JP2574089B2 - 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 1. Field of the Invention The present invention relates to a method for producing a thermosetting resin having excellent heat resistance and a novel thermosetting resin composition used therefor. More specifically, using a thermosetting resin composition with good handleability and moldability, such as low liquid viscosity and curing at a relatively low temperature, the heat resistance, chemical resistance, mechanical properties, and electrical properties are improved. The present invention relates to a method for producing an excellent cured resin and a novel thermosetting resin composition used for the method.

[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, a reaction-molding type resin using a reactive monomer or oligomer, that is, a resin that simultaneously performs molding and polymerization using a relatively low-viscosity (preferably, liquid at room temperature) raw material is attracting attention. ing.
Such resins include polyurethane resins, epoxy resins,
Unsaturated polyester resins, vinyl ester resins, polydicyclopentadiene resins, and the like are known, and some of them are commercialized.

[0003] However, these resins each have advantages and disadvantages. For example, polyurethane resins have low heat resistance,
Unsaturated polyester resins and epoxy resins are superior in heat resistance to polyurethane resins, but have the problem that they are hard and brittle, or their reactivity is not always sufficiently high.

As a method of improving the heat resistance of a polyurethane resin, a method of introducing an isocyanurate ring by trimerizing an isocyanate is disclosed, for example, in Japanese Patent Publication No. 44-16669.
It has been known for a long time in Japanese Unexamined Patent Publication (Kokai) No. HEI 9 (1995) and has been put to practical use. However, in this method, the heat resistance is improved by about 20 to 30 ° C. as compared with the ordinary method, and the heat deformation temperature is at most 150 to 160 ° C., and the viscosity of the resin liquid is not necessarily low. .

As a thermosetting resin using this polyisocyanate as one raw material, a thermosetting resin utilizing an oxazolidone ring formation which is a ring reaction between an isocyanate group and an epoxy group has been known for a long time. Kaisho 6
2-isocyanate as disclosed in JP-A-2-62879.
A combination of a quantified isocyanurate ring and this oxazolidone ring formation has also been proposed. This is because the cured resin has high heat resistance, but since epoxy resin is used, the viscosity of the resin liquid is not always sufficiently low and the reaction temperature is not always sufficiently low, so that there is a problem in handleability and moldability.

JP-B-53-31515 discloses a method for producing a polymerizable resin, which comprises reacting a polyisocyanate with an acrylate or an α-alkyl acrylate having an epoxy group. Have been. In this method, an isocyanate group and an epoxy group are reacted in advance to form an oxazolidone ring to form a polymerizable resin, and then a radical catalyst is added to polymerize the remaining vinyl group to obtain a thermosetting resin. Therefore, this polymerizable resin has a high viscosity and is not suitable for reaction molding.

Further, the above-mentioned Japanese Patent Publication No. 53-31515 does not generally describe the use ratio of polyisocyanate and an acrylate or an α-allyl acrylate having an epoxy group. Only an example using an equivalent amount of an epoxy group is shown.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid thermosetting resin composition suitable as a reactive resin having a low viscosity and a high reactivity and having excellent handleability. is there.

Still another object of the present invention is to provide a method for producing a cured resin molded article having excellent heat resistance using the above-mentioned thermosetting resin composition.

[0010]

According to the present invention, the above objects are attained by providing a polyisocyanate compound (a), (β-methyl) glycidyl (meth) acrylate (b), a radical catalyst (d) and a ring catalyst ( c) and a thermosetting resin composition containing a polyol compound (e) and / or a polyepoxy compound (f) if necessary and containing each of the above components at a specific ratio; and a polyisocyanate compound (a) , (Β-methyl) glycidyl (meth) acrylate (b) and, if necessary, a polyol compound (e) and / or a polyepoxy compound (f) are added to a radical catalyst (d) and a ring catalyst (c). A method for producing a thermosetting resin molded product by reacting in the coexistence.

That is, the present invention provides a solution A comprising at least one kind of polyisocyanate compound (a);
It comprises a combination of methyl) glycidyl (meth) acrylate (b) and at least one type of ring catalyst (c) with a liquid B, and the liquid A and / or the liquid B contains at least one radical catalyst (d). Is a multi-part type thermosetting resin composition.

Solution B further contains a polyol compound (e)
And / or a polyepoxy compound (f).

Solution B can be divided into a first solution (i) consisting of (β-methyl) glycidyl (meth) acrylate (b) and a second solution (ii) consisting of a ring-forming catalyst (c). . The first liquid (i) and / or the second liquid (ii) can contain a polyol compound (e). Further, the first liquid (i) can contain a polyepoxy compound (f).

Further, the present invention provides a method for producing a cured resin molded product using the multi-part type thermosetting resin composition comprising the liquid A and the liquid B, wherein the liquid A and the liquid B are mixed at the time of molding.
It includes a method for producing a cured resin molded product, which comprises injecting a mixed solution into a predetermined mold and curing the mixture by heating.

The polyisocyanate compound (a) used in the present invention has at least two isocyanate groups in its molecule. Examples of the aliphatic polyisocyanates include hexamethylene diisocyanate, 2,2,4 And 2,4,4-trimethylhexamethylene 1,6-diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated meta or para 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. Soshi Sulfonates, 1,5-naphthalene diisocyanate, can be mentioned meta or para-xylylene diisocyanate and the like.

Further, polyphenylenepolymethylene polyisocyanate prepared by isocyanating polyamine obtained by condensation of aniline and formalin with phosgene or carbodiimide-modified or polyol-modified polyisocyanate can also be used.

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

These can be used alone or in a mixture of two or more. Of these, carbodiimide or polyol-modified 4,4'-diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, 2,4- or 2,6-tolylene diisocyanate which is liquid at room temperature and has low viscosity (about 25 poise or less) Isocyanates and the like are preferably used.

The component (b) used in the present invention is (β-methyl) glycidyl (meth) acrylate, specifically, glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, and β-methyl glycidyl methacrylate. These can be used alone or in a mixture of two or more.
The use ratio of the component (a) and the component (b) is
Methyl) glycidyl (meth) acrylate (b) 100 equivalents of epoxy groups of the above polyisocyanate (a)
Isocyanate group of 120 to 1000 equivalents, preferably 150 to 900 equivalents, particularly preferably 160 to
800 equivalents.

The polyol compound (e) used in the present invention has at least two aliphatic and / or alicyclic hydroxy groups in its molecule.

Examples of the polyol include (a) polyether-based polyols; for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; a polyol obtained by adding ethylene oxide, propylene oxide, or the like to an aromatic polyol such as bisphenol A; (B) polyester-based polyols such as propylene glycol, glycerol, pentaerythritol, sorbitol, trimethylpropanol, polyol obtained by adding ethylene oxide and / or propylene oxide to N-diethanolamine, and the like; adipate-based polyol, polycaprolactone-based polyol , Polycarbonate polyols and the like, or (c) polyether polyester polyols and polyester amide polyols. And (d) polyalkylene glycols having a certain number of repeating units such as ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, 1,4- or 1,5-hexanediol. Glycerin, pentaerythritol, sorbitol, trimethylolpropane, aromatic, alicyclic, aliphatic N-mono-
Substituted ethanolamines and the like and (e) alicyclic polyols; for example, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and the like can be mentioned. Further, (f) polybutadiene having terminal hydroxy, polybutadiene-styrene copolymer, and polybutadiene-acrylonitrile copolymer are also used as the polyol.

These polyols can be used alone or in a mixed state. However, in order to balance the properties of the cured resin such as heat resistance and impact resistance and the practical properties such as moldability and reactivity, use these polyols in a mixed form. Is preferred.

Among these polyol compounds, those polymerized to some extent from the viewpoint of impact resistance are preferable, and from the viewpoint of heat resistance and water resistance, polyether polyols are mainly used, and other polyol compounds are used in addition to these. Is preferred.

From the viewpoint of moldability, those which are liquid or nearly liquid at room temperature are preferably used.

