JPH0395213A - Liquid curable composite resin composition - Google Patents

Abstract

PURPOSE:To prepare a liq. curable composite resin compsn. giving a molding with excellent mechanical properties and heat resistance without being accompa nied by foaming by compounding a polyisocyanate, a cyclotrimerization catalyst thereof, a polyepoxide, and a curing agent thereof, and lowering the water content of the epoxy curing system below a specified value. CONSTITUTION:A liq. curable composite resin compsn. is prepared by compounding a polyisocyanate, a cyclotrimerization catalyst thereof, a polyepoxide, and a curing agent thereof under such conditions that the water content of the epoxy curing system in the compsn. is 500ppm or lower; the curing agent, which is a part of the epoxy curing system, is one selected from the group consisting of imidazole, amide, and cationic curing agents; and the wt. ratio of the isocyanate cyclotrimerization system to the epoxy curing system is (15:85)-(80:20). The obtd. compsn., highly heat-resistant and easily moldable, can give a molding with excellent mechanical properties and heat resistance without being accompanied by foaming. To obtain the molding, lowering the water content of the polyepoxide below a specified value is important; one means for achieving this is a pretreatment of the polyepoxide by mixing it with the polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composite curable liquid resin composition that has both high heat resistance and easy moldability. More specifically, by combining various reactions such as epoxy curing reaction, cyclization trimerization of polyisocyanate 1 compound, and oquinazolidone ring formation from epoxide and isocyanate, thermal and mechanical properties are improved with less foaming. The present invention relates to a Vr-standard curable liquid resin composition that provides a cured product.

[Prior art] Cyclization of isocyanate-1 group as shown in the following reaction formula (
It has been known that an isocyanurate ring is formed by CyclotrimerizaNon (for example, V. V. Kroshak, Vysoc
omol, soyed. A 16, 926-943
, (1974)).

○ In this cyclization reaction, if a polyfunctional diisocyanate compound is used, a cured resin with high heat resistance can be provided. As an example of industrial application of such a curable liquid composition, it is widely used for the purpose of producing polyurethane-based foams with a particularly elevated thermal softening point (for example, Japanese Patent Publication No. 46-250173). On the other hand, curable liquid compositions of epoxides with polyisocyanates are also known (e.g., U.S. Pat. No. 3,020,262).In addition to isocyanurate rings, these curing systems contain oxazolidone rings or the curing process described below. It is thought that this occurs during the process.

Furthermore, this polyisocyanate. 2 made of epoxide
There have already been reports of a cured resin system containing an epoxy curing agent as a third component in contrast to the Kaibun system (
For example, N. K+njo etat. , J, A
t) pl. Polym. Sci,,28. 1729
-174t, 1983>.

The resin or molded article obtained from the above-mentioned isocyanate/epoxy composite curable liquid composition has a high thermal softening point and is widely used mainly for producing foam molded articles with improved heat resistance. However, this curable liquid composition has a remarkable tendency to foam during the curing reaction, which is rather a drawback when producing ordinary non-foamed shaped articles. The main cause of such foaming is considered to be foaming caused by carbon dioxide as expressed by the reaction formula below.

-NGO + Mouth 20 → 1N 2 +CO22 × 1 N
1 0 → − N=C=N
+CO2 In this case, it goes without saying that if the air bubbles generated in the molded product are removed as much as possible, the mechanical properties of the molded product will be improved, and a technology for producing a molded product with virtually no foaming will be developed. is strongly held.

OBJECTIVE OF THE INVENTION 1 The present invention seeks to provide a curable liquid resin composition that provides molded articles with substantially no foaming compared to conventionally known polyisocyanate/epoxide curable resin systems.

That is, the present inventors have conducted research to eliminate the above-mentioned causes of foaming as much as possible and to provide molded products with high heat resistance and excellent mechanical properties. They discovered that it is important to lower the moisture content of epoxide in a liquid composition to a certain level, and as one specific means for lowering the moisture content, the epoxide was once mixed with an isocyanate compound. The present invention has been achieved based on the discovery that pretreatment is effective.

[Structure of the Invention] The present invention achieves the above j objects, and provides a composite curable liquid composition composed of a polyisocyanate, a cyclization trimerization catalyst thereof, a polyepoxide, and an epoxy curing agent. , the moisture content of the epoxy curing system in the composition is 500 ppm or less, and the epoxy curing agent constituting the epoxy curing system is imidazole-based. Amine type, cation type. One or more types selected from the group of various merkabut type curing agents, and furthermore, the weight ratio of the total amount of cyclization curing system components to the total amount of epoxy curing system components is 15/8
This is a composite curable liquid resin composition characterized in that the ratio is 0 to 80/20.

Hereinafter, each component constituting the liquid resin composition of the present invention and a method for producing a cured resin molded article from the components will be described in detail.

polyisocyanate Basically, a polyisocyanate having two or more functionalities is used.

