition is generally highly reactive and easily prepared at room temperature. It was found that the polymerization and curing reaction proceeded rapidly, causing an increase in viscosity, gelation, or the generation of insoluble materials, resulting in problems in the reproducibility of the characteristics of the molded product and the stability of molding.

On the other hand, as a method for producing a resin molded product from such a composition, for example, Japanese Patent Application Laid-Open No. 59-221321 discloses a method in which a first component comprising a liquid mixture of a polyisocyanate and an epoxy compound, a specific catalyst, ie, aziridine. A method is known in which a liquid mixture comprising a compound and a tertiary amine is divided into a second component obtained by adding an active hydrogen compound as necessary, and these are mixed at a predetermined compounding ratio, and then injected into a mold or injection molded. Proposed.

However, the present inventors conducted further studies on such a method in detail, and found that the polyisocyanate compound and the epoxy compound gradually reacted, and that a gel-like substance and an insoluble substance were liable to be generated over time. . This phenomenon was remarkable particularly when a polyepoxy compound having two or more epoxy groups was used as the epoxy compound. This means that the liquid for molding cannot be stored, which is an industrial problem.

[0010]

SUMMARY OF THE INVENTION Therefore, one object of the present invention is to maintain good impact resistance in a composition comprising a polyisocyanate compound, a polyol compound, a polyepoxy compound and a curing catalyst as described above. Another object of the present invention is to provide a composition that can stably and reproducibly produce a cured resin molded product having excellent heat resistance.

Another object of the present invention is to provide a method for industrially producing a cured resin molded product having good impact resistance, heat resistance, cutting workability and the like using the composition.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above-mentioned problems and, as a result, selected the ratios of the polyisocyanate compound, the polyol compound and the polyepoxy compound to be cured by reaction within a certain range. The present inventors have found that this can be achieved by forming a multi-part composition in which the components and the curing catalyst are divided into a plurality of liquids, and have reached the present invention.

That is, the composition of the present invention comprises (A) a solution A comprising at least one kind of polyisocyanate compound (a) having two or more isocyanate groups;
A combination of at least one polyol compound having at least one hydroxyl group (b), at least one polyepoxy compound having at least two epoxy groups (c), and a curing catalyst (d) with a liquid B. And the mixing ratio of each of the above components in both the AB solution is 10 to 40 equivalents of hydroxy groups in the polyol compound, 5 to 20 equivalents of epoxy groups in the polyepoxy compound, and 100 equivalents of isocyanate groups in the polyisocyanate compound. A multi-component thermosetting resin composition, wherein the sum of the hydroxyl group and the epoxy group is in a ratio of 15 to 45 equivalents relative to 100 equivalents of the isocyanate group.

In the multi-part composition of the present invention, the B liquid is a liquid in which the polyol compound (b), the polyepoxy compound (c) and the curing catalyst (d) are uniformly mixed, or A mixture of the first liquid (i), wherein the liquid B is a mixture of a part of the polyol compound (b) and the entire amount of the polyepoxy compound (c), the remainder of the polyol compound (b), and the curing catalyst (d) And a second liquid (ii).

The method for producing a molded product according to the present invention is characterized in that the liquid A and the liquid B are mixed at the time of molding, the mixed liquid is poured into a predetermined mold, and the mixture is cured by heating in the mold. This is a method for producing a thermosetting resin molded product.

The multi-component thermosetting resin composition of the present invention comprises a polyisocyanate compound (a), a polyol compound (b), a polyepoxy compound (c) and a curing catalyst (d).
Consisting of the following components:

The polyisocyanate compound (a) used in the present invention has at least two isocyanate groups in its molecule, and aliphatic, alicyclic or aromatic isocyanates are used.

Examples of the aliphatic polyisocyanates include hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene 1,6-
Examples of diisocyanates include alicyclic polyisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated meta- or para-xylylene diisocyanate. Examples of the aromatic isocyanates include 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,4'- or 4,4'-diphenyl ether diisocyanate, and 1,5-naphthalene. Examples include diisocyanate, meta- or para-xylylene diisocyanate.

Further, polyphenylene polymethylene polyisocyanate prepared by isocyanating polyamine obtained by condensation of aniline and formalin with phosgene, carbodiimide-modified or polyol-modified polyisocyanate, and 4,4'-diphenylmethane diisocyanate can also be used.

Further, an isocyanurate ring-containing polyisocyanate obtained by trimerizing a polyisocyanate, for example, a trimer of tolylene diisocyanate can also be used.

These can be used singly or in a mixture of two or more types, but they must be liquid at least at the time of mixing before molding. Among them, carbodiimide-modified or polyol-modified 4,4'-diphenylmethane diisocyanate or polyphenylene polymethylene polyisocyanate which is liquid and low viscosity at room temperature, and a mixture of 2,4- and 2,6-tolylene diisocyanate are preferable. Used.

The polyol compound (b) used in the present invention has at least two hydroxyl groups in its molecule.
It has one.

As such a polyol compound (b),
Polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycols having ethylene oxide added to the terminal such as polypropylene oxide, glycerin, pentaerythritol, sorbitol, trimethylolpropane, bisphenol A, N-substituted diethanolamine Polyols to which ethylene oxide or propylene oxide are added, etc., or polyester-based polyols, for example, adipate-based polyols, polycaprolactone-based polyols, polycarbonate-based polyols, etc. Having a polymer polyol. Furthermore, ethylene glycol, propylene glycol, 1,3
-Butanediol, dipropylene glycol, 1,4-
Alternatively, 1,5-hexanediol, glycerin, pentaerythritol, sorbitol, trimethylolpropane, N-substituted diethanolamine and the like, cyclohexanediol, cyclohexanedimethanol, and bisphenol A can also be mentioned. Further, a polybutadiene having terminal hydroxy, a polybutadiene-styrene copolymer, and a polybutadiene-acrylonitrile copolymer are also used.