In the present invention, the heat segment is improved by the formation of an isocyanurate ring by the cyclization trimerization (tricyclization) of the isocyanate, and the soft segment is introduced by reacting the isocyanate with the polyol compound to form a urethane structure. Thus, the toughness of the resin can be improved.

When component (a), component (b) and component (e) are used in combination, the proportion of each component used is the same as that of (β-methyl) glycidyl (meth) acrylate (b)
The isocyanate group of the polyisocyanate (a) is 120 to 1000 equivalents, preferably 150 to 900 equivalents, particularly preferably 1 to 100 equivalents of the epoxy group of the polyisocyanate (a).
It is 60 to 800 equivalents. In addition, the equivalent of the isocyanate group of the polyisocyanate (a) defined within the above range is subtracted from the equivalent of the epoxy group of the (β-methyl) glycidyl (meth) acrylate (b), and the remaining isocyanate group is equivalent to 100 equivalents. The hydroxyl group of the polyol compound (e) is 5 to 75 equivalents, preferably 7 to 60 equivalents, particularly preferably 9 to 50 equivalents.

If the ratio is outside the above range, problems may occur such that the physical properties of the obtained cured resin are reduced, the liquid viscosity is increased, and the moldability is reduced.

The polyepoxy compound (f) used in the present invention has at least two epoxy groups in its molecule, and the following compounds are exemplified.

(I) Glycidyl ether compound:
2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone,
Aromatic polyols such as resorcinol, phenol novolak, cresol novolak, resorcinol novolak, naphthol novolak, dihydroxynaphthalene, dihydroxynaphthalene novolak; aromatic hydroxy compounds such as phenol, dihydroxybenzene, naphthol, dihydroxynaphthalene and glyoxal, glutaraldehyde; Polyols obtained by a dehydration reaction with an aldehyde such as p-hydroxybenzaldehyde, p-formylbenzoic acid, benzaldehyde in the presence of, for example, an acidic catalyst; hydrogenated bisphenol A, butanediol, polypropylene glycol, polyethylene glycol, glycerol, etc. Glycidyl ethers of polyols such as polyhydric alcohols.

(Ii) Glycidyl ester compounds: glycidyl esters of dicarboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid and naphthalenedicarboxylic acid.

(Iii) N-glycidyl compounds: Compounds in which active hydrogen bonded to the nitrogen atom of a nitrogen-containing compound such as aniline, isocyanuric acid, methylene dianiline or the like is replaced by a glycidyl group.

(Iv) Glycidyl ether ester compounds: glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid and hydroxynaphthoic acid.

(V) Alicyclic epoxy compounds: cyclopentadienedioxide, dicyclopentadienedioxide, vinylcyclohexenedioxide and compounds represented by the following formula:

[0034]

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(Vi) Others: triglycidyl compounds of p-aminophenol and the like.

Among these polyepoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and alicyclic epoxy compounds which can be liquid and have low viscosity at room temperature are preferably used. To improve heat resistance, phenol novolak and cresol novolak polyglycidyl ether are preferably used.
It is also preferable that these polyepoxy compounds are liquid or nearly liquid at room temperature. These epoxy compounds can be used alone or in a mixture of two or more.

The proportions of the components (a), (b) and (f) are as follows: (β-methyl) glycidyl (meth) acrylate (b) and polyepoxy compound (f)
The isocyanate of the above polyisocyanate (a) is 120 to 1000 equivalents, preferably 150 to 900 equivalents, and particularly preferably 160 to 800 equivalents, with respect to 100 equivalents of the total epoxy group.

The proportion of the components (b) and (f) within the above-mentioned range is 100 parts by weight of the polyepoxy compound (f) with respect to the (β-methyl) glycidyl (meth) acrylate (b). ) 10 to 1000 parts by weight, preferably 15 to 800 parts by weight, particularly preferably 20 to 750 parts by weight.

In an embodiment in which the above component (f) is blended in addition to the above components (a), (b) and (e), the proportion of each component used is the above (β-methyl) glycidyl (meth) acrylate (B) and polyepoxy compound (f)
The isocyanate group of the polyisocyanate (a) is from 120 to 1,000 equivalents, preferably from 150 to 900 equivalents, particularly preferably from 160 to 800 equivalents, based on 100 equivalents of the total epoxy groups.

The equivalent of the total of the epoxy groups of the (β-methyl) glycidyl methacrylate (b) and the polyepoxy compound (f) is calculated from the equivalent of the isocyanate groups of the polyisocyanate (a) specified in the above range. The hydroxyl group of the polyol compound (e) is 5 to 75 equivalents, preferably 7 to 60 equivalents, and particularly preferably 9 to 5 equivalents to 100 equivalents of the isocyanate groups remaining after subtraction.
It is 0 equivalent.

By using the polyol compound (e) and the polyepoxy compound (f) together as described above, an oxazoline ring structure formed from an epoxy group and an isocyanate group is formed in addition to the urethane structure described above. Has a high heat resistance and a linear structure, and thus has an effect of improving both heat resistance and toughness.

As the radical catalyst (d) constituting the composition of the present invention, organic peroxides and organic azo compounds are preferably used. Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl isobutyl ketone peroxide; hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; Peroxy esters such as tertiary butyl peroxy octoate, tertiary butyl peroxy benzoate and the like;
Dialkyl peroxides such as 1,3-bis (t-butylperoxyisopropyl) benzene, dicumyl peroxide, tris- (tert-butylperoxy) triazine; isobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, etc. Peroxyketals such as 1,1-di-tert-butylperoxycyclohexane, 2,2-di- (tert-butylperoxy) -butane; tert-butylperoxyisopropyl carbonate, bis And percarbonates such as (4-tert-butylcyclohexyl) peroxydicarbonate and di-3-methoxybutylperoxydicarbonate. As the organic azo compound, specifically, azobisisobutyronitrile,
Azobisal2 canonitriles such as azobiscarbonamide can be mentioned.

One or more of these radical catalysts can be used. These radical catalysts are used in an amount of 0.05 to 15% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 10% by weight, based on the total amount of the component (b) and the optional ethylenically unsaturated compound. 0.2 ~
The amount is about 5% by weight.

The above radical catalysts include organic salts of polyvalent metals such as octylates or naphthenates of cobalt, manganese, iron, copper and other heavy metals and, if necessary, organic salts of dimethylaniline and dimethylparatoluidine. 3
Addition of a small amount of a polymerization accelerator such as a secondary amine or a polymerization inhibitor such as hydroquinone, naphthoquinone, tertiary butyl catechol, p-benzoquinone, butylated hydroxytoluene, nitroxide radicals, etc. It can be preferably implemented for improvement.

On the other hand, as the ring-forming catalyst (c), a cyclization trimerization (tricyclization) catalyst for an isocyanate compound and a catalyst for forming a polyoxazolidone ring by reacting an isocyanate compound with an epoxy compound are most effective. Examples include tertiary amine compounds and quaternary ammonium salts.

Examples of tertiary amine catalysts include triethylamine, benzyldimethylamine, N, N-dimethylaniline, N, N-dimethyl-p-toluidine,
N'-dimethylpiperazine, N-glycidyl-N, N-
Dimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, pyridine, N, N, N ', N'-
Tetraglycidylmethylenedianiline, 1- (N, N-
Diglycidylamino) -4-glycidyloxybenzene,
N, N, N ', N'-tetraglycidyl-m-xylylenediamine, N, N, N', N'-tetraglycidyl-
Tertiary amino compounds such as p-xylylenediamine; imidazole, 2-methylimidazole, 2-ethyl-4-
Methylimidazole, 1-cyanoethyl-2-ethyl-
Imidazoles such as 4-methylimidazole; morpholine derivatives such as N-methylmorpholine; N, N ', N "-
Tris (dimethylaminopropyl) hexahydro-S-
Hexahydro-S-triazines such as triazine, 1,
8-diazabicyclo [5.4.0] -7-undecene,
Examples thereof include diazabicyclo compounds such as 1,4-diazabicyclo [2.2.2] octane.