Typical polyisocyanates are illustrated below.

a) Aromatic polyisocyanate; 4,4'-diphenylmethane diisocyanate and its condensed polyisocyanate (including carposiimide-containing modified products), 2.4- and/or 2.6-toluylene diisocyanate, 3.4' or 4.41-diphenyl ether diisocyanate, 1.4- or 1.5-naphthalene diisocyanate, 1.3- or 1.4-phenylene diisocyanate, biphenyl-4.4'-diisocyanate, benzene-1.2.4- Triisocyanate, xylene-1,4-diisocyanate, 4
．． 4' diphenylpropane diisocyanate and a polyisocyanate in which 1a1 or more of the hydrogen atoms on the aromatic ring are replaced with an Iw substituent that does not inhibit cyclization trimerization. Examples of such substituents include alkyl groups having up to 4 carbon atoms and aromatic groups such as phenyl groups. In addition, chlorine halogen atom,
Nitro group. An example is an alkoxy group.

b) Aliphatic and alicyclic polyisocyanates; hexamethylene diisocyanate, xylylene diisocyanate,
Isophorone diisocyanate etc.

In the present invention, known blocked isocyanates can also be used. Preferred blocking agents and inhibitors are one or more compounds selected from the group consisting of phenols, oximes, lactams and β-diketones.

Most preferred are monophenols, such as phenol. These include alkyl-substituted phenols such as those substituted with methyl and ethyl groups, and alkoxy-substituted phenols.

In the present invention, a thermosetting resin can also be produced by replacing a part of the above polyisocyanate compound with a (monofunctional) monoisocyanate compound.

Examples of such monoisocyanate compounds include aromatic monoisocyanates such as phenyl isocyanate and biphenyl isocyanate, in which one or more hydrogen atoms on the aromatic ring are replaced with the above-mentioned substituents that do not inhibit cyclization trimerization. It may be something.

Note that if the blending ratio of monoisocyanate increases too much, the resulting cured resin tends to become brittle. The preferred blending ratio of monoisocyanate is 67 mol% or less, more preferably 50 mol% or less, calculated as the substitution rate of polyisocyanate.

Polyepoxide Polyepoxide used in the present invention (epoxy monomer)
The ingredients are saturated or unsaturated aliphatic. Alicyclic family.
Aromatic. Examples include those of the heterocyclic group. Also,
It may have various substituents. Representative polyepoxides are disclosed in U.S. Pat. Nos. 2,633,458 and 3,3.
Among those described in No. 73,221 and No. 3,377,406@, those that can be liquefied in some form can be used according to the formulation of the present invention. For example, even if the monomer itself is solid or semi-solid, by mixing it with other epoxy monomers or other reactive diluents,
If it is liquid at a certain temperature, it can be used in the present invention.

Specific examples of polyepoxide are illustrated below.

a) Glycidyl ether compounds of alcohols and phenols; 2.2-bis(4-hydroxyphenyl)propane (to bisphenol), 4.41-dihydroxydiphenylmethane, 4.4'-dihydroxydiphenylsulfone, resorcinol, dihydroxynaphthalene , polyhydric phenols such as phenol novolak, cresol novolac, resorcinol novolak, dihydroxynaphthalene civolac, or phenols such as phenol, dihydroxynaphrene, glyoxal, glutaraldehyde, 0-hydroxybenzaldehyde, benzaldehyde, iso(tele)phthal Glycidyl ethers of polyhydric alcohols obtained by dehydration condensation (e.g. in the presence of an acidic catalyst) with aldehydes such as aldehydes, and glycidyl ethers of polyhydric alcohols such as butanediol, propylene glycol, polyethylene glycol, glycerol, etc. and its precursor polymer.

b) Glycidyl ester compounds of carboxylic acids; glycidyl esters of dicarboxylic acids such as phthalic acid, in(tere)phthalic acid, tetrahydrophthalic acid, naphthalene dicarboxylic acid, dimer acid, etc. and their precursor polymers, and glycidyl methacrylate, etc. .

C> Glycidyl ether ester compounds of oxycarboxylic acids; Glycidyl ether esters of oxycarboxylic acids such as ra-(p-)oxybenzoic acid and oxynaphthonic acid.

d) N-glycidyl compounds: N-glycidyl compounds derived from nitrogen-containing compounds such as aniline, isocyanuric acid, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenylmethane, and the like.

e) Others; Epoxy resins obtained from alicyclic compounds such as cyclopentadiene and dicyclopentadiene, triglycidyl compounds of p-aminophenol, and vinylcyclohexene dioxide.