These polyol compounds can be used alone or in the form of a mixture, but it is preferable to use a mixture of two or more of them in order to balance the properties of heat resistance and impact resistance.

Among such polyol compounds (b),
Molecular weight 300 to 70 polymerized to some extent from the viewpoint of impact resistance
00 is preferable, and it is preferable to use a polyether-based polyol or a polyester-based polyol as a main component, to which the same type of polyol having a different degree of polymerization or another polyol is added.

As the polyol compound (b), those which are liquid or nearly liquid at room temperature are suitably used from the viewpoint of moldability.

On the other hand, the polyepoxy compound (c) in the present invention has at least two epoxy groups in its molecule, and includes bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, Bifunctional epoxy compounds such as resorcinol diglycidyl ether, hexahydrobisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl phthalate, triglycidyl isocyanurate, phenol novolak polyglycidyl ether, An epoxy compound having three or more functions such as cresol novolak polyglycidyl ether and a tetraglycidyl compound represented by the following formula (1) is used. Rukoto can.

[0028]

Embedded image [However, in the above formula (1), Y is -CH _2- , -C
(CH ₃ ) _2- , -O-, -SO _2- , -S- or-
C (CF ₃ ) —, G ¹ , G ² , G ³ and G
⁴ represents any of the following: G ¹ , G ² , G ³ and G
^It is preferable that all of ⁴ are the same, but some or all of them may be different. ]

[0029]

Embedded image

Among these polyepoxy compounds (c), bisphenol A diglycidyl ether and bisphenol F glycidyl ether which can be liquid and have low viscosity at room temperature are preferably used. In order to improve heat resistance, phenol novolak polyglycidyl ether or cresol novolak polyglycidyl ether is preferably used.

Further, the tetraglycidyl compound represented by the above formula (1) is a preferable compound since a cured resin excellent in both heat resistance and impact resistance can be obtained.

As such a tetraglycidyl compound,
N, N, N ', N'-tetraglycidylmethylene dianiline, N, N, N', N'-tetraglycidyl ether dianiline, N, N, N ', N'-tetraglycidyl sulfodianiline, N, N, N ', N'-tetraglycidyl sulfide dianiline and the like are preferably used.

The various polyepoxy compounds as described above may be used alone or as a mixture of two or more.

In the thermosetting composition of the present invention, the above components (a), (b) and (c) are used in the polyol compound (b) based on 100 equivalents of isocyanate groups in the polyisocyanate compound (a). 10 to 40 hydroxyl groups
Equivalent, the epoxy group in the polyepoxy compound (c) is 5 to 5.
20 equivalents and the sum of hydroxy and epoxy groups is 15
It is contained at a ratio of up to 45 equivalents.

The reaction between the polyisocyanate compound (a) and the polyol compound (b) produces a polyurethane. Polyurethane is preferably used in a large amount from the viewpoint of improving the impact resistance of the cured resin, but when the amount is large, the heat resistance is reduced.
Therefore, from the viewpoint of the balance between heat resistance and impact resistance of the cured resin, in the present invention, with respect to 100 equivalents of isocyanate groups,
The amount of the hydroxyl group is 10 to 40 equivalents, preferably 15 to 30 equivalents. When the hydroxyl group is less than 10 equivalents, the cured resin obtained has a low impact resistance and easily foams during a reaction (at the time of molding). On the other hand, if it exceeds 40 equivalents, the heat resistance of the cured resin will decrease.

The epoxy group in the polyepoxy compound (c) reacts with the polyisocyanate to form an oxazolidone ring. The oxazolidone ring is a ring having high heat resistance, and the epoxy group and the isocyanate group react in a linear structure instead of a network structure. Although it is preferable also from the viewpoint of impact properties, it requires a higher reaction temperature than polyurethane formation or isocyanurate ring formation by trimerization of isocyanate, so that it is later than polyurethane formation or isocyanurate ring formation during curing. Therefore, when the number of epoxy groups is increased, the number of unreacted epoxy groups increases, so that the heat resistance of the cured resin, particularly the heat distortion temperature, does not increase. As a result of the study by the present inventors, it has been found that the amount of the epoxy group in the composition is preferably 5 to 20 equivalents, and more preferably 7 to 18 equivalents, per 100 equivalents of the polyisocyanate group.

The sum of all hydroxy groups and epoxy groups in the composition must be 45 equivalents or less. If the sum exceeds 45 equivalents, the ratio of trimerization of the isocyanate groups decreases, and the heat resistance of the cured resin decreases. Particularly preferred is 35 equivalents or less. On the other hand, the minimum of the sum of the hydroxy group and the epoxy group is 15 equivalents, and if it is less than 15 equivalents, the crosslinked structure due to trimerization of the isocyanate increases and the heat resistance of the cured resin increases, but the resin becomes brittle.

The curing catalyst (d) used in the present invention
As the catalyst, a catalyst that functions as a catalyst for cyclizing and trimerizing the polyisocyanate compound (a) is effective.