On the other hand, quaternary ammonium salts include cyclization trimerization (hereinafter referred to as tricyclization) catalysts for isocyanate compounds and catalysts for forming a polyoxazolidone ring by reacting an isocyanate compound with an epoxy compound. A specific quaternary ammonium salt represented by the following formula (I) is used.

[0048]

Embedded image

In the above formula (I), R _{1 to} R ₄ are the same or different and each is an aliphatic, alicyclic or aromatic hydrocarbon having 1 to 20 carbon atoms which may be substituted by a hydroxyl group or a halogen. And the total number of carbon atoms contained in the substituents represented by R _{1 to} R ₄ is 12 or more. Where X
Is chlorine or fluorine.

Specific examples of R _{1 to} R _{4 in} the above formula (I) include methyl, ethyl, propyl, butyl, decyl, tetradecyl, 2-hydroxyethyl, benzyl, cyclohexyl, phenyl and the like.

Accordingly, specific examples of the quaternary ammonium salt include tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, benzalkonium fluoride, benzalkonium chloride, and n-tetradecyltrimethyl. Ammonium Fluoride, n-
Examples include tetradecyltrimethylammonium chloride, benzyldi (2-hydroxyethyl) methylammonium fluoride, benzyldi (2-hydroxyethyl) methylammonium chloride and the like.

Each of the above quaternary ammonium salts has R ₁ to
The total number of carbon atoms contained in the substituent represented by R ₄ is 12 or more. If the total number is smaller than 12, the solubility is poor and a heterogeneous system is not preferred.

Although the above quaternary ammonium salts are used alone, it is also preferable to use a mixture of two or more of them for the purpose of controlling the reaction and improving the solubility.

The reaction in the production of the cured resin of the present invention includes a tricyclization reaction of an isocyanate, a ring formation reaction such as an oxazolidone ring formation reaction between an isocyanate and an epoxy group, and a radical polymerization of a vinyl group. At this time, if the tricyclization reaction occurs prior to the radical polymerization, the obtained molded article has good physical properties, but if the radical polymerization occurs first, the obtained molded article is cracked or becomes brittle. When a quaternary ammonium salt is used as a catalyst, the reactivity of the ring reaction is slower when a counter ion is iodine or bromine than when chlorine or fluorine is used. It is hard to get things.

The fourth catalyst functioning as the ring catalyst described above.
Among the quaternary ammonium salts, compounds having a counter ion of fluorine are particularly preferable because the physical properties of the molded product are better than those of a compound having a counter ion of chlorine.

The above-mentioned ring catalyst may be used alone, but may be used as a mixture of two or more kinds for the purpose of controlling the reaction. For example, by using approximately equal weights of imidazoles and triazine type catalysts, it is possible to increase the reactivity compared to using each alone,
When a low-reactivity catalyst such as 2,4,6-tris (dimethylaminomethyl) phenol or a quaternary ammonium salt is used in combination with a triazine-type catalyst, the reaction rate can be controlled by the amount ratio thereof.

The amount of the above ring-forming catalyst is 0.001 to 1 with respect to 100 parts by weight of the polyisocyanate compound (a).
0 parts by weight, preferably 0.005 to 5 parts by weight. If the amount of the catalyst is large, the curing reaction is too fast and foaming is liable to occur. On the other hand, when the amount of the catalyst is small, the tricyclization reaction of the isocyanate becomes extremely slow, which is not preferable.

The above tertiary amines coexist with epoxide groups and ripen to increase the ability as a ring catalyst,
The curing reaction becomes very fast. Therefore, when the composition containing the catalyst has a high ability to supply the resin liquid, the composition can be cycled up and is a preferable composition. On the other hand, in the composition using the quaternary ammonium salt as described above, the reaction is slower than when the tertiary amine catalyst is used,
However, since the reactivity is stable, it can be applied to an apparatus in which the supply capacity of the resin liquid is not so high, and is also useful in a case where it is preferable that the curing speed is not so high as in RTM, for example.

In the present invention, an acidic stabilizer or the like can be further added for stabilizing the storage of the composition.

In the present invention, the above (a), (b),
(C), (d), (e), (f) In addition to each component, (a) and / or (b) and / or
Alternatively, a compound capable of reacting with the component (e) and / or the component (f) can also be used for improving physical properties and the like. Examples of the compound include a polyamine compound capable of improving the mechanical properties of a cured resin by introducing a soft segment into the system by reacting with an isocyanate group of the component (a) to form a urea bond, and a vinyl group of the component (b). To improve the handleability by lowering the viscosity of the entire system, or to improve the mechanical properties and heat resistance, such as monomers having an ethylenically unsaturated bond, unsaturated polyesters, vinyl esters, maleimides, allylimides, etc. A compound having an ethylenically unsaturated bond, a monoepoxy compound which reacts with an isocyanate group of the component (a) to improve the handleability by lowering the viscosity of the entire system, and an epoxy group of the component (b) and the component (f) Epoxy curing agents such as polyphenols, which can improve the mechanical properties and control the reaction rate, and the components (b) and (f). Such as carboxymethyl group and (e) a cyclic imino ether compound is reacted with the hydroxy groups of component may improve the mechanical properties can be exemplified as preferred.

Further, when a polyol component (e) is added in addition to the radical catalyst (d) and the ring catalyst (c),
In particular, when a quaternary ammonium salt is used as a ring-forming catalyst, it is also preferable to add a tin-based urethane reaction catalyst such as dibutyltin dilaurate, or a carbodiimide forming catalyst depending on other components to be added as necessary. It is also preferable to add another catalyst such as an epoxy curing accelerator.

A particularly preferred combination of the components in the present invention is described below. As a polyisocyanate compound (a), 4,4'-diphenylmethane diisocyanate and / or tolylene diisocyanate modified to a liquid having a viscosity at 25.degree. Using isocyanate, (β
It is preferable to use glycidyl methacrylate as (-methyl) glycidyl (meth) acrylate (b) and use a polyether polyol or polyester polyol as the polyol compound (e). The radical catalyst (d) and the ring-forming catalyst (c) are required. It can be appropriately selected depending on the reaction conditions (reaction temperature, reaction time) to be obtained.

In the method of the present invention, as a method of thermally curing the above-mentioned thermosetting resin composition to obtain a cured resin molded product, there are a two-component method and a three-component method described below.

The two-liquid method specifies a polyisocyanate compound (a), (β-methyl) glycidyl (meth) acrylate (b), a catalyst, a polyol compound (e) added as required, and a polyepoxy compound (f). The mixture is mixed intimately with each other, and further heated and dissolved as necessary to obtain two types of mixed liquids. These two types of mixed liquids are mixed by a mixing head or the like at the time of molding to obtain a thermosetting composition. After the product is formed, it is injected directly into the mold of the desired shape, which has been brought to the reaction temperature in advance, and reacted or coated,
There is a method of reacting by means such as spraying and dipping.

In the case of the two-liquid method, the polyisocyanate compound (a) is used as liquid A, and (β-methyl) glycidyl (meth) acrylate (b), a ring-forming catalyst (c) and, if necessary, are added separately. A and B2 liquids in which a polyol compound (e) and / or a polyepoxy compound (f) are mixed and dissolved together to form a liquid B, and at least one of them contains a radical catalyst (d). It is preferred to prepare and store the liquids A and B separately until molding, because of good storage stability. However, depending on the type of the radical catalyst (d), it may be preferable that a part of the radical catalyst is dissolved in the solution A to improve the storage stability. In the case where the two liquids are divided into the A and B liquid types as described above, it is preferable that the two liquids are uniformly mixed immediately before or during the molding to perform the reaction molding.

In the three-liquid method, a liquid material of the polyisocyanate compound (a) is used as the liquid A (first component), and (β-methyl) glycidyl (meth) is used as the first liquid (i) (second component) of the liquid B. The acrylate (b) and the second liquid (ii) (third component) of the liquid B are divided into three types of the ring-forming catalyst (c).
At least one of the liquids contains the radical catalyst (d), and immediately before or simultaneously with molding, all at once or in advance, the first liquid (i) of liquid B and the second liquid (ii) of liquid B are mixed in advance. It is preferable from the viewpoint of storage stability of the solution that the solution A is rapidly mixed with the solution A, poured into a predetermined mold and cured by heating.