Among the various polyepoxides mentioned above, from the viewpoint of physical properties such as ease of availability, strength of resin to be cured and heat resistance,
2. Diglycidyl ether of 2-bis(4-hydroxyphenyl)pavan (bisphenol A), 4.4'
- diglycidyl ether of dihydroxydiphenolmethane, polyglycidyl ether of phenol novolak, polyglycidyl ether of naphthol novolak, various aldehydes for phenol (glyoxal,
Glutaraldehyde, benzaldehyde. p-oxybanzaldehyde etc.> in the presence of an acidic catalyst, polyglycidyl ether of polyols, diglycidyl ether of polybrobylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of butanediol, diglycidyl ether/triglycidyl ether of glycerol, N. N. N
'N'-tetraglycidylmethylene dianiline, m-(
Preferred are glycidinolether esters of oxycanolebonic acids such as p-)oxybenzoic acid and oxynaphthoic acid, triglycidyl compounds of p-aminophenol, and vinylcyclohexene dioxide. In particular, diglycidyl ether of bisphenol 8, diglycidyl ether of bisphenol, phenol, polyglycidyl ether of cresol novolak, polyglycidyl ether of α-naphthol novolak, various aldehydes (glyoxal, glutaraldehyde,
benzaldehyde, p-oxybenzaldehyde, etc.) in the presence of an acidic catalyst, diglycidyl ether of polyols, diglycidyl ether of polypropylene glycol, diglycidyl ether of polyethylene glycol, and di-butanediol. Glycidyl ether, diglycidyl ether/triglycidyl ether of glycerol, N,N. N'N'-tetraglycidylmethylene dianiline, m-(1)-)oxybenzoic acid, glycidyl ether ester of oxycarboxylic acids such as oxynaphthoic acid, triglycidyl compound of p-aminophenol, and vinylcyclohexene dioxide is preferred.

These polyepoxides can be used alone or in combination.

The moisture content of polyepoxide and its reduction method The moisture content of polyepoxide used in the present invention is determined by the epoxy curing system (
In other words, the moisture content of polyepoxide + curing agent) is soo
It is necessary that it is less than pp+++, preferably 3
It is 50 ppl or less. 500DDII! If the temperature exceeds I!, foaming often occurs in the cured molded product, so products with good mechanical properties are recommended. It becomes difficult to build.

For this purpose, there are methods to obtain and use raw materials with low moisture content, but methods that utilize azeotropy with aromatic hydrocarbons, etc.
The moisture content of polyepoxide with a high moisture content may be reduced by methods such as Japanese Patent Publication No. 48-35720). Furthermore, by using polyepoxide mixed with 0.1 to 10% by weight of an isocyanate compound and subjected to pretreatment such as heating as necessary, good cured molded products with virtually no foaming can be obtained. It can be manufactured. The temperature and time conditions for pretreatment heating depend on the type of polyepoxide and isocyanate compound used, but are usually room temperature to 100°C.
A period of several hours to several tens of hours is preferable. The isocyanate compound used may be monofunctional, such as phenol isocyanate.

For the purpose of the above pretreatment, aromatic isocyanates are preferred when long-term flow stability is required.

This is thought to be due to the fact that the reactivity of a certain amine produced by reacting with moisture in the polyepoxide is slower for aromatic amines than for aliphatic amines.

Cyclization Trimerization Catalyst The cyclization trimerization catalyst that can be used in the present invention includes Pol
Yurethanes Chemistry and
Technology, p. 94. (196
2) , Encyclopedia of Poly
merScience and Technology
y, Vol. 7, page 743 can be used. Representative ones are listed below.

a) Tertiary amine type; N-methylmorpholine, triethylamine, tributylamine, triethylenediamine, N,N'-dimethylaniline, N-ethylbiverizine, N,N'-dimethylviperazine, aziridine, (dimethylamino methyl) phenol, 2,4.6-tris(dimethylaminebrobyl)-hexahydro-s-h riazine, Mannitz j:A group of phenolic compounds, etc.

b> Epoxide or tri-bamate used in combination with tertiary amine; glycidyl methyl ether. Glycidyl ethyl ether, glycidyl phenyl ether. Diglycidyl ether to bisphenol, etc.

The weight used is 0.5 to 2 times, preferably 0.8 to 1.2 times, relative to the tertiary amine.

C) Phosphine series; triethylphosphine etc.

d> Alkoxide type: sodium methoxide, potassium methoxide, sodium phenoxide, etc.

e) Metal oxide/halide type; Tinnic chloride. Potassium fluoride etc.

``) Carboxylic acid salts; potassium acetate, potassium 2-ethylhexanoate, zinc octoei 1.. Bismuth octoate, lead octoate, panadium octoate, cobalt naphthoate, ′
f! 4 naphthoate, potassium naphthoate, etc.

g) Organometallic compounds of tin and antimony; di-n-butyltin dilaurylate, tetraphenyltin, tributylantimony oxide, etc.

h) quaternary ammonium salt; Tetraethylammonium hydroxide etc.

