JPH0464603B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a heat-resistant polyisocyanurate resin molded article, and more particularly to a method for easily molding the molded article using a two-component reaction injection or injection molding machine. The present invention also relates to a technique for obtaining industrially valuable polyisocyanurate resin molded articles having excellent heat resistance and mechanical properties. Generally, polyisocyanurate resins obtained from organic polyisocyanates have good hardness,
Fire resistant and also relatively high temperature e.g.
It is known to have mechanical resistance even at 180°C. Polyisocyanurate resin is produced by mixing a trimerization catalyst with organic polyisocyanate and performing a polymerization reaction by isocyanurate formation. During this process, polyurethane produced by mixing organic polyisocyanate and polyol In comparison, it is accompanied by significant difficulties in molding. First, when the blending ratio of the trimerization catalyst to the organic polyisocyanate is small, and this is measured and blended using a two-component reaction injection or an injection molding machine,
The problem is that this cannot be done accurately. Secondly, under similar circumstances, it is very difficult to mix organic polyisocyanate and trimerization catalyst due to the mechanism of the mixing device, often resulting in poor mixing and obtaining good polyisocyanurate resin molded products. I can't do that. In particular, when the polymerization promoting ability of the trimerization catalyst is increased, this poor mixing becomes a major problem in molding. In such a situation, uneven curing of the molded product occurs, making it impossible to obtain an industrially valuable product. In order to solve these problems, we have developed a system whose main component is an organic polyisocyanate (this is called the first component) and a system whose main component is a trimerization catalyst (this is called the second component). It is necessary to increase the amount of the first component and the second component so that the blending ratio of the first component and the second component approaches 1:1. Generally, as a means to solve this problem, a polyol is blended into the second component, and a trimerization catalyst is blended into the first component using the polyol as a medium. Using these first and second components, 2
Polyisocyanurate-based resin molded products molded using component reaction injection or injection molding machines are called urethane-modified polyisocyanurate, but urethane-modified polyisocyanurate can be easily molded by the conventional method described above. Many isocyanurate resins have poor heat resistance and lack industrial value. This is because in urethane-modified polyisocyanurate resins that can be easily molded, a large amount of urethane bonds that impair thermal stability are introduced into the polyisocyanurate resin, which causes a decrease in heat resistance. be. In order to improve moldability, it is necessary to introduce a large amount of a low molecular weight, low viscosity polyol into the second component, but this method does not yield a urethane-modified polyisocyanurate resin with good heat resistance. On the other hand, when a polyisocyanurate resin is obtained from an organic polyisocyanate and a trimerization catalyst, a means to efficiently mold it using a two-component reaction injection or an injection molding machine is required, and at the same time, a molded product that exhibits sufficient heat resistance is required. That is what is required. In conventional polyisocyanurate resin molding and processing techniques, there is an induction period before the polymerization reaction, a two-component reaction injection, a low polymerization reaction rate during and after injection, and an insufficient degree of polymerization reaction completion. Therefore, the molded product is brittle and easily destroyed during demolding, making it particularly difficult to obtain a molded product with a complicated shape. In addition, if a molded product is heated to 110 to 170°C and curing is started, cracking, softening deformation, or foaming will occur, so it is necessary to complete the reticulation reaction of the polyisocyanurate resin to create a molded product with sufficient heat resistance. I can't do it. In other words, conventional polyisocyanate resin molded products are surprisingly inferior in heat resistance. On the other hand, when polyisocyanate resin molded products are used as industrial materials, they are generally hard and brittle, and have a particularly low impact strength. This has been a major drawback when applied as a structural member of transportation equipment that is susceptible to damage. In general, materials that have both heat resistance and impact resistance are more valuable as industrial materials, and it has long been hoped that polyisocyanurate resin molded products would have these properties. I was unable to achieve this. The present invention has been made to solve the above problems, and has the following objects. 