In this case, the polyol compound (e) can be contained in the first liquid (i) and / or the second liquid (ii) of the liquid B. Further, the first liquid (i) may contain a polyepoxy compound (f). First liquid (i) and / or
Alternatively, the second liquid (ii) may contain the polyol compound (e), and the first liquid (i) may further contain the polyepoxy compound (e).

The two-liquid method and the three-liquid method described above can be industrially suitably carried out, and are excellent in storage stability of the liquid, handling such as reaction control, and workability.

Solution B was treated with (β-methyl) glycidyl (meth)
The method of dividing into the first liquid (i) composed of the acrylate (b) and the second liquid (ii) composed of the ring-forming catalyst (c) is a particularly preferable method which has solved all the problems of the storage property 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 reaction temperature varies depending on the polyisocyanate compound, (β-methyl) glycidyl (meth) acrylate, polyol compound, the type of the fourth component and catalyst added as required, the proportion of the catalyst used, and the like.
The temperature is preferably 280 ° C, more preferably 15 to 240 ° C or less, especially preferably 20 to 200 ° C or less.

Further, after curing at the above-mentioned reaction temperature, the molded product may be further heated and post-cured, for the purpose of improving the heat resistance of the cured resin molded product.

The reaction time may be sufficient to sufficiently cure the target resin. The time varies depending on the type of each component used, the proportion used, the reaction temperature, etc., but is preferably from 10 seconds to 24 hours. The time is preferably from 20 seconds to 10 hours, particularly preferably from 30 seconds to 6 hours.

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

The above-mentioned thermosetting resin composition to be cured may contain, if necessary, fibrous reinforcing materials such as thermoplastic polymer fibers, aramid fibers, inorganic fibers, carbon fibers, glass fibers, various fillers, Elastomers, fillers, pigments,
It may contain a coloring agent, an oxidation stabilizer, an ultraviolet absorber, a release agent, a thermoplastic polymer, a low-shrinking agent such as a bicyclo compound and a spiro compound, an elastomer, and the like. For example, in the case of a fibrous reinforcing material, the fibrous reinforcing material is inserted into a reaction mold in advance in the form of a woven fabric or a mat as necessary, and the thermosetting resin composition is applied thereon. be able to. In such a case, the heating reaction of each component is performed, for example, in the presence of a fibrous reinforcing material, and the thermosetting resin can be obtained as a resin containing these reinforcing materials, for example, as a composite material.

[0075]

According to the present invention, since a thermosetting resin composition which is liquid at room temperature is used, it can be injected into a mold or the like at a low pressure, and has excellent impregnation when a reinforcing fiber is used. In addition, workability and handleability are excellent, for example, the filling amount of the filler can be increased. Moreover, the resin cured by reaction has an isocyanurate structure formed by cyclization and trimerization (tricyclization) of isocyanate and an oxazolidone ring structure formed by reaction of isocyanate and epoxy, so that heat resistance, chemical resistance and mechanical properties are obtained. To give a molded article excellent in quality. When a polyol compound is further added, the reaction-cured resin has a urethane structure formed by the reaction of an isocyanate and a hydroxy group, and when a polyepoxy compound is added, the reaction-cured resin is reacted by an isocyanate and an epoxy. Since the formed oxazolidone ring structure is increased, it is possible to give a molded article having excellent mechanical properties such as heat resistance and toughness.

According to the production method of the present invention, the reaction,
Since curing is caused during molding, it is possible to produce a cured resin having various excellent properties as described above while maintaining the above-described good workability and handleability.

[0077]

Hereinafter, the present invention will be described in detail with reference to Examples.
These examples are illustrative and do not limit the invention.

[0078]

Examples 1 to 3 Predetermined amounts of (β-methyl) shown in Table 1
A solution obtained by adding and dissolving glycidyl (meth) acrylate and a predetermined amount of a catalyst shown in Table 1 is referred to as a liquid B. Separately, 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) is used as solution A. Liquid A and liquid B are both liquids having low viscosity.

The above A and B2 liquids were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and mixed and poured into a 3 mm thick mold at room temperature (about 30 ° C.). After 15 minutes, it was removed to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 150 ° C. for 2 hours.

This molded plate was made by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
Table 1 shows the results of measuring the heat distortion temperature (HDT) using an SP tester.

[0081]

[Table 1]

[0082]

Example 4 N, was added to 140 g of glycidyl methacrylate.
N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine 2.1 g, imidazole 2.1
g and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene were uniformly dissolved in a solution B.

Separately, the polymethylene polyphenyl polyisocyanate shown in Table 2 was used as solution A.

The above-mentioned liquids A and B2 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at room temperature (about 30 ° C.) while mixing therein. After 15 minutes, it was removed to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 150 ° C. for 2 hours.

The heat distortion temperature (HDT) of this product is shown in Table 2, and it was found that each resin was a resin having high heat resistance.

[0086]

[Table 2]

[0087]

Examples 5 to 14 Glycidyl methacrylate 14.0
g was added with a predetermined amount of the catalyst shown in Table 3 and dissolved therein.
Liquid.

Separately, carbodiimide-modified 4,4'-
28.4 g of diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) is used as the liquid A. At this time, the solution B prepared immediately before the test is used.
After the above liquids A and B were placed in a tester and mixed quickly and uniformly, the time until the mixture lost its fluidity and gelled in a bath at the temperature shown in Table 3 was measured. The results are shown in Table 3, but depending on the catalyst, the reaction can be performed very quickly.
It was also found that the reaction was easy to control and the resin composition was excellent in handleability.

[0089]

[Table 3]

[0090]

Examples 15 to 18 70 g of glycidyl methacrylate
A solution obtained by adding 1.06 g of benzyldimethylamine to 2.12 g of BPOB (same as that described in Table 1) and further adding phenol and bisphenol A in the amounts shown in Table 4 and aging at room temperature for 24 hours is referred to as solution B.

Separately, carbodiimide-modified 4,4'-
142 g of diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) is used as the liquid A.

The viscosity of the liquid B using a B-type viscometer, 7.0 g of the liquid B and 14.2 g of the liquid A were placed in a tester, mixed rapidly and uniformly, and then subjected to fluidity at room temperature (about 30 ° C.). Time until disappearance and gelation, 20 g of solution B and 4 g of solution A
0.6 g at 100 ° C. according to the molding method shown in Examples 5 and 6.
The curing reaction was carried out for 30 minutes, and this was post-cured at 180 ° C. for 2 hours.

The results obtained by measuring the liquid viscosity, the gelation time and the heat distortion temperature of the molded product in the same manner as described above using the solution B left at room temperature for the number of days shown in Table 4 are shown in Table 4. It was found to be excellent in stability and excellent in handleability and heat resistance even after lapse of time.

[0094]

[Table 4]

[0095]

Example 19 70 g of glycidyl methacrylate, 1.06 g of benzyldimethylamine, 2.12 g of BPOB (the same as those shown in Table 1), and the acrylonitrile / butadiene liquid rubber (vinyl-terminated,
A solution obtained by adding and dissolving a molecular weight of 3500 acrylonitrile component (16.2% by weight) is referred to as a liquid B.

Separately, 159 g of polyol-modified 4,4′-diphenylmethane diisocyanate (isocyanate equivalent: 6.29 × 10 ⁻³ equivalent / g) is used as solution A.

The above liquids A and B were put into a tester, mixed quickly and uniformly, then degassed in vacuum, and poured into a 3 mm-thick mold heated to 100 ° C. in advance. 3mm after 30 minutes
A thick molded plate was obtained. The obtained molded plate was further cured (post-cured) at 180 ° C. for 2 hours.