) Imidazole type; 2-ethyl-4-methylimidazole and the like.

J) Alkoxyalene: Methoxyalene, butoxyalene, etc.

The amount of the cyclization catalyst added to the above-mentioned poly(V) cyanate is 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on the total amount of the polyisocyanate used.
It is 1 to 5%. In addition, in order to increase the curing speed, an appropriate co-catalyst may be used in addition to the above.

Epoxy curing agent/accelerator The polyepoxide used in the present invention reacts with polyisocyanate to form an oxazolidone ring, and a part of the oxazolidone ring is formed by simultaneously carrying out a so-called epoxy curing reaction using an epoxy curing agent. It is possible to impart properties such as flexibility to molded products. Various substances are known as epoxy curing agents, but carboxylic acid-based substances cannot be used because they generate carbon dioxide.

Specific compounds suitable as curing agents in the present invention are listed below.

a) Tertiary amine/imidazole curing agent: 2-methylimidazole, 2-ethyl-4methylimidazole, 2
-Phenylimidazole. Various imidazole derivatives such as 2-pendylimidazole can be mentioned.

b) Curing agent such as cationic polymerization catalyst system; Cationic polymerization catalysts such as borates, borane, and inorganic acids can be used. Specifically, phosphite esters such as triphenyl phosphite and trimethyl phosphite, benzenesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, trifluoromethanesulfonic acid, etc. acids, protonic acid esters such as dimethyl sulfate and methyl p-toluenesulfonate, Lewis acids such as tin tetrachloride, shaped titanium chloride, zinc chloride, ferric chloride, and aluminum chloride, and Lewis acids such as trifluoroborane ether complexes. Examples include acid complexes, other gold fflM compounds, alkyl halides, and iodine. Furthermore, boron trifluoride amine adduct, dicyandiamide, dicyan acid dihydrazide,
Latent curing agents such as guanamine and melamine that exhibit curing ability at a constant temperature can also be used as needed.

There are no particular restrictions on the use of these curing agents, but their preferred role is 0.01 to 20 mol%, based on the epoxide used.
More preferably 0.05 to 15 mol%, particularly preferably 0.1 to 10 mol%.

C) Amide-based curing agent: Saturated/unsaturated low-molecular or high-molecular polyamides can also be used as curing agents. For example, U.S. Patent No. 2,450
, 940, various polyamides known under the registered trademark of VERSAMID, etc. can be used in the present invention.

Amine curing agents are widely used for curing epoxides, and can be blended in a certain amount in the present invention for the purpose of modification.

The liquid resin composition of the present invention contains isocyane-1-.

Comparing the reaction rate of isocyanate cyclization and urea formation reaction with amine, the latter reaction generally proceeds faster. Therefore, if more amine is used than the equivalent amount of isocyanate in the composition, cyclization cannot occur. Therefore, the amines to be incorporated in the present invention are as follows:
It should not exceed 80% of the total equivalent weight of isocyanate;
It is preferably 60% or less, particularly preferably 40% or less.

In the present invention, primary and/or secondary aliphatic and aromatic amines can be used within the above range. In the case of a curing reaction at a relatively low temperature, an aliphatic diamine is used, and an aromatic diamine is used at a high temperature. A molded article cured using aromatic diamine has better heat resistance and milder reactivity with isocyanate, so it can be more preferably used in the present invention.

Aliphatic amine-based curing agents include ethylenediamine and diethylenetriamine. triethylenetetramine, tetraethylenepentamine 2diaminodicyclohexylmethane,
Aminoethylbiperacin, menthanediamine. Isophorone diamine, xylone diamine, polyoxyalkylene amine (e.g., registered trademark JEFFAMINE)
For example, On the other hand, examples of aromatic amine curing agents include diaminodiphenyl sulfone, diaminodiphenyl ether, and diaminodiphenylmethane.

The curable liquid resin composition of the present invention can be formulated with an appropriate low-shrinkage agent to reduce shrinkage during curing.
It is possible to prevent warpage, cracks, etc. of molded products, or to improve surface properties. Typical shrinkage reducing agents are illustrated below.

Thermoplastic polymer polyvinyl acetate. Polymethacrylic acid ester. Polystyrene, polyester, and polyurethane 1-reactive liquid polymers (such as carboxyl-terminated butadiene-acrylic O nitric polymers) can be used. Also, a cobolymer graft polymer selected from two or more of the above thermoplastic polymer repeating units. Protoxypolymer and mixtures can also be incorporated into the liquid resin composition of the present invention.

The standard blending amount of these thermoplastic polymers is about 4 to 10 weight percent of the liquid resin component.

Filler Various inorganic and organic fillers or fillers are basically non-shrinkable during the curing reaction, and if they are blended into the liquid resin composition of the present invention, the total resin composition As a result, it becomes possible to reduce shrinkage. Generally, the inorganic filler is used in a larger amount than the amount of the thermoplastic polymer described above.