Examples of such catalysts include triethylamine, tripropylamine, tributylamine, triethylenediamine, N-methylmorpholine, N, N'-dimethylpiperazine, N, N ', N "-tris (dialkylaminoalkyl) hexahydro -S-triazine, triethylenemelamine, 1,4-diazabicyclo-2,2,
2-octane, N, N-dimethylbenzylamine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Tertiary amine compounds such as N, N ', N "-tris (dimethylaminopropyl) hexahydro-S-triazine or metal compounds such as sodium methoxide, lead naphthenate, and a chelate compound of salicylaldehyde and potassium. A quaternary ammonium salt represented by the following formula (2) is also preferable.

[0040]

Embedded image [However, in the above formula (2), R _{1 to} R ₄ are the same or different and each is an aliphatic having 1 to 20 carbon atoms, an alicyclic or aromatic hydrocarbon having 6 to 12 carbon atoms, and The total number of carbon atoms contained in the substituents represented by R _{1 to} R ₄ is 1
2 or more. In the formula, X represents halogen. ]

Specific examples of R _{1 to} R _{4 in} the above formula (2) include methyl, ethyl, propyl, butyl, decyl, tetradecyl, benzyl, cyclohexyl, phenyl and the like. However, if the total number of carbons contained in the substituents represented by R _{1 to} R ₄ is smaller than 12, the solubility becomes poor and the system becomes non-uniform, so that the total number of carbons is 12 or more.

In the above formula (2), X represents a halogen and is iodine, bromine, chlorine or fluorine, but the curing reaction is neither too fast nor too slow, and an appropriate curing speed is obtained. From above, bromine and chlorine are preferred.

Specific examples of such quaternary ammonium salts include tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, n-tetradecyltrimethylammonium chloride, benzalkonium chloride and the like. Among them, when the multi-component thermosetting composition of the present invention is used for RTM or S-RIM, a certain amount of time is required until curing.
From that point of view, R _{1 to} R ₄ having 4 to 5 carbon atoms, for example, tetra-n-butylammonium bromide, are preferable since curing is slightly slow.

The use of a quaternary ammonium salt as a curing catalyst brings about the storage stability of a mixed solution of a polyol compound and a polyepoxy compound to which this catalyst has been added, and is very effective in practical use. When this quaternary ammonium salt is used as a curing catalyst, if a small amount of a titanium-based or tin-based compound is added thereto, the curability is further improved, and a cured molded article having both high heat distortion temperature and high impact resistance is obtained. give.

It is particularly effective to use the quaternary ammonium salt in combination with a tin compound as a mixed catalyst. Examples of such tin-based compounds include inorganic and organic tin compounds.
Organic tin compounds such as tin and stannic chloride are di-n-
Examples thereof include butyltin dilaurate, di-n-butyltin diacetate, tri-butyltin acetate, and tetra-n-butyltin. In these,
-Butyltin dilaurate and di-n-butyltin diacetate are preferred because of their good handleability.

Although the optimum range of the amount of the curing catalyst varies depending on the molding method employed in the present invention, it is generally 100 parts by weight of the total resin composition (that is, the total weight of the polyisocyanate, polyol and polyepoxy compounds). Against
It is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight.

When the curing catalyst is a quaternary ammonium salt, the amount used is determined by the total resin composition (total weight of each compound of polyisocyanate, polyol and polyepoxy).
0.3 to 3 parts by weight, preferably 0.1 to 100 parts by weight.
35 to 1 part by weight. The tin compound to be mixed with the quaternary ammonium salt is 0.001 to 100 parts by weight of the total amount.
To 0.25 parts by weight, preferably 0.005 to 0.2 parts by weight.

If the amount of the catalyst is too large, the curing reaction is fast, and problems often arise in the handling of molding, and foaming is liable to occur.

By adding a tin compound to the catalyst system,
The heat distortion temperature (HDT) of the obtained cured resin is increased, and the toughness is also improved. However, if the amount is too large, curing will be too fast, and the heat distortion temperature of the cured resin will be rather lowered.

As described above, if a polyisocyanate compound and a polyepoxy compound are mixed and left to stand, agar-like substances and insoluble precipitates are likely to be formed even in the absence of a catalyst. The generation of agar-like substances is particularly frequently observed in commonly used polyepoxy compounds such as "Epicoat 828" and "Epicoat 815" manufactured by Yuka Shell. The structure of these polyepoxy compounds is not a monomer, but is polymerized to some extent, and contains a hydroxyl group in the structure, and the hydroxyl group gradually reacts with the isocyanate group. It is thought that it is.

However, even a polyepoxy compound having no hydroxyl group in its structure, when mixed with a polyisocyanate compound, produces a precipitate or a gel without a catalyst. This is due to the high reactivity of the isocyanate group, which is presumed to cause a slow reaction with the epoxy group and its adduct. Of course, mixing and storing a polyisocyanate compound and a polyol compound is practically inconvenient since both react gradually without the presence of a catalyst.

That is, in producing a cured resin molded article from the multi-component thermosetting resin composition of the present invention, the above-mentioned compounds and curing catalyst are used as a liquid A (first component) as a polyisocyanate compound (a). And a liquid mixture of a polyol compound (b), a polyepoxy compound (c) and a curing catalyst (d) as liquid B (second component), and separately prepared and stored. Immediately before molding or simultaneously with molding, the two are rapidly mixed and poured into a predetermined mold to be cured by heat reaction, or as a liquid A (first component), a liquid of the polyisocyanate compound (a), Liquid mixture of a part of the polyol compound (b) and the polyepoxy compound (c) as the first liquid (i) (second component) of the liquid B, and as the second liquid (ii) (third component) of the liquid B Polyol compound (b The balance being divided into three liquid substance of the liquid mixture of the curing catalyst (d), at the same time all the previous or molded to shape in the same manner at a time, or in advance B
Solution (i) and solution B (ii) are mixed to form solution B, and
From the viewpoint of storage stability of the liquid, a method in which the liquid is rapidly mixed, poured into a predetermined mold, and cured by heating is preferable.