[0098] This molded plate is made of HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The results of measuring the heat distortion temperature (HDT) using an SP tester are shown in Table 5 together with the values of the notched Izod (NI) impact strength.

The cured resin obtained from the resin composition of the present invention was found to be excellent in heat resistance and mechanical properties.

[0100]

[Table 5]

[0101]

Example 20 A solution B was prepared by adding 0.11 g of benzyldimethylamine and 0.22 g of BPOB (same as that shown in Table 1) to 7.0 g of glycidyl methacrylate and dissolving the solution.

Separately, carbodiimide-modified 4,4'-
Liquid A is 14.2 g of diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g).

The above liquids A and B were put into a tester, mixed quickly and uniformly, then lightly coated on a NaCl plate and kept in an oven at 100 ° C. for 30 minutes and then in an oven at 180 ° C.
After time treatment, the infrared absorption spectrum was measured.

[0104] As a result the absorption of isocyanate group of 2258cm ^-1, absorption of vinyl bonds of 1638cm ^-1, 904cm ^-1
The absorption based on the isocyanurate ring disappeared, and a peak based on the isocyanurate ring was observed at 1710 cm ^-1. It has been verified that this is caused by the formation of crosslinks and the accompanying increase in crosslink density.

[0105]

Example 21 A solution obtained by adding 5.3 g of benzyldimethylamine and 10.6 g of BPOB (same as that shown in Table 1) to 350 g of glycidyl methacrylate was used as solution B.

Separately, carbodiimide-modified 4,4'-
710 g of diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) is used as the liquid A.

The above liquids A and B were vacuum-degassed in advance, passed through an inlet tube provided with a static mixer, and placed in a 38 mm × 48 cm 3 mm thick mold pre-heated to 100 ° C. to form a plain woven glass cloth (195.6 g / m 2 basis weight). ² ) was pressed into a mold in which 15 sheets were installed. The required pressure is 2.5kg
/ Cm ² , it was found that the resin composition of the present invention had low viscosity and could be injected under low pressure. Demold 20 minutes after liquid injection and thickness 3
A glass fiber reinforced composite material with no voids and good impregnation was obtained. This plate was post-cured at 180 ° C. for 2 hours.

The heat distortion temperature (HDT), notched (NI) Izod impact strength of the obtained plate, and the formed plate were cut out to a width of 12.7 mm and a length of 60 mm, and a 30-ton universal testing machine (UCT manufactured by Orientec) -30) using span 48
As a result of performing a three-point bending measurement at a head speed of 2 mm / min, the HDT was 300 ° C. or higher, and the Izod impact strength was 110.
kg · cm / cm, flexural strength 44 kg / mm ² , flexural modulus 189
It was 0 kg / mm ² , indicating that the resin composition of the present invention was excellent in moldability and the obtained cured resin was excellent in mechanical properties such as heat resistance, impact strength and bending properties.

[0109]

Comparative Example 1 A 213-necked flask equipped with a calcium chloride tube, a stirrer, and a reflux tube was charged with 700 g of toluene, 140 g of glycidyl methacrylate, and 0.337 of hydroquinone.
g, and 159 g of a polyol-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.29 × 10 ⁻³ equivalent / g) was added thereto.
When the temperature reaches 0 ° C., 1.04 g of benzyldimethylamine
Was added. Shortly after the addition, white turbidity occurred, and 2 hours later, a white solid precipitated entirely. This solid has a melting point of 300 ° C
Thus, it could not be used for the subsequent molding. In place of the above polyol-modified 4,4'-diphenylmethane diisocyanate, carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 ×
A similar experiment was performed using 142 g and 284 g of (10 ⁻³ eq / g), but a solid having a melting point of 300 ° C. or higher was formed and could not be subjected to subsequent molding.

[0110] From the above experimental results,
In the method described in JP-A No. 15, when an isocyanate cyclization (trimerization) catalyst such as a tertiary amine catalyst used in the present invention is used, crosslinking by isocyanate cyclization at the stage of producing a polymerizable prepolymer is performed. It has been found that it is practically difficult to produce a cured resin using this.

[0111]

Comparative Example 2 Production of a polymerizable prepolymer was attempted according to the method described in JP-B-53-31515. That is, 700 g of toluene was placed in the same device as used in Comparative Example 1,
Glycidyl methacrylate 140 g, hydroquinone 0.
337 g, carbodiimide-modified 4,4′-diphenylmethane diisocyanate (isocyanate equivalent 6.90 ×
(10 ⁻³ eq / g) of 142 g was charged and heated with stirring in a nitrogen atmosphere. When the temperature reached 120 ° C., 0.474 g of tetrabutylammonium iodide was added, and the reaction was continued for 6 hours.
After the solution was cooled to room temperature, toluene was distilled off under reduced pressure. Although the obtained reaction mixture was a viscous liquid, the steel balls did not fall and the viscosity could not be measured by the falling ball viscosity method using steel balls.

Based on the above experimental results,
In the method for producing a cured resin via a polymerizable prepolymer as described in JP-A No. 15, it has been found that the viscosity of the prepolymer is high and the handleability is extremely poor.

[0113]

Example 22 A solution obtained by uniformly dissolving 4.24 g of 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane in 140 g of glycidyl methacrylate is referred to as Liquid B. Separately, carbodiimide modified 4,
284 gA of 4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was prepared.

Separately, 2.12 g of N, N-dimethylbenzylamine was used as solution C.

The above liquids A, B and C3 were vacuum-defoamed in advance, passed through an inlet tube provided with a static mixer, and injected into a 3 mm thick mold at 100 ° C. while mixing therein. It was removed after 30 minutes to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 15 hours.

[0116] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) measured using an SP tester was 285 ° C., indicating that the resin composition of the present invention gave a cured resin having high heat resistance.

[0117]

Example 23 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) 324 g was used as solution A. Separately, 213 g of glycidyl methacrylate was added to N, N ′, N ″.
-Tris (dimethylaminopropyl) hexahydro-S
A solution was prepared by adding and dissolving 2.1 g of -triazine and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene, and this solution was used as solution B.

The viscosity of Solution A and Solution B at 40 ° C. was 45 cps and 5 cps or less, respectively, as measured by a B-type viscometer, and both were low-viscosity liquids.

The liquids A and B2 were previously degassed in vacuum, passed through an inlet tube equipped with a static mixer, and mixed and poured into a 3 mm-thick mold at room temperature (about 30 ° C.). After 15 minutes, a molded plate having a thickness of 3 mm was obtained. The obtained molded plate was post-cured at 150 ° C. for 2 hours.

[0120] This molded plate is made of HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
When the heat distortion temperature (HDT) was measured using an SP tester, it was 253 ° C., indicating that the resin was a cured resin having high heat resistance.

[0121]

Example 24 In Example 23, instead of the above carbodiimide-modified 4,4'-diphenylmethane diisocyanate, the solution A was replaced with a polyol-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9).
The same molding as in Example 23 was carried out using 484 g of (0 × 10 ⁻³ equivalent / g). HDT was measured in the same manner for the obtained molded plate, and it was found that the HDT was 250 ° C., indicating that it was a cured resin having high heat resistance.

[0122]

Example 25 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.2
(9 × 10 ⁻³ eq / g) 142 g was used as solution A, and benzyldimethylamine 1.0 was added to 70 g of glycidyl methacrylate.
A and B2 solutions were prepared by using a solution obtained by adding 6 g and 2.12 g of 1,3-bis (t-butylperoxyisopropyl) benzene and dissolving the solution at room temperature for 24 hours as a solution B.

The viscosity of the solution B was measured with a B-type viscometer immediately after the preparation of the solution and one day later.
It was below.

14.2 g of the above solution A and 7.0 g of the solution B (the solution B used was stored for one day after the preparation) were put into a test tube, mixed quickly, and then mixed at room temperature (about 30 ° C.). The time until disappearance and gelation was measured and was 12 seconds.