1 When manufacturing polyisocyanurate resin molded products using a two-component reaction injection or injection molding machine, the liquid ratio and viscosity of the first and second components should be suitable for measuring and mixing to facilitate molding. At the same time, to obtain the above resin molded product having excellent heat resistance. 2. To efficiently produce a polyisocyanurate resin molded article using a two-component reaction injection or injection molding machine, and to obtain the resin molded article having excellent heat resistance. 3. A polyisocyanurate resin molded product having good heat resistance and impact resistance can be efficiently produced using a two-component reaction injection or injection molding machine. 4 Even if post-curing is started at a temperature of 110 to 170°C, no defects will occur in the polyisocyanurate resin molded product, and the above-mentioned resin molded product with excellent heat resistance and mechanical properties can be finally obtained. . The present invention has been made as a result of extensive research in order to achieve the above object. That is, in molding a polyisocyanurate resin molded article using a two-component reaction injection or injection molding machine, the present invention includes an organic polyisocyanate and/or isocyanurate group-terminated prepolymer and an epoxy compound as the first component. In addition, the second component is a polyol, an ethylenically unsaturated bond-containing compound,
When using a liquid mixture of an aziridine compound and a tertiary amine, (1) the liquid weight ratio of the first component and the second component is 1:1 to
(2) In the blended system consisting of the first component and the second component, the value obtained by subtracting the hydroxyl molar concentration from the isocyanurate group molar concentration is 4 to 6 mmol/
g (3) The hydroxyl value of the polyol is 120 or less (4) The liquid viscosity of the ethylenically unsaturated bond-containing compound is 2000 cps/25°C or less (5) The weight ratio of the polyol and the ethylenically unsaturated bond-containing compound is The present invention is directed to a method for producing a polyisocyanurate heat-resistant resin molded article, which is characterized by using a first component and a second component having a ratio of 1:9 to 9:1. Items (1), (4), and (5) in the invention facilitate measuring and mixing in two-component reaction injection molding or injection molding, and enable the production of homogeneous molded products. This is because the liquid ratio becomes closer and the liquid viscosity of the second component can be adjusted to an appropriate value by the polyol and the ethylenically unsaturated bond-containing compound.
In addition, items (2), (3), and (5) are conditions that simultaneously satisfy the heat resistance and impact resistance of the molded product, but these are the conditions for trimerization catalysts for epoxy compounds, aziridine compounds, and tertiary amines. At the same time, the present invention allows two-component reaction injection or injection molding to be carried out extremely efficiently. These reasons are not well understood, but by using the first and second components of the present invention, it is possible to produce polyisocyanurate by converting organic polyisocyanate into isocyanurate, and to convert organic polyisocyanate and polyol into This is thought to be due to the simultaneous reaction of polyurethanization and polymerization of the ethylenically unsaturated bond-containing compound to form an optimal composite polymer network, and also because these processes proceed at a speed suitable for molding and the reaction is sufficient. It seems to be for the sake of completion. The two-component reaction injection or injection molding machine used to carry out the present invention is RIM (Reaction Injection Molding Machine).