The standard blending amount is 50-250% by weight of the liquid resin component.
It is preferably 75 to 150%.

Typical fillers include metal carbonates and oxides such as calcium carbonate, and glass and ceramics. grain. Plastic powder. Examples include short fibrous materials and flake-like materials.

In general, shaped products made by blending and hardening fillers are opaque. For the purpose of imparting transparency, a filler having a refractive index comparable to that of cured street resin (1.48 to 1.62 in the case of unsaturated polyester) can be blended. Examples of such fillers include various glass powders, beads, fibers, aluminum hydroxide, barium sulfate, and the like.

Bicyclo A/Subiro 4 These compounds often show expansion properties during ring-opening polymerization (anti-1; i5), and monomers with such chemical structures,
Oligomer. When a polymer is blended into the liquid resin composition of the present invention, it exhibits lower shrinkage than when it is not blended.

Such subi-O compounds include subi-orthocarbonate. Bicycloorthoesters are well known, and bicycloorthoesters are also known to be effective in reducing shrinkage (for example, JP-A-62-29
See No. 5920>. Furthermore, there is a double bond within the molecule. Low shrinkage can be achieved by blending into the liquid resin of the present invention various monomers, oligomers, etc. that have both functional groups such as amines and carboxylic acids, and the above-mentioned subiro-orthoester structure.

These undergo ring-opening reactions in the presence of cationic catalysts, radical initiators, or acid anhydrides. Examples of typical intercyclic catalysts are as follows.

a) Cation catalyst Examples of cation catalysts include boron trifluoride etherate and Lewis acids such as tin chloride [WJ. Bailey
and T. Endo. J. Polym. Sc
i. : Polym, CheIll. Ed. ,1
4.1735 (1976) etc. 1.

b) Radical initiator heat. Examples of radical initiators that can be used in ring-opening reactions using microwaves, infrared rays, and ultraviolet rays include alkyl peroxides such as di-1-butyl peroxide and dicumyl peroxide. Examples include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, peroxycarbonates such as diisobrobyl peroxycarbonate, and azos such as azobisisobutyl nitrile [W
, J., 3ailey and T. Endo. J
．． Polym, Sci, ; Polym,
Chem, Ed,, i3, 2535 <1975
), etc. References.

Among these, those used as curing agents for epoxides can be used. Examples include: polyvinylphenol. Low-molecular-weight phenols (cresol, alkylphenol, etc.), novolak-type and resol-type resins made from bisphenol or these as starting materials, and succinic acid. Polybasic acids such as itaconic acid and maleic acid and their oxidized anhydrides; biromellitic acid, trimellitic acid, penzophenonetetracarboxylic acid, etc. and their acid anhydrides.

Derivatives having a carboxylic acid or acid anhydride group at the terminal/side chain of the molecule obtained from these polybasic acids or their acid anhydrides, various carboxylic acid type polyesters prepared from polybasic acids and polyols (for example, special ljfl 1982-
49228).

Composition ratio of each component In the curable liquid composition of the present invention, the weight ratio of the total amount of preservatives consisting of polyisocyanate and cyclization trimerization catalyst to the total amount of epoxy system components consisting of epoxide and epoxy curing is 15 ~80~80/20. If the total amount of polyisocyanate and cyclized trivalent component is less than 15% by weight, the degree of improvement in heat resistance is insufficient, while if it exceeds 80% by weight, the molded product becomes brittle.

Strain 1' By combining the above polyisocyanate with a monoisocyanate as necessary, mixing a cyclization trimerization catalyst, polyepoxy and an epoxy curing agent, and heating as necessary, a highly heat resistant and strong product can be obtained. It is possible to produce molded products. When using a composition that satisfies the constituent requirements of the present invention,
Almost no foaming occurs in the molded product.

The curable liquid composition of the present invention can be injected and mixed as a single component or divided into two or more components, and then cured in a mold. Depending on the purpose, this in-mold curing may be non-reinforced.
lyl olding) or reinforcement bodies such as glass fiber (Resin RransferMoldin).
g) can also be carried out.

It goes without saying that when carrying out the one-component method, it is necessary to use a resin solution prepared while the mixed resin solution maintains fluidity. Longer pot life (shel
If a fl ife) is desired, a two-component type is used.

That is, A consisting essentially of an epoxide/cyclization trimerization catalyst
One example is a method in which a B liquid consisting essentially of a liquid and a polyisocyanate/epoxy curing agent is mixed immediately before the mold. Some epoxy curing agents also act as isocyanate cyclization trimerization catalysts. In such cases, it is better to incorporate a latent epoxy curing agent into the epoxide/m-forming trimerization catalyst (liquid A) side.As a latent curing system, one using heating or a two-part curing agent such as an accelerator may be used. Mixing is known.An example of the latter is a cyclization trimerization catalyst.Some components such as epoxy curing agents exhibit high activity only when mixed with a promoter, and in such cases, the catalyst component and promoter Mix the ingredients with the liquid on the opposite side of A and B, 2
It is also possible to blend the materials so that a substantial curing reaction occurs only upon liquid mixing. Specific combinations are illustrated below.