Further, 40.6 g of the solution A and 20 g of the solution B were previously degassed in vacuum, passed through an introduction tube provided with a static mixer, and mixed therein, while being poured into a mold having a thickness of 3 mm. A curing reaction was performed for 30 minutes, and the obtained molded plate was further post-cured (post-cured) at 180 ° C. for 30 minutes.

[0126] This molded plate is made of HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
As a result of measuring the heat distortion temperature (HDT) using an SP tester, it showed an extremely high heat resistance of 292 ° C.

[0127]

Example 26 The solution B of Example 25 was left at room temperature for 60 days after preparation. Thereafter, the liquid viscosity and the gelation time were measured in the same manner as in Example 25. The liquid viscosity and the gelation time were 5 cps or less and 18 seconds, respectively, and it was confirmed that there was substantially no difference between immediately after preparation and good storage stability. Next, the solution B left after standing for 60 days was mixed with the solution A of Example 25 in the same manner as in Example 25, molded, and post-cured. Good moldability,
The HDT of the obtained molded plate was 295 ° C. According to this experiment, it was found that a cured resin molded product having excellent heat resistance can be obtained even when molding was performed using the aged B liquid.

[0128]

Example 27 As solution A, carbodiimide-modified 4,
Using 710 g of 4′-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g),
As liquid B, 5.3 g of benzyldimethylamine in 350 g of glycidyl methacrylate, and BPOB (1,3-bis (t-butylperoxyisopropylbenzene)) 10.
Using a solution in which 6 g had been added and dissolved, the mixture was molded by a two-liquid method.

That is, the above liquids A and B were vacuum-defoamed in advance, passed through an inlet tube provided with a static mixer, and placed in a 38 mm × 48 cm 3 mm thick mold pre-heated to 100 ° C., into a plain woven glass cloth (195.6 g in basis weight). / M ² ) to 2
It was pressed into a mold with two sheets inserted. The pressure required at this time was 4.5 kg / cm ² , and it was found that the resin composition used in the present invention had low viscosity and could be injected under low pressure. After liquid injection 3
The mold was released in 0 minutes to obtain a glass fiber reinforced composite material having a thickness of 3 mm. The plate was subsequently post-cured at 180 ° C. for 2 hours.

The heat distortion temperature (HDT) of the obtained plate was 30.
The temperature was not lower than 0 ° C., and the notched (NI) Izod impact strength was 121 kg · cm / cm. Further, the formed plate was cut into a width of 12.7 mm and a length of 60 mm, and a span of 48 mm was obtained using a 30-ton universal testing machine (UCT-30 manufactured by Orientec).
As a result of three-point bending measurement at a head speed of 2 mm / min, the bending strength was 54 kg, mm ² , and the flexural modulus was 30,30 kg.
/ Mm ² .

From these results, according to the production method of the present invention, a composite material having a high fiber content can be produced by utilizing the excellent moldability of the resin composition, and the obtained composite material has heat resistance and impact strength. It was found to be excellent in mechanical properties such as bending characteristics.

[0132]

Examples 28 to 31 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was used as solution A, and separately from this, a predetermined amount of glycidyl methacrylate shown in Table 6 The polyether polyol having an OH value of 56 mg KOH / g in which ethylene oxide is added to the terminal hydroxyl group of a predetermined amount of glycerin and the OH value of ethylene oxide having been added to the terminal hydroxyl group of polypropylene polyether boryl are 280 mg KOH / g shown in Table 6. A polyether polyol obtained by mixing the polyether polyol with a weight ratio of 7: 3,
2.0 g of benzylmethylamine and 1,3-bis (t-
A solution in which 4.2 g of (butylperoxyisopropyl) benzene was added and dissolved was prepared, and this solution was used as solution B.

The above liquids A and B were vacuum-defoamed in advance, passed through an inlet tube provided with a static mixer, and injected into a 3 mm-thick mold heated to 100 ° C. while mixing therein. After 30 minutes, it was removed from the mold to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured at 180 ° C. for 5 hours.

[0134] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) and the notched Izod impact strength measured using an SP tester were measured.
However, it was found that each was a cured resin having high heat resistance and toughness.

[0135]

[Table 6]

[0136]

Example 32 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) 284 g was used as solution A, and 47.3 g of glycidyl methacrylate was separately used as solution B. Separately, ethylene oxide was added to terminal hydroxyl groups of glycerin to obtain an OH value of 56 mgKOH / g. OH value 28 obtained by adding ethylene oxide to terminal hydroxyl groups of polyether polyol and polypropylene polyether polyol.
47.3 g of polyether polyol obtained by mixing 0 mg KOH / g of polyether polyol in a ratio of 7 to 3 by weight,
1.89 g of N, N-dimethylbenzylamine and 1,1-
A solution obtained by adding and dissolving 3.79 g of di-t-butylperoxy-3,3,5-trimethylcyclohexane was designated as liquid C.

The above liquids A, B and C3 were vacuum-defoamed in advance, passed through an inlet pipe provided with a static mixer, and poured into a 3 mm thick mold at 120 ° C. while mixing therein.
It was removed after 30 minutes to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

[0138] This molded plate was used as HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) was measured using an SP tester. The result was 277 ° C, and the notched Izod impact strength was 4.1 kg.
-Cm / cm, indicating that the resin composition of the present invention gives a cured resin having high heat resistance and toughness.

[0139]

Example 33 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) 284 g was used as solution A, separately from this, 47.3 g of glycidyl methacrylate, and an OH value of 5 in which ethylene oxide was added to terminal hydroxyl groups of glycerin.
66.2 g of 6 mg KOH / g polyether polyol and t
A solution in which 4.26 g of butyl peroctoate was dissolved was used as a solution B. Separately, a polyether polyol 2 having an OH value of 280 mgKOH / g in which ethylene oxide was added to terminal hydroxyl groups of polypropylene polyether borol was used.
2.13 g of N, N-dimethylbenzylamine in 8.4 g
The solution in which was dissolved was used as solution C.

The above liquids A, B, and C3 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at 120 ° C. while mixing therein.
It was removed after 30 minutes to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

[0141] This molded plate was used as HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) was measured using an SP tester. The result was 244 ° C., and the notched Izod impact strength was 4.8 kg.
-Cm / cm, indicating that the resin composition of the present invention gives a cured resin having high heat resistance and toughness.

[0142]

Examples 34 and 35 426 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90.times.10.sup.- ³ equivalent / g) was used as solution A. Separately, a predetermined amount of glycidyl methacrylate shown in Table 7 was used. Is a polyether polyol (OH) obtained by adding propylene oxide to a predetermined amount of bisphenol A shown in Table 7.
138 mgKOH / g), 2.0 g of benzylmethylamine
And 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene were added and dissolved to prepare a solution.

The above liquids A and B2 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm-thick mold heated to 100 ° C. while mixing therein. After 30 minutes, it was removed from the mold to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was post-cured at 180 ° C. for 5 hours.

[0144] This molded plate was used as HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) and the notched Izod impact strength measured using an SP tester were measured.
However, it was found that each was a cured resin having high heat resistance and toughness.

[0145]

[Table 7]

[0146]

Examples 36 and 37 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.90 × 10 ⁻³ equivalent / g) was used as solution A. Separately, 47 g of glycidyl methacrylate was added to ethylene at the terminal hydroxyl group of glycerin. A polyether obtained by mixing a polyether polyol having an OH value of 56 mgKOH / g with an oxide added thereto and a polyether polyol having an OH value of 280 mgKOH / g with an ethylene oxide added to a terminal hydroxyl group of a polypropylene polyether polyol with a weight ratio of 7: 3. A solution was prepared by adding and dissolving a predetermined amount of the catalyst shown in Table 8 to 142 g of the polyol, and this solution was used as solution B.

The above liquids A and B were vacuum degassed in advance, passed through an inlet tube provided with a static mixer, and mixed therein, and poured into a 3 mm-thick mold preheated to a predetermined temperature shown in Table 8. did. After 30 minutes, a molded plate having a thickness of 3 mm was obtained. The obtained molded plate was post-cured at 180 ° C. for 5 hours.