In the production method of the present invention, a liquid mixture of the polyol compound (b), the polyepoxy compound (c) and the curing catalyst (d) is employed as the liquid B, and in particular, the third liquid is used as the curing catalyst (d). When a tertiary amine compound is used, there is a possibility that the polyepoxy compound undergoes ring-opening polymerization with the tertiary amine compound, and that the tertiary amine forms some adduct with an epoxy group, and the isocyanate is trimerized. The type and amount of the tertiary amine must be optimized to increase the catalytic activity of the reaction.

N, N-dimethylbenzylamine is suitable as a tertiary amine compound which can suppress the activation of the catalyst to a certain extent and prevent the ring-opening polymerization of the epoxy compound from occurring to some extent, and provides the stability of the solution B. The amount is also preferably in the range of 0.15 to 0.05 parts by weight based on 100 parts by weight of the total resin composition.

The solution B is mixed with the polyol compound (b) to be used.
Consisting of a part of the polyepoxy compound (c) and the entire amount of the polyepoxy compound (c)
The method of dividing into the liquid (i) and the second liquid (ii) composed of the remainder of the polyol compound (b) and the curing catalyst (d) is a particularly preferable method that has solved all the problems of the storage properties of the prepared liquid. In this method, there is no problem of high activation of the catalyst due to the epoxy group of the tertiary amine, and there is no limitation on the type and amount of the tertiary amine curing catalyst. Further, the point that the amount of the curing catalyst is small and difficult to measure is overcome by mixing the curing catalyst with the polyol compound, and the handling property is improved.

The polyol compound (b) contained in the first liquid (i) and the polyol compound (b) contained in the second liquid (ii) are not necessarily the same, but are generally the same. Is preferably used in an appropriate amount.

The order of mixing the three liquids is not limited as long as they are mixed in a very short time.
It is preferable to first mix the first liquid (i) with the second liquid (ii) with B, and then mix the liquid A with this mixture.

In any of the two-liquid split type and the three-liquid split type, the mixing method may be any of a collision mixing method, a static mixer method, and a dynamic method.

In the present invention, a liquid mixture of each component is injected into a mold for molding, and is cured by heating in the mold. The reaction temperature varies depending on the type of the polyisocyanate compound, the polyol compound, the polyepoxy compound and the curing catalyst to be used, the proportion used, and the like, but is preferably from room temperature (10 ° C) to 280 ° C. In order to carry out the ring polymerization sufficiently, at least 150 ° C
It is necessary to go through once. Here, once passed, the case where the temperature is raised to 150 ° C. or more during molding in the mold, and the case where the temperature is reduced to 150 ° C. or less in the mold, and then the mold is removed from the mold for 1 hour
The method includes heating to 50 ° C. or higher. Further, the temperature may be raised to 150 ° C. or higher by so-called post-curing (post-curing). In order to prevent defects such as air bubbles from occurring in the molded product, the latter method in which molding is performed first at a low temperature and then post-cured is suitable. The upper limit of the reaction temperature is 280 ° C, preferably 240 ° C, particularly preferably 200 ° C.

The reaction time may be any time that is sufficient for the desired resin to be sufficiently cured, and this time varies depending on the type of raw material used, the proportion used, the reaction temperature, and the like.
It is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 10 hours, particularly preferably about 5 minutes to 10 hours, particularly preferably about 10 minutes to 6 hours.

The reaction can be carried out under normal pressure to pressurization. At this time, the reaction is carried out in an atmosphere of an inert gas such as nitrogen, helium, argon or the like in order to prevent intrusion of water in the air and oxidative deterioration of the resin. Is preferred.

The composition of the present invention can be molded by a commonly used method except that the respective liquids are mixed at the time of molding. Examples of the molding method include compression molding, cast molding, transfer molding (RTM), vacuum molding, centrifugal molding, injection molding, reaction injection molding (RIM), and structural RIM (S-RI).
M) and the like. Among them, transfer molding (RTM), reaction injection molding (RIM) and S-RIM
The method is preferably used.

One or both of the liquids constituting the multi-part type thermosetting resin composition of the present invention may contain, if necessary, fibrous reinforcing materials such as thermoplastic polymer fibers, carbon fibers, glass fibers, and aramid fibers. It can contain fillers, fillers, pigments, colorants, oxidation stabilizers, ultraviolet absorbers, release agents, and the like. When a fibrous reinforcing material is used, the above-mentioned fibrous reinforcing material is optionally inserted into a molding die in the form of a woven fabric or mat, and the composition of the present invention is applied thereon. can do. In such a case,
The heating reaction of each component in the present invention is carried out, for example, in the presence of a fibrous reinforcing material, and a curable resin containing these reinforcing materials, that is, a composite material is obtained.

[0064]

According to the present invention, there is provided a stable and easy-to-handle multi-part type thermosetting resin composition which is liquid at room temperature, and is used for heat resistance, chemical resistance and mechanical properties. Characteristic,
In particular, a cured resin molded product having excellent impact resistance can be efficiently manufactured with good stability, reproducibility, and good performance.