Cyclization tricarboxylic catalyst Accelerator tertiary amine Epoxide epoxy initiator Accelerator polyamine Imidazole compound Suitable reaction temperature varies depending on the components used, but is usually room temperature to 140°C, more preferably 40 to 120°C It is.

The reaction time varies depending on the above-mentioned components used, reaction temperature, and other conditions, but is usually 1 to 30 minutes, preferably 3 to 15 minutes.

The liquid resin composition of the present invention can be applied to various moldings as it is or by adding a thickener, etc., to give useful resin molded products, especially composite material molded products. A typical detergent strategy using the liquid resin composition of the present invention is described below.

b) Reaction injection method (RIM method: resin-containing transfer molding method, structure-RIM method) A method in which a liquid resin composition is injected into a mold and hardened to produce a shaped article. If the reinforcing material is not set in the mold, so-called RIM (reaction injection molding, R
eactiOnInjecttonMaidi
ng) are widely used in the urethane industry. In recent years, along with advances in reinforcement preforming technology, the placement and deterioration of reinforcement materials has improved. It is expanding as a precept method with a high degree of freedom in combinations, product reliability, and reproducibility. A pair of male and female molds (
After placing and clamping the reinforcing material in the gap of this mold in advance, liquid resin is press-fitted through the injection hole provided at the appropriate position, and is cured integrally with the reinforcing material in the mold.
This is a method to remove the mold later. If necessary, it is also possible to adopt a vacuum assisted resin injection method in which resin is injected while reducing the pressure inside the mold.

Reinforced molded products using extremely fast-curing RIM-based liquid resins (polyurea-based, dicyclopentadiene metathesis-based, etc.) are generally referred to as S-R IM, and those using other reactive resins are referred to as RTM. I'm used to calling it that.

In addition to the injection under reduced pressure described above, various improvements have been made to the RTM molding method, such as attaching foam to the core and injecting resin into the reinforcing material set in the gap between the core and the mold. , TERTM (The he
rmal ExpansionRes+n Tr
The resin composition of the present invention can also be applied to the ansfer Moldir+g) method.

Hand lay-up method: Place the sheet-like reinforcing material on top of the mold, and then apply the liquid resin composite matrix on top of it using a roller or brush. While applying with a rubber spatula, the reinforcing material layer is impregnated with resin, piled up in the required number of braises and shaped, and left to stand at room temperature or, if necessary, cured by heating with hot air or the like.

C) Bulk Molding Combined (BMC) method Low shrinkage agent 2 material based on the liquid resin composition of the present invention,
Colorant, play accelerator. A compound consisting of a thickener and a reinforcing agent such as Chopped 1-Land are kneaded in a second machine to form a mixed composition. ! ! do. This product is molded by heating and curing to obtain a desired shaped product. Generally, compression molding, transfer molding, extrusion molding, etc. can be employed as the molding method. When the above-mentioned mixed composition is in the form of a bun, it is sometimes referred to as dough molding compound (DMC).

Generally, when a high viscosity liquid resin composition is used, the reinforcing material is significantly damaged at the beginning of kneading, resulting in a significant decrease in mechanical strength. Therefore, a method is usually adopted in which the viscosity of the resin liquid is reduced at the beginning of mixing, and the viscosity is increased during molding to obtain a smooth surface of the molded product without bubbles or holes, thereby minimizing damage to the reinforcing material. Since the liquid resin composition of the present invention has a relatively low viscosity, it is suitable for the above purpose. Thickening methods include chemical thickening by blending WA organic oxide, etc., and physical thickening as seen in the example of using swelling of polyester resin with vinyl chloride resin paste resin, depending on the purpose. Any suitable method can be adopted.

2) Coating The composition of the present invention can also be used as a liquid resin for surface protection of various shaped articles or coating for paint. Depending on the purpose, additives such as thixotropic agents, antioxidants, pigments, and dyes can be mixed and used. It can also be used as an in-mold coating resin.