Molding) or LIM (Liquid Injection)
In this type of molding equipment, two types of component liquids are simultaneously introduced under pressure into a mixing chamber and mixed, then injected into a closed mold, and reacted and hardened within the mold to obtain a molded product. Furthermore, a device that discharges and injects two types of liquids under normal pressure, such as a two-liquid urethane foaming machine or other two-liquid compounding machine, or a similar molding device system can also be used. Among these, RIM equipment is particularly preferred for efficient molding. Examples of the organic polyisocyanates used in the present invention include aliphatic, alicyclic, aromatic-substituted aliphatic, aromatic or heterocyclic polyisocyanates such as hexamethylene-1,6-diisocyanate, 2 , 2,4- or 2,2,6-trimethylhexamethylene-1,6-diisosialate-, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane-cis
or trans-cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-
Diisocyanate, ω, ω′-diisocyanatocyclohexane, isopropylidene dicyclohexyl-1,4-diisocyanate, tolylene-2,
4- or 2,6-diisocyanate, diphenylmethane-2,4'- or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, bitolylene diisocyanate, dianisidine diisocyanate, m- or p-phenylene Diisocyanate, xylylene-1,3- or -
Diisocyanates such as 1,4-diisocyanate, 4-isocyanatomethyloctamethylene-1,8-diisocyanate, triphenylmethane-4,4′,4”-triisocyanate, tris(4-isocyanatophenyl)thiophosphate,
undecane-1,6,10-triisocyanate,
A type of polyphenyl obtained by condensing a trifunctional or higher-functional polyisocyanate such as diphenylmethane-3,3',4,4'-tetraisocyanate, or alinine with formalin to synthesize a polyfunctional amine, and then phosgenating these. Polymethylene polyisocyanate, diphenylmethane diisocyanate isocyanate which is liquid at room temperature and has a cambodiimide group or uretonimine group as described in Japanese Patent Publication No. 38-4576, or urethane bond, allophanate bond, urea bond, biuret bond, Examples include the above-mentioned modified polyisocyanates containing an oxazolidone bond, an isocyanurate ring structure, and a uretidinedione ring structure. These organic polyisocyanates can be used alone or as a mixture of two or more. Among the above organic polyisocyanates, diphenylmethane diisocyanate-based liquid polyisocyanates and polyphenylene polymethylene polyisocyanates have advantages in handling, such as being industrially easily available, having low vapor pressure, and being liquid at room temperature. etc. are particularly suitable. The isocyanate group-containing prepolymer used in the present invention is obtained by reacting an active hydrogen compound with an excess of organic polyisocyanate, and includes, for example, ethylene glycol, propanediol,
Low molecular weight diols such as butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and neopentyl glycol; low molecular weight trifunctional or higher functional polyols such as glycerin, trimethylolpropane, and pentaerythritol; alkylene oxide. and water or low molecular weight polyols, hydroxyl group-terminated polyethers obtained from low molecular weight amines or low molecular weight alkanolamines, hydroxyl group terminated polyesters obtained from lactone and low molecular weight polyols, adipic acid, phthalic acid, tricarballylic acid, etc. Hydroxyl group polyesters obtained from polybasic acids and low molecular weight polyols, and other hydroxyl group-containing oligomers used in the polyurethane industry, such as polycarbonate polyols, polybutadiene polyols, polyolefin polyols, castor oil polyols, etc. It is prepared by reacting one or more kinds of polyols (approximately 500 to 8,000) with an excess of organic polyisocyanate. The organic polyisocyanate or isocyanate group-containing prepolymer can be used alone or as a mixture in any mixing ratio. The isocyanate group concentration of these products alone or in combination is 4
~12 mmol/g is preferred, particularly preferred is 5
~8 mmol/g. Isocyanate group concentration
If it is less than 4 mmol/g, too little isocyanate ring structure is introduced into the cured product, making it impossible to obtain a polyisocyanurate resin molded product with good heat resistance. On the other hand, when the isocyanate group concentration exceeds 12 mmol/g, the polyisocyanurate ring network density formed from the organic polyisocyanate becomes extremely large, and the network formation reaction cannot be completed sufficiently due to effects such as steric hindrance. Therefore, it is essentially difficult to obtain molded products with excellent heat resistance and impact resistance. The epoxy compounds used in the present invention are mono- or polyepoxy compounds, such as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, P- or o-propylphenyl glycidyl ether, P- or o-
Butylphenyl glycidyl ether, P or o
- Monoepoxy compounds such as nonylphenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, glycidyl ester of versatile acid, diglycidyl ether of pisphenol A, butadiene diepoxide, 3,
4-Epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, bicyclohexene dioxide, 4,4'-di1,2-epoxyethyl)biphenyl, 2,2-bis(3,
4-epoxycycloheicyl)propane, diglycidyl ether of resorcinol, bis(2,3-epoxycyclopentyl)ether, 2-(3,4
-epoxy)cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4, Diepoxides such as 5-epoxy-1,2-cyclohexanedicarboximide), triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,
5-(1,2-epoxyethyl)benzene-2,
2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane,
Epoxy compounds having trifunctionality or more are used, such as polyglycidyl ether of phenolmaldehyde novolak, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane. The above epoxy compounds may be used alone or as a mixture of two or more. The epoxy compound is an organic polyisocyanate and/or an isocyanate group-containing prepolymer.