Particularly when a quaternary ammonium salt and a tin-based catalyst are used in combination as a curing catalyst, the heat of reaction is extremely low, and a thick cured resin molded product can be easily obtained.
For example, a molded article having a thickness of 20 cm or more can be molded. In this case, the center of the molded article does not become black due to heat generation.

Moreover, the cured resin molded product obtained from the composition of the present invention has good cutting workability, and can be processed into a square shape or a circular shape using a usual metal cutting machine. The inside can be easily hollowed out.

Accordingly, the manufacturing method of the present invention can be applied to various mechanical parts, such as gears, rollers, encapsulants, structural materials, automobile and airplane parts, electric and electronic parts such as cast insulating materials, semiconductor encapsulation. It can be applied to the production of materials and furniture parts, such as chairs and trunks, car casters, sporting goods, building components, resin mold materials, sample molding materials, prototype materials, and the like.

[0068]

EXAMPLES The present invention will be described in detail below with reference to examples, but the examples are for explanation, and the present invention is not limited to these examples. In addition, the part in an Example shows a weight part unless there is particular notice.

The test methods of the various tests performed in the present example are as follows. (1) Heat distortion temperature (HDT) HDT tester manufactured by Toyo Seiki Seisaku-sho, Model S3-ME
Measured with H at a load of 18.5 kg / cm ² . (2) Notched Izod impact strength (NI) Measured at a thickness of 3 mm according to JIS K6911. (3) Flexural strength and flexural modulus (flexural modulus) Measured according to ASTM D-790. (4) Molding Shrinkage The specific gravity (A) of the liquid mixture and the specific gravity (a) of the molded resin are measured, and are represented by values calculated according to the following equation. Molding shrinkage (%) = (1-A / a) × 100

[0070]

Example 1 Carbodiimide-modified 4,4'-diphenyl
Methane diisocyanate (isocyanate equivalent 6.90
× 10^-3Solution A (first component) consisting of
Was. Separately, as the liquid B (second component), the molecular weight
A mixture of two different polyether polyols
Polyether polyol (OH equivalent 3.70 × 10 ^-3
80 equivalents / g) and a polyepoxy compound ("Epicoat"
828 "epoxy equivalent 5.21 x 10^-3Equivalent / g) 20
Parts and 0.24 parts of N, N-dimethylbenzylamine
Was prepared.

Solution B was stored sealed at room temperature for 30 days.
The liquid viscosity was 402 cps (30 ° C.) at first, but increased slightly to 518 cps (30 ° C.) after 30 days, but was a clear liquid with no precipitate or gel.

Using a RTM molding machine, these two types of liquids were mixed in a static mixer mixing method to obtain 200 parts of liquid A and B
Supply and mix the liquid so that the composition becomes 100 parts,
Was injected into the mold. The mixture was heated in a mold for 30 minutes, then removed from the mold, and post-cured at 180 ° C. for 5 hours to obtain a red-brown transparent resin plate having a thickness of 3 mm. The characteristics of the obtained molded product are shown below.

Flexural strength 14.0 kg / mm ² Flexural modulus 410 kg / mm ² Heat distortion temperature (HDT) 235 ° C. Notched Izod impact strength 5.8 kg · cm / cm Hardness (Shore D) 90

[0074]

Example 2 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90)
× 10 ⁻³ eq / g) of solution A (first component). On the other hand, the same mixed polyether polyol (OH
30 parts of an equivalent of 3.70 × 10 ⁻³ equivalent / g) and polyepoxy (“Epicoat 828” epoxy equivalent of 5.21 × 10 ⁻³⁾
Equivalent / g) 20 parts of solution B (i) (second component) was prepared. Further, the above polyether polyol (OH equivalent: 3.
A liquid B (ii) (third component) comprising 50 parts of 70 × 10 ⁻³ equivalents / g) and 0.90 parts of N, N-dimethylbenzylamine was prepared.

Each of the above-mentioned liquids was stored at room temperature for 60 days or more. However, no change was observed in the viscosity and appearance, and the liquids were stable.

Using these three kinds of liquids, using an RTM molding machine, 200 parts of liquid A (first component), 50 parts of liquid B (i) (second component), and liquid B (ii) (third component) ) Supply 50 parts, mix with a static mixer, and immediately add 14 parts.
It was supplied to a mold at 0 ° C. After 15 minutes, remove it from the mold,
Post-curing was performed at 180 ° C. for 4 hours. The characteristics of the obtained molded product are shown below.

[0077] Flexural strength 13.9 kg / mm ² flexural modulus 412 kg / mm ² heat distortion temperature (HDT) 241 ° C. notched Izod impact strength 5.9 kg · cm / cm Hardness (Shore D) 90

[0078]

Example 3 A solution (first component) of hexamethylene diisocyanate (isocyanate equivalent 11.90 × 10 ⁻³ equivalent / g) was prepared. On the other hand, the same mixed polyether polyol as in Example 1 (OH equivalent 3.70 × 10 ⁻³ equivalent /
g) 20 parts of a polyepoxy compound ("Epicoat 81")
5 "Epoxy equivalent: 5.26 × 10 ^-3 equivalent / g) 20 parts to prepare a liquid B (i) (second component). Further, the above polyether polyol (OH equivalent 3.70 × 10 ⁻³⁾
(Equivalent / g) 40 parts and 0.6 part of N, N-dimethylbenzylamine were prepared as liquid B (ii) (third component).