[0148] This molded plate was used as HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) measured using an SP tester is shown in Table 8, and it was found that each was a cured resin having high heat resistance.

[0149]

[Table 8]

[0150]

Examples 38 to 40 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was used as solution A, and separately from this, a predetermined amount of (β A polyether polyol having an OH value of 56 mgKOH / g obtained by adding ethylene oxide to the terminal hydroxyl group of glycerin to methyl-glycidyl (meth) acrylate and an OH value of 280 mgKOH / g obtained by adding ethylene oxide to the terminal hydroxyl group of polypropylene polyether polyol; Polyether polyol 14 obtained by mixing polyether polyol with a weight ratio of 7: 3
A solution prepared by adding a predetermined amount of the catalyst shown in Table 9 to 2 g and dissolving it was designated as solution B.

The liquids A and B were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and mixed and poured into a 3 mm thick mold at 70 ° C. After 10 minutes, it was removed to obtain a molded plate having a thickness of 3 mm. The obtained molded plate is post-cured at 180 ° C. for 5 hours and post-cured (post-cured)
did.

[0152] This molded plate was used for HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
Table 9 shows the results of measuring the heat distortion temperature (HDT) using an SP tester.

[0153]

[Table 9]

[0154]

Example 41 A polyether polyol having an OH value of 56 mg KOH / g obtained by adding ethylene oxide to the terminal hydroxyl group of glycerin to 47 g of glycidyl methacrylate and an OH value of 280 KOH mg / g obtained by adding a terminal hydroxyl group of polypropylene polyether polyol to ethylene oxide were used. A solution was prepared by dissolving 142 g of polyether polyol obtained by mixing polyether polyol with 7: 3 by weight, 2.0 g of benzyldimethylamine and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene. This was designated as solution B. Separately, a predetermined amount of polyisocyanate shown in Table 10 was used as solution A.

The above liquids A and B were vacuum degassed in advance, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at 100 ° C. while mixing therein. 30
Minutes later, a molded plate having a thickness of 3 mm was obtained. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

Table 1 shows the heat distortion temperature (HDT) of this molded plate.
Although 0 is shown, it turned out that all resins are resins with high heat resistance.

[0157]

[Table 10]

[0158]

Examples 42 and 43 47 g of glycidyl methacrylate
OH value 56 mg KOH / g of polyether polyol obtained by adding ethylene oxide to the terminal hydroxyl group of glycerin and 280 KOH mg of OH value obtained by adding terminal hydroxyl group of ethylene oxide to polypropylene polyether polyol.
/ G of polyether polyol in a ratio of 7 to 3 by weight, a solution prepared by adding and dissolving 47 g of polyether polyol, 2.0 g of benzyldimethylamine and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene. Was prepared and used as a solution B. Separately, a predetermined amount of polyisocyanate shown in Table 11 was used as solution A.

The above liquids A and B were degassed in advance in a vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at 100 ° C. while mixing therein. 30
Minutes later, a molded plate having a thickness of 3 mm was obtained. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

Table 1 shows the heat distortion temperature (HDT) of this molded plate.
As shown in FIG. 1, all of the resins were found to be resins having high heat resistance.

[0161]

[Table 11]

[0162]

Examples 44 and 45 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90.times.10.sup.- ³ equivalent / g) was used as solution A. Separately, a predetermined amount of glycidyl methacrylate shown in Table 12 was used. In Table 12, an OH value obtained by adding ethylene oxide to a terminal hydroxyl group of a predetermined amount of glycerin shown in Table 12 is 56 mgKOH /
g of polyether polyol and a polyether polyol having an OH value of 280 KOH mg / g in which terminal hydroxyl groups of polypropylene polyether polyol are added to ethylene oxide in a ratio of 7: 3, and a bisphenol having an epoxy equivalent of 158 g / eq. F
Type epoxy distillate, benzyldimethylamine 2.0
g and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene were added and dissolved to prepare a solution.

The liquids A and B were vacuum-defoamed in advance, passed through an inlet tube provided with a static mixer, and poured into a 3 mm-thick mold heated to 100 ° C. while mixing therein. After 30 minutes, a molded plate having a thickness of 3 mm was obtained. The obtained molded plate was further post-cured at 180 ° C. for 5 hours.

[0164] This molded plate is made of HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) and the notched Izod impact strength measured using an SP tester are shown in Table 12, and all were found to be cured resins having high heat resistance and toughness.

[0165]

[Table 12]

[0166]

Example 46 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ eq / g) 284 g was used as solution A, separately from this glycidyl methacrylate 107 g epoxy equivalent 15
8 g / eq bisphenol F type epoxy distillate 7
g and a solution of 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene as Solution B. Separately, a polyether having an OH value of 56 mg KOH / g to which terminal hydroxyl ethylene oxide of glycerin is added. OH value of 280 KO obtained by adding ethylene oxide to terminal hydroxyl groups of polyol and polypropylene polyether polyol
Solution C was prepared by dissolving 2 g of N, N-dimethylbenzylamine in 34 g of a polyether polyol obtained by mixing Hmg / g of a polyether polyol with a weight ratio of 7: 3.

The above liquids A, B and C3 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at 100 ° C. while mixing therein.
It was removed after 30 minutes to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

[0168] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
As a result of measuring the heat distortion temperature (HDT) using an SP tester, the notched Izod impact strength at 273 ° C was 3.1 kg.
cm / cm, indicating that the resin composition of the present invention gives a cured resin having high heat resistance and toughness.

[0169]

Example 47 Carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent: 6.9)
0 × 10 ⁻³ equivalents / g) 5680 g was used as solution A, 946 g of glycidyl methacrylate was separately used as solution B, and a polyether having an OH value of 56 mg KOH / g obtained by adding ethylene oxide to the terminal hydroxyl group of glycerin was used separately. OH value 28 obtained by adding ethylene oxide to terminal hydroxyl groups of polyol and polypropylene polyether polyol.
N, N was added to 946 g of a polyether polyol obtained by mixing 0 mg KOH / g of a polyether polyol in a ratio of 7: 3 by weight.
-Dimethylbenzylamine 37.8 g 1,1-di-t-
A solution obtained by adding and dissolving 75.8 g of butylperoxy-3,3,5-trimethylcyclohexane was used as solution C.

The above liquids A, B, and C3 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and pre-heated to 100 ° C. in a mold having a thickness of 38 cm × 48 cm and a thickness of 30 mm. (2.6 g / m ² ) was pressed into a mold in which 220 sheets were inserted. The mold was released 30 minutes after the liquid injection to obtain a glass fiber reinforced composite material having a thickness of 30 mm.
The plate was subsequently post-cured at 180 ° C. for 2 hours.

The heat distortion temperature (HDT) of the obtained plate was 30.
The temperature was not lower than 0 ° C., and the notched (NI) Izod impact strength was 138 kg · cm / cm. Furthermore, the formed plate was cut into a width of 12.7 mm, a length of 60 mm, and a thickness of 3 mm, and a three-point bending measurement was performed using a 30-ton universal testing machine (UCT-30 manufactured by Orientec) with a span of 48 mm and a head speed of 2 mm / min. Is 53 kg / mm ² and the flexural modulus is 298
0 kg / mm ² was shown.

If the polyether polyol is excluded from the present composition, reaction heat and molding shrinkage are large. Therefore, when a molded plate having a thickness as large as 30 mm is formed, burns and cracks may be partially generated due to self-heating. With this composition, molding was possible without any problem, and the releasability from the mold was further improved.

From these results, according to the production method of the present invention, a composite material having a high fiber content can be produced by taking advantage of the excellent moldability of the resin composition, and further, thick molding can be performed. The obtained composite material was found to be excellent in heat resistance and mechanical properties such as impact strength and bending properties.

[0174]

Examples 48-52, Comparative Example 3 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90.times.10.sup.- ³ equivalent / g) was added to A
Glycidyl methacrylate 140
g shows the various polyepoxy compounds and N,
2.1 g of N ', N "-tris (dimethylaminopropyl) hexahydro-S-triazine and 1,3-bis (t
A solution in which 4.2 g of (-butylperoxyisopropyl) benzene was added and dissolved was prepared.