Gel coating method The liquid resin composition of the present invention can be used for the purpose of surface treatment of FRP or shaped products. The thickness of the gel coat layer is generally in the order of 0.3 to 0.5, and a surface mat etc. can be used in combination as necessary. The liquid resin composition used for the above purpose is required to have the following properties: ・Relatively high viscosity and stable thixotropy ・Fast leveling and rapid defoaming As a means of imparting properties suitable for gel coat. , Pigment if necessary outside the thixotropy imparting agent,! i! By appropriately blending polymerization accelerators or polymerization inhibitors, various defects (sagging, bubbles, etc.) that occur in gel coats can be avoided. Pinholes, color separation. By taking measures to avoid cracks, etc., it is possible to achieve stable surface quality.

f) Spray-up method This is a molding method that speeds up and saves labor by using mechanical force to speed up the lamination process in the hand lay-up method. That is, the liquid resin composition and the hardening agent are continuously and quantitatively mixed by using a spraying device called a chopper gun while cutting the glass roving into a predetermined length continuously and quantitatively. Supply and spray to Sub1 gun.

For the liquid resin composition of the present invention, suitable thixotropy, viscosity, gelation time, etc. can be selected by appropriately selecting the above-mentioned curing agent 2 additives.

g) Bag molding method The following bag molding methods can be selected: vacuum bag method, pressurized bag method: combined vacuum and pressure method, autoclave method, cableclave method, rubber plunger method/rubber pack method ．． Foldable rubber bag method. Combined mold or mold method
This is a compression molding method that cures and molds at low pressure and relatively low molding temperature. In order to apply the liquid resin composition of the present invention to this molding method, it is important to select a resin composition and a curing agent that harden at a relatively low temperature, and it is also necessary to make the demolding time slightly longer.

ri) Matted metal die method A brief form is set as necessary in a pair of G1 male molds heated to a predetermined temperature, and pressure is applied to the molding material at a predetermined speed through the molds using a hydraulic press or the like. Manufacture a shaped product.

n) Sheet Molding Compound (SMC) Method A resin-impregnated reinforcement sheet is prepared using a reinforcement roving such as glass and a film such as polyethylene coated with a liquid resin (combound).

Generally used SMCIs include drum type and conveyor type. The former has a compact machine body and S
Uniform impregnation can be carried out from both sides of the MC, and manufacturing conditions can be set relatively easily. On the other hand, the latter manufacturing method enables measures such as improved impregnation by low-pressure insufflation or meandering/shaking of the SMC. The thus prepared unthickened ')
The SMC is thickened to an appropriate degree by treatment such as heating, and then stored in a cold storage or the like.

Next, the SMC cut into the required shape and size is subjected to hot pressure molding using a press machine.

2) Filament winding method The continuous fiber tow is impregnated with liquid resin and wound around a mold called a mandrel. After winding up to a specified thickness, it is left at room temperature or cured by heating, and the mandrel is pulled out as necessary. Manufacture molded products. Since the liquid left silk composition of the present invention has a relatively low viscosity, there is a wide selection range of viscosity that provides a suitable impregnation rate, and also has good adhesion to reinforcing materials. Furthermore, the gelling/curing time can be advantageously selected from a wide range by selecting suitable catalysts and curing agents.

(w) Centrifugal molding method This method is widely used for button sheet materials for shirts, FRP resin mortar pipes, pipe bodies of large septic tanks, various tanks, pipes, silos, etc.

The principle of molding is to use the inner surface of a cylinder and use centrifugal force while rotating the cylindrical mold to flow the resin/glass tan inside the mold, or to spray or wind it onto the inner surface of the mold using centrifugal force. This is a method of pressing to form a uniform tube. Depending on the intended molded product, the viscosity of the liquid resin composition of the present invention, the shape and wall thickness of the molded product, the length and content of glass fibers, the specific gravity, particle size, and content of the filler (agent) to be kneaded are determined.
The mixing ratio etc. can be suitably adjusted to the curing temperature and centrifugal force.

W) Continuous wave/flat plate method: Normally, two rolls of film are stretched and unwound using a drawer attached to the end of the molding machine, and the gap between the two films is unwound. FR which underwent various treatments sequentially
After sandwiching the P plate-shaped buribreg and thoroughly removing air pockets and bubbles, heat and harden while shaping into the desired corrugated or flat plate, cut to desired width and length, and finish by removing the film. Various kinds of articles can be made from the liquid resin composition of the present invention.

Retrusion method is generally developed as a continuous method for materials with a relatively small cross-sectional area or relatively small diameter rods and pipes.
It is gradually being applied to the production of large-sized round products. usually,
Since the molded product is manufactured by running reinforcing continuous fibers in the same direction, it is suitable for products that require high strength and high dimensional accuracy.

The specific molding method is first 3! The continuous fibers are pulled out and sufficiently impregnated with a liquid resin composition that has been blended in advance. Next, fibers with other shapes and angles and fibers with other characteristics are added to sufficiently impregnate the liquid resin composition, and the fibers are passed through a die having the desired cross-sectional shape. At this time, the catalyst, curing agent, temperature conditions, and drawing speed are selected so that the curing progresses sufficiently. A series of pulling drives are performed continuously,
The resulting continuous shaped body is cut and finished to the desired length to create a molded product! Jl will be built.

y) Bibreg forming method The above-mentioned press forming method. The liquid resin composition of the present invention can be used for the purpose of preparing a resin-impregnated reinforcing material used in autoclave molding methods and the like. That is, a liquid resin composition containing a curing agent and a radical initiator may be used as it is, or a volatile solvent may be used. Filler agent. A composition containing various additives such as flame retardants is applied and impregnated onto a reinforcing material such as a delicate mat or woven fabric, and if necessary, heated rolls or
As a B-stage (semi-cured state) using a press etc.
After imparting various properties suitable for the desired cutting process, such as flow properties during heating, it is sent to the next manufacturing process. Pre-regs prepared using the liquid resin composition of the present invention as a starting material can be formed into high-performance laminates by dry laminating them mutually or with other materials and heating and curing them under appropriate pressure and temperature conditions. You can get the goods.

[Effects of the Invention] The curable liquid composition of the present invention as described above undergoes an epoxy curing reaction during curing. Various reactions such as cyclization of polyisocyanate and oxazolidone ring formation occur in combination, and there is virtually no foaming that tends to occur during curing due to cyclization of aromatic polyisocyanate compounds, resulting in high heat resistance and mechanical properties. We can provide excellent molded products.

[Examples] Examples of the present invention will be described in detail below, but the present invention is not limited thereto.

In the examples, the monomers, catalysts, etc. used are shown in parts by weight unless otherwise specified. In addition, the following abbreviations are used in the examples.

・Polyisocyanate MDI diphenylmethane diisocyanate oligo MDI
2 The above oligomer TDI: Tolylene diisocyanate urethanization catalyst Tin catalyst: Dibutyltin dilaurylate polyepoxide EP-815 Modified product of bisphenol diclycidyl ether with low viscosity epoxy (epoxy value = 1)
90) - Epoxy curing agent EC-1371 Imidazole curing agent Reference example 1 Here, an example of pre-treatment (moisture content reduction) of polyepoxide with an isocyanate compound is shown.

EP-815 with 0.5% MDI and 0.0% tin catalyst
1% of I7D was added and dried at 50° C. for 10 hours.

The moisture content, which was originally 16001)I)lm, was 470p
It dropped to pm.

Examples 1 to 5, Comparative Example 1 As polyisocyanate, oligo MDI/TO>2/
1, a Mannitz base-based catalyst composition (polyisocyanate/cyclization trimerization catalyst) as a cyclization trimerization catalyst;
100/3 to 5; weight ratio>, EP-815 treated as in Reference Example 1 above as the epoxide, imidazole-based EC-1371 as the epoxy curing agent (EP-
815/E C-1371-100/3 (weight ratio) or a composition having the compounding ratio shown in Table 1, a molded plate was prepared as follows.

a> Mixing of each component, defoaming, casting into mold (100℃ x 2
0 minutes> b) Demolding → Post-curing (150°C x 5 hrs) The physical properties of each molded plate obtained are shown in Table 1 below.

Table 1 Implementation VA7 Meta-xylylene diisocyanate as polyisocyanate, Mannich base as cyclization catalyst, bisphenol-F diglycidyl ether (EP-807) as epoxide, E C- as curing agent for epoxide. A composite liquid resin composition was prepared using 1371. The mixing ratio between each component was the same as in Example 4, and after mixing and molding, a molded sample of high-mouth DT was obtained by post-curing.

Implementation 1! il8 A composition consisting of isophorone diisocyanate as the polyisocyanate, finely pulverized KF (fukkapotassium) as the cyclization catalyst, EP-815 as the epoxide, and EC-1371 as the epoxide curing agent was used, and between each component The mixing ratio was the same as in Example 4.
After molding, a molded sample of high-mouth DT was obtained by post-curing.

Comparative Example 2 EP-815 used in Reference Example 1 was treated without being pretreated with an isocyanate compound (moisture content 1600pp).
A molded plate was prepared in exactly the same manner as in Example 7 except that m> was used. A large number of air bubbles with an average particle size of several hundreds of meters were observed in the obtained molded plate.

Claims (2)

[Claims] (1) In a composite curable liquid resin composition composed of a polyisocyanate, its cyclization trimerization catalyst, polyepoxide, and an epoxy curing agent, the moisture content of the epoxy curing system in the composition is 500 ppm or less. , and the epoxy curing agent constituting the epoxy curing system is one or more selected from the group of various imidazole-based, amide-based, and cationic curing agents, and the total amount of the cyclization curing system components and the epoxy curing agent are The weight ratio to the total amount of system components is 15/8
1. A composite curable liquid resin composition, characterized in that the composition is within a range of 0 to 80/20. (2) The polyepoxide used is 0.1 to 10% by weight
The composite curable liquid resin composition according to claim 1, which is mixed and pretreated with an isocyanate compound.