It was confirmed that each of the above liquids had no problem in storage. Using these three kinds of liquids, an RTM machine was used to obtain a solution A, a solution B (i) and a solution B (ii) each of 120.
, 40 parts, and 40 parts, and the mixture was immediately introduced into a 140 ° C. mold. After 15 minutes, it was removed from the mold and post-cured at 180 ° C. for 3 hours. The characteristics of the obtained molded product are shown below.

Heat Deformation Temperature (HDT) 183 ° C. Notched Izod Impact Strength 66 kg · cm / cm Hardness (Shore D) 88

[0081]

Example 4 Polyphenylene polymethylene polyisocyanate (isocyanate equivalent 6.82 × 10 ⁻³ equivalent /
g) Solution A (first component) was prepared. Separately, as a liquid B (second component), a mixed polyether polyol (OH equivalent 2.18) prepared by mixing different molecular weights.
× 10 ⁻³ equivalent / g) 125 parts, polyepoxy compound (“Epicoat 828” epoxy equivalent 5.21 × 10 ⁻³⁾
(Equivalent / g) A liquid was prepared by mixing 25 parts and 1.1 parts of N, N-dimethylbenzylamine.

Using a RTM molding machine, the two kinds of liquids were mixed with 200 parts of liquid A by a static mixer mixing method.
Parts and solution B are supplied and mixed so as to have a composition of 150 parts.
It was poured into a 35 ° C. mold.

The resin was heated in a mold for 30 minutes, then removed from the mold, and post-cured at 200 ° C. for 3 hours to obtain a red-brown transparent resin plate having a thickness of 3 mm.

The heat distortion temperature (HDT) of the obtained molded plate was 221 ° C., and the notched Izod impact strength was 5.2 kg ·
cm / cm.

[0085]

Example 5 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90)
× 10 ⁻³ equivalents / g) was prepared. Separately, a polyether polyol (OH equivalent 3.15 × 10
⁻³ equivalents / g) 100 parts, polyepoxy compound (“Epicoat 828” epoxy equivalent 5.20 × 10 ⁻³ equivalents / g)
20 parts and tetrabutylammonium bromide 1.6
Part B, a liquid mixture (second component) was prepared from a mixture of 0.03 parts of dibutyltin dilaurate.

The solution A and the solution B were supplied and mixed using an RTM machine so that 200 parts of the solution A and 121 parts of the solution B were mixed.
It was poured into a 40 ° C. mold. The mixture was heated in a mold for 30 minutes, then taken out of the mold, and post-cured at 180 ° C. for 5 hours to obtain a red-brown transparent resin plate having a thickness of 3 mm. The characteristics of the formed plate are shown below.

[0087] Flexural strength 13.9 kg / mm ² Flexural modulus 415kg / mm ² heat distortion temperature (HDT) 236 ° C. notched Izod impact strength 6.2 kg · cm / cm Hardness (Shore D) 91.

When the solution A and the solution B were separately stored for 60 days, respectively, the solution viscosity was 45 cps (3
(0 ° C.) and 365 cps (30 ° C.), there was no change at all, and the characteristics of the molded plate obtained by molding under the same molding conditions after 60 days were not different from those at the beginning.

[0089]

Example 6 The solution A and the solution B of Example 5 were used.
The mixture was supplied and mixed using an RTM machine, and poured into an aluminum cylinder of 20 cmφ (placed on an aluminum plate at the bottom and sealed with an adhesive at the bottom) to a height of about 30 cm.

When left at room temperature, heat was generated after about 15 minutes, and curing started. It hardened in about 1 hour, but the temperature outside the aluminum cylinder was up to 92 ° C. As it is, place it in a hot air drier, initially at 140 ° C for 1 hour, then 180
The temperature was raised to ° C. for 5 hours.

Thereafter, the mixture was cooled to room temperature and taken out from the aluminum cylinder to obtain a red-brown transparent block-shaped cured product having a diameter of 20 cm and a height of 30 cm. The molded product was uniform without blackening of the center and was not foamed.

When the outside of the block-shaped cured molded product was cut to a diameter of 19.5 cm using a metal cutting machine, the block could be easily cut off, and the center portion had an inner diameter of 15 mm.
When it was cut out to a length of 10 cm in cm, it could be easily cut without cracking. The finish was good and beautiful.

[0093]

Example 7 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90)
× 10 ⁻³ eq / g) of solution A (first component). On the other hand, a mixed polyether polyol (OH equivalent: 3.25 × 10 ⁻³ equivalent / g) obtained by mixing different molecular weights is used.
Part and N, N, N ', N'-tetraglycidylmethylene dianiline (epoxy equivalent 9.48 × 10 ^-3 equivalent / g) 1
1 part, 1.6 parts of tetrabutylammonium bromide,
A liquid B (second component) comprising 0.03 parts of dibutyltin dilaurate was prepared. Solution B is slightly turbid, but its turbidity is 6
Even after storage for 0 days, it did not proceed, no precipitation occurred, and the liquid viscosity did not change. Liquid A did not show any change in viscosity after 60 days.

Then, using an RTM molding machine,
Parts and B liquid 112 parts, and mixed.
It was poured into a mold heated to ° C.

After 30 minutes, remove from the mold, and then
Post-curing was performed at 5 ° C. for 5 hours to obtain a molded plate having a thickness of 3 mm. The properties of this molded product are shown below.