The above liquids A and B2 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm thick mold at room temperature (about 30 ° C.) while mixing therein. After 30 minutes, it was removed from the mold to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured at 150 ° C. for 5 hours.

[0176] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) measured using an SP tester was measured, and the results are shown in Table 13. As a result, it was found that each was a cured resin having high heat resistance.

[0177]

[Table 13]

[0178]

Embedded image

[0179]

Example 53 47 g of glycidyl methacrylate, 47 g of bisphenol F type epoxy having an epoxy equivalent of 158 g / eq, 2.0 g of tetra-n-butylammonium fluoride, 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene And dissolve the solution
Liquid. Separately, carbodiimide-modified 4,4'-
Liquid A was 284 g of diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g).
Liquid A and liquid B were both liquids having low viscosity.

The above liquids A and B2 were previously degassed in vacuum, passed through an inlet tube provided with a static mixer, and poured into a 3 mm-thick mold preheated to 120 ° C. while mixing therein. After 15 minutes, it was removed to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

[0181] This molded plate was manufactured using HDT & V manufactured by Toyo Seiki Seisaku-sho
The heat distortion temperature (HDT) was measured using an SP tester. The HDT was 232 ° C., the Izod impact strength with a notch was 2.0 kg · cm / cm, and the resin composition of the present invention exhibited heat resistance and toughness. It was found to give a high cured resin.

[0182]

Example 54 A solution B was prepared by adding 47 g of bisphenol F type epoxy having an epoxy equivalent of 158 g / eq and 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene to 47 g of glycidyl methacrylate. Separately, 284 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was used as solution A. Separately, 1.89 g of N, N-dimethylbenzylamine
Was used as solution C. The liquids A, B, and C were all liquids having low viscosity.

The above liquids A, B and C3 were previously degassed by vacuum, passed through an inlet tube provided with a static mixer, and injected into a 3 mm-thick mold premixed at 120 ° C. while mixing therein. After 15 minutes, it was removed to obtain a molded plate having a thickness of 3 mm.
The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 5 hours.

[0184] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The heat distortion temperature (HDT) was measured using an SP tester. The HDT was 238 ° C., the Izod impact strength with notch was 2.1 kg · cm / cm, and the resin composition of the present invention had heat resistance and toughness. It was found to give a high cured resin.

[0185]

Examples 55-59, Comparative Example 4 A solution prepared by adding a predetermined amount of the catalyst shown in Table 14 to 7.0 g of glycidyl methacrylate and dissolving the solution was designated as solution B. Separately, 14.2 g of carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10 ⁻³ equivalent / g) was used as solution A. At this time, the solution B prepared immediately before the test was used. After the solutions A and B2 were placed in a test tube and mixed quickly and uniformly, the time required for the mixture to lose its fluidity and to gel at 100 ° C. was measured. Table 14 shows the results.

As Comparative Example 5, a tertiary amine, dimethylbenzylamine, and a radical catalyst shown in Table 14 were dissolved in 7.0 g of glycidyl methacrylate and aged for 2 days. Table 14 also shows the gel time when the experiment was performed. From Table 14, it is clear that the composition of the present invention has a slow reaction and can be applied to an apparatus having a low resin liquid supply capacity.

The solution B used in Examples 55 to 59 was
After standing for a month, the same gelation test as above was performed, but the gelation time hardly changed, and it was confirmed that all the systems had good storage stability.

[0188]

[Table 14]

[0189]

Examples 60 to 62, Comparative Example 5 A solution prepared by adding a predetermined amount of a catalyst shown in Table 15 to a predetermined amount of glycidyl methacrylate shown in Table 15 and dissolving the solution was used as Liquid B. Separately, carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 10
⁽⁻³ equivalents / g) was used as solution A. Liquids A and B were vacuum-defoamed in advance, passed through an inlet tube equipped with a static mixer, and heated to 100 ° C. while mixing therein.
pour it into a mold with a thickness of mm, take out the mold after 30 minutes,
A 3 mm thick formed plate was obtained. The obtained molded plate was further subjected to 180
Post-curing was performed at 2 ° C. for 2 hours.

[0189] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
Table 15 shows the results of measuring the heat distortion temperature (HDT) using an SP tester.

As Comparative Example 5, the same molding was carried out by adding glycidyl methacrylate to the above polyisocyanate in an amount having an epoxy group equivalent to an isocyanate group.
Table 15 also shows the results of measuring the heat distortion temperature. Table 15 shows that the resin compositions of the present invention all give cured resins having high heat resistance.

The abbreviations in the catalyst column in Table 15 represent the following compounds, respectively. TBAF: Tetra-n-butylammonium fluoride BPOB: 1,3-bis (t-
Butyl peroxyisopropyl) benzene

[0193]

[Table 15]

[0194]

Examples 63 to 65 2.0 g of tetra-n-butylammonium fluoride was added to a predetermined amount of (β-methyl) glycidyl (meth) acrylate shown in Table 16 below.
A solution in which 4.2 g of 1,3-bis (t-butylperoxyisopropyl) benzene was added and dissolved was used as solution B. Separately, carbodiimide-modified 4,4'-diphenylmethane diisocyanate (isocyanate equivalent 6.90 × 1
0 ^-3 eq / g) 284 g was A solution. Liquid A and liquid B were both liquids having low viscosity.

The above liquids A and B were vacuum-degassed in advance, passed through an inlet tube provided with a static mixer, and poured into a 3 mm-thick mold preheated to 100 ° C. while mixing therein. After 15 minutes, it was removed to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 150 ° C. for 5 hours.

[0196] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The results of measuring the heat distortion temperature (HDT) using an SP tester are shown in Table 16, and it was found that each of the resin compositions of the present invention gave a cured resin having high heat resistance.

[0197]

[Table 16]

[0198]

Examples 66 and 67 Glycidyl methacrylate 140
g to tetra-n-butylammonium fluoride
A solution prepared by dissolving 12 g and 4.24 g of 1,3-bis (t-butylperoxyisopropyl) benzene was used as solution B. Separately, a predetermined amount of polyisocyanate shown in Table 17 was used as solution A.

The above liquids A and B were vacuum-defoamed in advance, passed through an inlet tube provided with a static mixer, and poured into a 3 mm-thick mold preheated to 100 ° C. while mixing therein. It was removed after 30 minutes to obtain a molded plate having a thickness of 3 mm. The obtained molded plate was further post-cured (post-cured) at 180 ° C. for 2 hours.

[0200] This molded plate was prepared by using HDT & V manufactured by Toyo Seiki Seisaku-sho, Ltd.
The results of measuring the heat distortion temperature (HDT) using an SP tester are shown in Table 17, and it was found that each of the resin compositions of the present invention gave a cured resin having high heat resistance.

[0201]

[Table 17]

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-124417 (32) Priority date Hei 3 (1991) April 30 (33) Priority claim country Japan (JP)

Claims (4)

(57) [Claims] 1. A liquid comprising at least one polyisocyanate compound (a) and a B liquid comprising (β-methyl) glycidyl (meth) acrylate (b) and at least one ring-forming catalyst (c). A multi-part thermosetting resin composition comprising the liquid A and / or the liquid B containing at least one radical catalyst (d). 2. A method for producing a cured resin molded article using the multi-component thermosetting resin composition comprising the liquid A and the liquid B according to claim 1, wherein the liquid A and the liquid B are mixed during molding. And injecting the mixture into a predetermined mold and curing the mixture by heating. 3. Liquid B is divided into a first liquid (i) composed of (β-methyl) glycidyl (meth) acrylate (b) and a second liquid (ii) composed of a ring-forming catalyst (d). The method for producing a cured resin molded product according to claim 2, wherein: 4. A process for producing the cured resin molded product according to claim 3 containing the first liquid (i) and / or the second fluid (ii) the polyol compound (e).