It is used as a subcomponent in the first component liquid. The weight fraction of the epoxy compound in the first component is from 0.1 to 30%, particularly preferably from about 0.5 to 10%.
If the content of the epoxy compound is less than 0.1%, the degree of reaction completion in the latter half of the polyisocyanurate formation reaction is insufficient, and demolding becomes difficult during two-component reaction injection or molding with an injection molding machine. Furthermore, if the content of the epoxy compound exceeds 30%, the heat distortion temperature of the cured resin decreases, and the heat resistance decreases accordingly. The first component is preferably liquid and low viscosity at room temperature, but even if it can be made liquid and low viscous by heating, or it contains a solid dispersion, it may have poor fluidity, metering properties, etc. in a two-component injection or injection molding machine. Any material may be used as long as it does not impede mixability, injection or injection properties. However, for the sake of mixability, injection/injection properties, or simplification of the structure of the molding machine, it is particularly preferred that these be liquid at room temperature and have a viscosity of 50 poise or less. The polyol used in the present invention is a polyol with a relatively high molecular weight (molecular weight of about 500 to 8,000), as exemplified as the raw material for producing the isocyanate group-containing prepolymer, and its hydroxyl value is
120 or less. Polyols with a hydroxyl value exceeding 120 are not preferable because when they are introduced into the polyisocyanurate resin structure through urethane bonding, they significantly reduce the heat resistance and also have a small effect on imparting toughness such as impact resistance. . In particular, the preferred polyol has a hydroxyl value of 30 to 90. The ethylenically unsaturated bond-containing compound used in the present invention has the following formula: (In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and Z is a residue of an n-functional monoalcohol or polyol excluding the hydroxyl group, n is 1 to 4
For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, amyl acrylate , hexyl acrylate, lauryl acrylate,
Acrylic acid alkyl esters such as stearyl acrylate and corresponding methacrylic acid alkyl esters, alkyl esters of acrylic acid such as methoxyethyl acrylate and ethoxyethyl acrylate, ethylene glycol acrylate, diethylene glycol acrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol acrylate, neopentyl glycol diacrylate, polypropylene glycol (molecular weight 200-2000) diacrylate, polyethylene glycol (molecular weight 200-2000) diacrylate, trimethylolpropane triacrylate, etc. Acrylic acid ester of polyol and methacrylic acid ester corresponding to these, or b the following formula (In the formula, Y represents a residue of an m-functional carboxylic acid excluding the carboxyl group), and m is an acrylic ester monomer of 1 to 4, such as allyl penzoate, diallyl phthalate, diallyl isophthalate, Diallyl adipate, diallyl chlorendate, triallyl trimellitate, tetraallyl pyromellitate, diallyl maleate, diallyl fumarate, diallyl citraconate, dially itaconate, or other ethylene with a viscosity of 1000 cps/25°C or less Compounds containing unsaturated bonds such as vinyl acetate, styrene, vinyltoluene, α-methylstyrene,
Divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallylbenzene phosphonate, pentaerythritol diallyl ether, N-vinylpyrrolidone, or α,β
-Oligotesters made from unsaturated dicarboxylic acids and diols with a viscosity of 1000 cps/25°C or less, e.g.
Polydiethylene glycol fumarate with a molecular weight of 300, polydiethylene glycol itaconate with a molecular weight of 400, etc. can be used. These can be used singly or as a mixture of two or more, but those that can be quickly and simultaneously polymerized during trimerization of polyisocyanate are preferred, and polymethacrylate of polyol (a), diallyl phthalate (b), etc. are particularly preferred. . The aziridine compound used in the present invention has the following formula: (In the formula, R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₃ is a hydrogen atom or a hydroxyl group, X is a hydrogen atom or n is a functional residue, l
is a number from 1 to 6), for example, 2-
(1-Alidinyl)ethyl methacrylate, 2(1
-aziridinyl)ethyl methacrylate, 2-
(1-aziridinyl)ethyl acrylate, ω-
Methyl aziridinylpropionate, ethylene glycol bis(ω-aziridinylpropionate), trimethylolpropane tris(ω
-aziridinylpropionate), pentaeryloritol tetra(ω-aziridinylpropionate), sorbitol hexa(ω-aziridinylpropionate), β-(2-methylaziridinyl)ethyl Methacrylate, diethylene glycol bis[ω-(2-methylaziridinyl)propitonate], 1,3,6-
Aziridine compounds containing an ester bond such as hexanetriol tris [ω-(2-ethylaziridinyl)propionic acid ester], 1-(2
-hydroxyethyl)aziridine, 1-(2-hydroxyethyl-2-methylaziridine, 1-
(2-hydroxyethyl)-2-ethylaziridine, 1-(2-hydroxy-2-pheniethyl)
Aziridine compounds containing hydroxyl groups such as aziridine, 1-(2-hydroxy-2-phenylethyl)-2-methylaziridine, 1-(2
-Aziridine compounds containing a nitrile group such as -cyanoethyl)aziridine, 1-(2-cyanoethyl)-2-methylaziridine, 1-(2-cyanoethyl)-2-ethylaziridine, ω-aziridinylpropionic acid, ω -Aziridinyl compounds containing a carboxyl group such as (2-methylaziridinyl)propionic acid, ω-aziridinylpropionic acid amide, ω-(2-ethylaziridinyl)
Aziridine compounds containing an amide group such as propionic acid amide, aziridine compounds containing an ether bond such as 1-(β-methoxyethyl)aziridine, 1-(β-methoxyethyl)-2-ethylaziridine, 1- Ethylaziridine, 1-(β
-phenylethyl)-2-methylaziridine, or b the following formula (In the formula, R ₄ is a hydrogen atom or a carbon number of 1 to 5
Triethylene melamine derivatives represented by triethylene melamine (alkyl groups), such as triethylenemethimine, tris(2-methylethylene)melamine, tris(2-methylethylene)melamine, tris(2-methylethylene)melamine, tris(2-methylethylene)melamine,
-ethylethylene melamine), etc. The above aziridine compounds can be used alone or as a mixture of two or more. The tertiary amine used in the present invention is, for example,
triethylamine, tri-n-propylamine,
Tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-tertiary butylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, triundecyl Amine, tridodecylamine, triotadecylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tetramethylbutanediamine, tetramethylhexanediamine,
Bis(N,N-dimethylaminoethyl)adipate, dimethylaminopropylamine, bis(N,
Aliphatic tertiary amines such as N-dimethylaminoethyl) ether, alicyclic tertiary amines such as N,N-dimethylcyclohexylamine and N-methyldicyclohexylamine, tribenzylamine,
aromatic substituted aliphatic tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol;
N-methylmorpholine N-ethylmorpholine, N
-dodecylmorpholine, N,N'-dimethylpiperazine, 1,8-diazapicyclo[5,4,0]
undecene-7,N,N',N''-tris(dialkylaminoalkyl)hexahydro-8-triazine, 1,4-diazabicyclo[2,2,2]octane, 2-methyl-1,4-diazahicyclo[2, 2,2] Heterocyclic tertiary amines such as octane.These can be used singly or as a mixture of two or more.In the method for molding the polyisocyanurate heat-resistant resin of the present invention, In order to simultaneously convert the isocyanate into polyisocyanurate and polymerize the ethylenically unsaturated bond-containing compound, an epoxy compound blended into the first component system, an aziridine compound blended into the second component system, and a tertiary Each amine plays an important role. (1) Aziridine compound: Eliminates the induction period for IPN formation and enables simultaneous polymerization. For this purpose, the amount of aziridine compound is 0.2 to 20% by weight based on the total amount of the first and second components. %, preferably 0.5 to 10% by weight. (2) Tertiary amine: Enables the polymerization of the polyisocyanate and the ethylenically unsaturated bond-containing compound. 0.1 to 10% by weight based on the total amount, preferably 0.2 to 5% by weight
% by weight. (3) Epoxy compound: promotes the polymerization of polyisocyanate and compounds containing ethylenically unsaturated bonds,
Enables rapid curing. For this reason, the first
It is present in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the component and the second component. Further, in the present invention, the liquid ratio of the first component and the second component is 1:1 to 5:1.
Based on the weight ratio, one or both of the above components may include pigments, blowing agents, filling reinforcing materials, surfactants, radical polymerization initiators such as peroxides, stabilizers such as antioxidants and light stabilizers, Alternatively, other compounding materials may be included, but in this case, the liquid ratio of the first component to the second component is 1:1 to 5:1 by volume of the former to facilitate molding. It is preferable to keep each component at a viscosity of 5000 cps or less at a temperature of 100° C. or less. Liquid reaction molding uses the above two-component system, and measures and mixes it with a two-component low-pressure blender or a two-component high-pressure blender,
This is carried out by flowing a predetermined amount into a mold with an open end treated with a release agent, or by injecting it into a closed mold via a runner. The molded product hardened in the mold,
The mold is removed from the mold or molded, and cured if necessary. After curing is carried out at an appropriate temperature of 110 to 170℃ for the necessary time, if necessary,
Appropriate post-curing is performed within or outside this temperature. The initial post-cure time is about 2 to 8 hours. According to the present invention, large, thin-walled molded products and small parts that are strong and have complex shapes can be efficiently produced, and the molded products have excellent heat resistance, so they can be extremely useful industrial materials. These uses include, for example:
Main shells of televisions, VTRs or audio equipment, switch covers, printed circuit boards, lamp covers, electrical equipment parts such as semiconductor encapsulation molded products, household items such as frying pan handles, iron handles, oven plates, etc., engines. Industrial materials such as room bulkheads, parts around engines, lamp covers, structural parts around heaters, etc., solar thermal equipment, structural parts for nuclear reactors, sliding parts of machinery, etc. are extremely heavy, and Useful. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. Examples 1 to 10, Comparative Examples 1 to 7 The first and second components shown in Table 1 were filled into each tank of Twin Flow VR (normal pressure two-component compounding machine manufactured by Naka Seiki) and heated to 30°C. After controlling the temperature, the liquid was pumped using a piston pump to achieve a predetermined mixing ratio, and mixed using a mechanical stirrer equipped with a pin type roller. was injected (open). After the resin in the mold had hardened, it was removed from the mold, and the molded product was cured for a predetermined period in a gear oven, and then its physical properties were measured. Table 1 shows the evaluation results of the molded products according to the present invention (Nos. 1 to 10) and comparative examples (Nos. 1 to 7). Note that the first component and the second component were degassed for about 1 hour under 10 Torr prior to injection molding.

【table】

【table】

【table】

[Table] Examples 11-17, Comparative Examples 8-11 Molding was performed in the same manner as Examples 1-10 and Comparative Examples 1-7 using the first and second components shown in Table 2. Table 2 shows the evaluation results of the molded products according to the present invention (Nos. 11 to 17) and comparative examples (Nos. 8 to 11).

【table】 Example 18 The first component and second component shown below

Fill each tank of the TK-10RIM machine (polyurethane engineering two-component reaction injection molding machine) with [Table], adjust the temperature of each liquid to 30℃, and measure the liquid ratio of the first component/second component using a piston cylinder. were set to have a weight ratio of 121/33, and mixed using an impingement stirring method, and injected into a closed mold pre-coated with a fluororesin mold release agent and temperature-controlled at 50°C. When the mold was opened 120 seconds later, the resin molded product was sufficiently cured and could be easily removed from the mold without breaking. Next, 140℃×2h＋180℃×
After post-curing for 2 hours, the physical properties of the molded product were as follows. Appearance: No cracks, foaming, or other defects are observed. Density 1.34 Heat distortion temperature >250℃ Barcol hardness 58 Tensile strength 1450Kg/cm ² Tensile modulus 58900Kg/cm ² Izotsu impact strength, notched 3.8Kg・cm/cm Tensile strength retention after 1 month at 200℃ 98% Tensile strength retention rate after 3 months at 200℃ 93% Flammability test (0.6 mm thickness) UL94HB When the above molded product was used in the carburetor body of an automobile instead of aluminum die casting, the strength,
There were no problems in dimensional stability, stress relaxation resistance, and chemical resistance, and it was excellent in terms of light weight and manufacturing cost. Comparative Example 12 Plaxel 220 in the second component of Example 18 was added to NK
When it was used in the carburetor body of an automobile in the same manner as in Example 18 in place of ester NPG, it was found to be unsuitable for this purpose because it lacked strength and sometimes broke during driving. The physical properties of this molded article are as follows. Appearance: No cracks, blisters, etc. are observed. Density 1.33 Heat distortion temperature ＞250℃ Barcol hardness 59 Tensile strength 730Kg/cm ² Tensile modulus 61200Kg/cm ² Izotsu impact strength, notched 1.0Kg・cm/cm Tensile strength retention after 1 month at 200℃ 82% Tensile strength retention after 3 months at 200°C 57% Flammability test (0.6 mm thickness) UL94HB The formulations in Tables 1 and 2 are shown in parts by weight. In addition, each measurement value is as follows. (1) Density (g/cm ³ ): Measured by Archimedes method. (2) Barcol hardness: GYZJ934− according to JISK6911
One type was measured. (3) Tensile strength (Kg/cm ² ) and tensile modulus (Kg/cm 2 )
cm ² ): Measured according to JISK7113. (4) Heat distortion temperature (℃): According to JISK7207, load
Measured under 18.6Kg/ ^cm2 . (5) Izotsu impact strength (Kg・cm/cm):
Measured according to JISK7110. As is clear from the above description, the following effects can be obtained by the present invention. (1) Polyisocyanurate resins can be easily measured and mixed using a two-component reaction injection or injection molding machine, and molded products with uniform physical properties can be obtained without curing unevenly in injection or injection products. (2) Heat-resistant and tough polyisocyanurate resin molded products can be produced without sacrificing two-component reaction injection or injection molded products. (3) Polyisocyanurate resin prizes with good heat resistance and impact resistance can be efficiently produced using a two-component reaction injection or injection molding machine. (4) It is possible to produce polyisocyanurate resin molded products that do not produce defects such as cracks or blisters during post-curing, heat treatment, or heating.

Claims (1)

[Claims] 1. When molding a polyisocyanurate resin molded product using a two-component reaction injection or injection molding machine,
The first component is a liquid mixture of an organic polyisocyanate and/or an isocyanate group-containing prepolymer, and an epoxy compound, and the second component is a liquid mixture of a polyol, an ethylenically unsaturated bond-containing compound, an aziridine compound, and a tertiary amine. (1) The liquid weight ratio of the first component and the second component is 1:1 or more.
5:1, (2) in the blended system consisting of the first component and the second component, the value obtained by subtracting the hydroxyl molar concentration from the isocyanate group molar concentration is 4 to 6 mmol/g, (3) the hydroxyl value of the polyol is 120 or less, (4) the liquid viscosity of the ethylenically unsaturated bond-containing compound is 2000 cps/25°C or less, (5) the weight ratio of the polyol and the ethylenically unsaturated bond-containing compound is 1:9 to 9:1. A method for producing a polyisocyanurate heat-resistant resin molded article, the method comprising using certain first and second components.