Bending strength 14.5 kg / mm ² Bending modulus 436 kg / mm ² Heat distortion temperature (HDT) 258 ° C. Notched Izod impact strength 6.0 kg · cm / cm

[0097]

Embodiments 8 to 10 In Embodiment 7, N, N, N ',
Instead of N'-tetraglycidylmethylenedianiline,
A molding was obtained by performing the same operation as in Example 7, except that the three epoxy compounds shown in Table 1 were used. The properties of these molded products are also shown in Table 1. It should be noted that N.I.
I. Means Notched Izod impact strength.

[0098]

[Table 1]

[0099]

Examples 11 to 13 A liquid (solution A) of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was prepared.
Separately, 100 parts of a mixed polyether polyol (OH equivalent, 3.15 × 10 ⁻³ equivalent / g) prepared by mixing two kinds of polyether polyols having different molecular weights, a polyepoxy compound (“Epicoat 828”) 20 parts of epoxy equivalent 5.20 × 10 equivalent / g) and tetrabutyl-n
-A mixed solution (Solution B) consisting of 1.6 parts of ammonium bromide and 0.03 part of dibutyltin dilaurate was prepared.

A mold having a cavity of 30 cm square and a spacer thickness of 3 mm was prepared for preparing a plate-like composite material, and a glass cloth (manufactured by Nittobo Co., Ltd., W
F-230, N-100) were cut, and a plurality of sheets were laminated so as to have a predetermined V _f (volume content of fiber).

In the mold in which this glass cloth is set,
At room temperature, 200 parts of Solution A and 121 parts of Solution B
The mixture was supplied while being rapidly mixed in a mixing head so as to form parts. While overflowing, the supply was stopped when no air bubbles were observed during the overflow, and the mold was heated to 140 ° C. The mixture was heated in a mold for 30 minutes, then removed from the mold, and post-cured at 180 ° C. for 5 hours.

Thus, a thin red-brown glass fiber reinforced composite material was obtained. Table 2 summarizes the properties of the composite.

[0103]

[Table 2]

As a result, since the composition of the present invention has a low viscosity, it has an advantage that it can easily penetrate into the glass reinforcing material and the content of the glass reinforcing material can be increased, and the characteristics of the molded product are enhanced by the glass fiber. It turned out that it was greatly improved.

[0105]

EXAMPLE 14 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
(0 × 10 ⁻³ equivalent / g) of a liquid (solution A) (200 parts) was prepared. Separately, a mixed polyether polyol (OH equivalent, 3.15 × 10 ⁻³ equivalent / g) prepared by mixing two kinds of polyether polyols having different molecular weights 100
Parts, 20 parts of a polyepoxy compound (“Epicoat 828” epoxy equivalent 5.20 × 10 equivalents / g), 1.6 parts of tetrabutyl-n-ammonium bromide, 0.03 part of dibutyltin dilaurate, and liquid poly (acrylonitrile-butadiene) ) Rubber (terminal OH, molecular weight 3,0
(000-4,000) (16 parts) was prepared.

The liquids A and B were mixed, poured into a flat plate mold (thickness: 3.0 mm) at 140 ° C., heated in the mold for 30 minutes, then taken out of the mold and post-processed at 180 ° C. for 5 hours. A molded plate was obtained by curing. Table 3 shows the properties of the molded plate thus obtained.

From the results shown in Table 3, it can be seen that the impact resistance was improved without deteriorating other physical properties.

[0108]

[Table 3]

[0109]

Example 15 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) of solution A (first component) was prepared.
Separately, a mixed polyether polyol (OH equivalent 4.20 × 10 ⁻³ equivalent /
g) 70 parts, 10 parts of N, N, N ', N'-tetraglycidylmethylenedianiline (epoxy equivalent: 9.48 × 10 ^-3 equivalent / g), 1.4 parts of tetra-n-butylammonium bromide, dibutyltin A liquid B (second component) comprising 0.042 parts of dilaurate was prepared. Solution B was colorless and transparent, and the solution viscosity did not change even after being stored for 60 days.
Liquid A also showed no change in viscosity for 60 days.

Then, using an RTM molding machine,
, B and 81 parts of liquid B, and mixed.
Into a heated mold.

After 30 minutes, take out from the mold, and then
Post-curing was performed at 5 ° C. for 5 hours to obtain a molded plate having a thickness of 3 mm. The properties of this molded product are shown below.

Heat Deformation Temperature (HDT) 211 ° C. Notched Izod Impact Strength 6.6 kg · cm / cm

[0113]

Example 16 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) of solution A (first component) was prepared.
On the other hand, 80 parts of a mixed polyether polyol (OH equivalent: 3.80 × 10 ⁻³ equivalent / g) prepared by mixing two kinds of polyether polyols having different molecular weights, and N, N, N ′,
10 parts of N'-tetraglycidylmethylenedianiline (epoxy equivalent: 9.48 × 10 ⁻³ equivalent / g), tetra-n-
A liquid B (second component) was prepared comprising 1.4 parts of butylammonium bromide and 0.042 parts of dibutyltin dilaurate. Liquid B was colorless and transparent, and the liquid viscosity did not change.
Liquid A also showed no change in viscosity for 60 days.

Then, using an RTM molding machine,
Parts and B solution 91 parts and mixed at 140 ° C.
Into a heated mold.

After 30 minutes, take out from the mold, and then
Post-curing was performed at 5 ° C. for 5 hours to obtain a molded plate having a thickness of 3 mm. The properties of this molded product are shown below.

HDT (load 18.5 kg / cm ² ) 210 ° C. Notched Izod impact strength 6.9 kg · cm / cm

[0117]

Example 17 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ equivalent / g) (solution A) was prepared. Separately, a mixed polyether polyol (OH) prepared by mixing two kinds of polyether polyols having different molecular weights is used.
Equivalent, 3.15 × 10 ⁻³ equivalent / g) 90 parts, polyepoxy compound (“Epicoat 828” epoxy equivalent 5.20)
× 10 equivalents / g) 20 parts, N, N-dimethylbenzylamine 0.16 parts, tetra-n-butylammonium bromide 1.5 parts, dibutyltin dilaurate 0.03
A liquid mixture (solution B) was prepared.

The solution A and the solution B were supplied to an RTM machine so that 200 parts of the solution A and 111 parts of the solution B were mixed rapidly in the mixing head and injected into a mold at 140 ° C.
Heat in mold for 30 minutes, then remove from mold, 1
By post-curing at 80 ° C. for 5 hours, a red-brown transparent molded plate having a thickness of 3 mm was obtained. The heat distortion temperature (HDT) of this molded plate was 238 ° C., and the notched Izod impact strength was 6.0 kg · cm / cm.

When the solution A and the solution B were separately stored at room temperature for 30 days, the solution viscosity was as follows:
ps (30 ° C.), the B liquid is the original 365 cp
s (30 ° C.) was 395 cps (30 ° C.), there was almost no change, and the characteristics of the molded plate obtained by molding under the same molding conditions after 30 days were not different from those at the beginning.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-231978 (JP, A) JP-A-3-128916 (JP, A) JP-A-2-208381 (JP, A) JP-A 64-64 54077 (JP, A) JP-A-53-51298 (JP, A) JP-A-60-69122 (JP, A) JP-A-54-96598 (JP, A) JP-A-49-37999 (JP, A) JP-A-54-13595 (JP, A)

Claims (7)

(57) [Claims] (A) at least one polyisocyanate compound having two or more isocyanate groups (a)
A liquid comprising (a) at least one polyol compound having two or more hydroxyl groups (b), at least one polyepoxy compound having two or more epoxy groups (c), and a curing catalyst (d ), And the mixing ratio of each of the above components in both AB liquids is 10 to 40 equivalents of hydroxy groups in the polyol compound and 100 equivalents of isocyanate groups in the polyisocyanate compound. Epoxy group 5 in
A multi-part thermosetting resin composition, wherein the composition has a ratio of 15 to 45 equivalents with respect to 100 equivalents of an isocyanate group in an amount of from 20 to 20 equivalents. 2. The polyepoxy compound (c) in the liquid B,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, resorcinol diglycidyl ether,
Hexahydrobisphenol A diglycidyl ether,
Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl phthalate, triglycidyl isocyanurate, phenol novolak polyglycidyl ether, cresol novolac polyglycidyl ether, and a tetraglycidyl compound represented by the following formula (1): [However, in the above formula (1), Y is -CH _2- , -C (C
H ₃ ) _2- , -O-, -SO _2- , -S- and -C (C
F _{3) 2} - is more becomes group selected from the group, G ^1, G
² , G ³ and G ⁴ are respectively The same or different groups selected from The multi-component thermosetting resin composition according to claim 1, which is at least one compound selected from the group consisting of: 3. The curing catalyst (d) in the liquid B is triethylamine, tripropylamine, tributylamine, triethylenediamine, N-methylmorpholine, N, N '.
-Dimethylpiperazine, N, N ', N "-tris (dialkylaminoalkyl) hexahydro-S-triazine, triethylenemelamine, 1,4-diazabicyclo-
2,2,2-octane, N, N-dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine, Sodium methoxide, lead naphthenate, a chelate compound of salicylaldehyde and potassium, and a fourth compound represented by the following formula (2):
Grade ammonium compound [However, in the above formula (2), R ¹ , R ² , R ³ , and R ⁴ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms and 6 to 12 carbon atoms.
And the same or different groups selected from the alicyclic or aromatic hydrocarbon groups described above, and the total number of carbon atoms in R ¹ , R ² , R ³ and R ⁴ is 12 or more. X represents halogen. The multi-component thermosetting resin composition according to claim 1, which is at least one compound selected from the group consisting of: 4. A curing catalyst (d) comprising at least one quaternary ammonium compound represented by the above formula (2).
Salts of stannous, the stannic chloride, di -n- butyl tin dilaurate, di -n- butyl tin acetate, and characterized by including at least one tin compound selected from tributyltin acetate and tetra -n- butyltin The multi-part type thermosetting resin composition according to claim 3, wherein Of 5. The method of claim 1, wherein the polyisocyanate compound (a), polyol compounds (b), Ru using polyepoxy compound (c) and consisting of a curing catalyst (d) multi-part type thermosetting resin composition In the method of manufacturing a cured resin molded product,
A method for producing a cured resin molded product, comprising mixing a liquid A and a liquid B during molding, injecting the mixed liquid into a predetermined mold, and curing by heating. 6. A first liquid (i) comprising a mixture of a part of the polyol compound (b) and the whole amount of the polyepoxy compound (c) until the liquid B is subjected to molding; and a polyol compound (b). 6. The method for producing a cured resin molded product according to claim 5, wherein the second liquid (ii) comprising a mixture of the remainder of (a) and the curing catalyst (d). 7. When mixing each liquid, first, the first liquid (i) and the second liquid (ii) are mixed to prepare a liquid B, and the liquid B and the liquid A are further mixed. The method for producing a cured resin molded product according to claim 6 , characterized in that: