JP3073070B2 - Method for producing in-mold cured product having high glass transition temperature and in-mold cured product having high glass transition temperature obtained by the production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an in-mold cured product having a high glass transition temperature and to an in-mold cured product having a high glass transition temperature obtained by the production method. As a method for producing a molded product by curing the polymerizable composition in a mold, a resin transfer molding method (RTM) in which the polymerizable composition is transferred into a mold and cured, a cast molding method, and a reaction injection molding method ( RIM), a pultruding method in which a reinforcing fiber bundle is impregnated with a polymerizable composition in advance and cured in a mold is known. The present invention relates to a method capable of producing a molded article having a high glass transition temperature by curing a specific polymerizable composition in a mold, and a molded article having a high glass transition temperature obtained by the method. It is.

[0002]

2. Description of the Related Art Conventionally, in-mold curing molding using a polymerizable composition containing a radical polymerizable unsaturated (poly) ol having a radical polymerizable group and a hydroxyl group in a molecule, a polyisocyanate, and a vinyl monomer. There are the following proposals for things. 1) Examples of using a polymerizable composition containing a vinyl monomer such as an unsaturated polyester having hydroxyl groups at both ends, a polyisocyanate, and a vinyl aromatic hydrocarbon (U
SP48555368) 2) oligomeric unsaturated polyester, polyisocyanate or polyurethane polyisocyanate having a hydroxyl group at one end and a vinyl group at the other end;
3) having a saturated polyester chain or polyether chain in the main chain and having a (meth) acryloyl group and a hydroxyl group Example using a polymerizable composition containing an oligomeric monomer, a polyisocyanate, and a vinyl monomer having a (meth) acryloyl group and a hydroxyl group (JP-A-63-112615)

However, in the above-mentioned conventional proposal, only a molded product whose mechanical properties are easily deteriorated at high heat due to the structure of the radically polymerizable unsaturated (poly) ol or polyisocyanate used or a combination thereof can be obtained. If the mechanical properties of the molded product are apt to deteriorate at high heat, the processing conditions are significantly restricted when the molded product is subjected to secondary processing such as various surface treatments, and the use of the molded product is also significantly restricted. .

[0004]

The problem to be solved by the present invention is that, in the method for producing an in-mold cured molded product using a conventionally known polymerizable composition, only a molded product whose mechanical properties are liable to deteriorate at high heat is used. It is a point that cannot be obtained.

[0005]

Means for Solving the Problems By the way, the mechanical properties of an organic synthetic polymer compound under a temperature condition lower than a thermal condition under which the organic synthetic polymer compound undergoes a chemical change such as breaking of a molecular chain due to a thermal decomposition or an oxidation reaction or the like. The reason for the decrease is that the molecular chain whose molecular motion is constrained can easily undergo free molecular motion by heat. The glass transition temperature of the polymer compound is given as a temperature at which the restraint of the molecular chain is released and free molecular movement is possible. When the temperature rises, load deformation and volume change become remarkably large around the glass transition temperature. Therefore, an organic synthetic polymer compound having a higher glass transition temperature is a material that is less likely to have reduced mechanical properties when heated.

Accordingly, the present inventors have developed a molded product obtained by in-mold curing a polymerizable composition containing a hydroxyl compound, an isocyanate compound, and a vinyl monomer copolymerizable therewith, with respect to the hydroxyl compound, an isocyanate compound and a vinyl compound. As a result of studying the relationship between the chemical structure of the isocyanate compound and the glass transition temperature of the obtained in-mold cured molded product, an ethylenically unsaturated esterol having a specific structure was used as a hydroxyl compound, and an ethylenically unsaturated group was used as an isocyanate compound. It has been found that it is correct and suitable to use isocyanate compounds having a specific structure having a predetermined ratio.

That is, the present invention provides the following A, B and C:
The reaction ratio of A and B is OH / NCO =
0.8 to 1.2, and C / (A + B + C) = 0.1 to
A method for producing an in-mold cured product having a high glass transition temperature characterized by being cured in the presence of a catalyst at 0.9 (weight ratio), and a high glass transition temperature obtained by the production method And an in-mold cured product.

A: One or more of ethylenically unsaturated esterols represented by the following formula 1 B: One of isocyanate compounds having an ethylenically unsaturated group represented by the following formula 2 or 3 Or two or more C: one or two of vinyl monomers copolymerizable with A and B
More than species

[0009]

(Equation 1)

[0010]

(Equation 2)

[0011]

(Equation 3)

[In the formulas 1, 2, and 3, X¹, X^TwoA divalent to tetravalent port having no ethylenically unsaturated group;
A residue X obtained by removing a hydroxyl group from riol X^ThreeA tri- or tetra-valent poly having no ethylenically unsaturated groups
Residue Y except hydroxyl group from all¹From divalent to tetravalent polyisocyanate to isocyanate;
Residue Y excluding the^TwoA divalent polyisocyanate to an isocyanate group
Residue R excluding¹, R^Two, R^ThreeH or CH_Three  m, n; an integer of 1 to 3 and 2 ≦ m + n ≦ 4
P; an integer of 1 to 3 q, r; q = 1 to 3; r = 1 to 3;
S, t; s = 1 or 2, t = 2 or 3, and s + t = 3.
Or satisfy 4)

The ethylenically unsaturated esterol represented by the formula 1 is a (meth) acrylic acid partial ester of a polyol (hereinafter referred to as esterol). Esterols include (meth) acrylic acid and polyols, each of which is derived from dihydric to tetrahydric alcohols, polyether polyols, polyester polyols or polyester ether polyols, and has 1 to 3 free hydroxyl groups in the molecule. (Meth) acrylic ester monol, (meth) acrylic ester diol, and (meth) acrylic ester triol. When such an esterol is derived, the molar ratio of (meth) acrylic acid to 1 mol of the polyol is determined so that 1 to 3 free hydroxyl groups remain.

(Meth) acrylic ester monools include: 1) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 1,6-hexanediol monoacrylate, etc.
Mono (meth) acrylates of diols, 2) glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, 5-methyl-
1,2,4-heptanetriol dimethacrylate,
1,2,6-hexanetriol dimethacrylate, ethylene glycol monoglyceryl ether dimethacrylate, (poly) ethoxylated trimethylolpropane dimethacrylate, (poly) propoxylated trimethylolpropane diacrylate, (poly) ethoxylated glycerin, etc. , Triol di (meth) acrylates,
3) Tetraol tri (meth) acrylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, diglycerin triacrylate, (poly) ethoxylated pentaerythritol trimethacrylate, and ethylene glycol diglyceryl ether trimethacrylate.

(Meth) acrylic ester diols include: 1) glycerin monoacrylate, glycerin monomethacrylate, trimethylolpropane monomethacrylate, 5-methyl-1,2,4-heptanetriol monomethacrylate, 1,2,6-hexane Triol monomethacrylate, ethylene glycol monoglyceryl ether monomethacrylate, (poly) ethoxylated trimethylolpropane monomethacrylate, (poly)
Mono (meth) acrylates of triols, such as propoxylated trimethylolpropane monoacrylate, (poly) ethoxylated glycerin monomethacrylate,
2) Tetraol di (meth) acrylates such as pentaerythritol diacrylate, pentaerythritol dimethacrylate, diglycerin diacrylate, (poly) ethoxylated pentaerythritol dimethacrylate, and ethylene glycol diglyceryl ether dimethacrylate.

Examples of the (meth) acrylic ester triol include tetraols such as pentaerythritol monoacrylate, pentaerythritol monomethacrylate, diglycerin monoacrylate, (poly) ethoxylated pentaerythritol monomethacrylate, and ethylene glycol diglyceryl ether monomethacrylate. Mono (meth) acrylates are exemplified.

As the polyol used to derive the esterol as exemplified above, those having a molecular weight of 100 or less per hydroxyl group contained in the molecule can be advantageously used, and those having a molecular weight of 80 or less are particularly preferred. It can be used to advantage.

The isocyanate compound having an ethylenically unsaturated group represented by the formula 2 is a urethanization product of the aforementioned (meth) acrylic ester monool and a polyisocyanate having no ethylenically unsaturated group, It has 1 to 3 free isocyanate groups in the molecule.

Examples of the polyisocyanate having no ethylenically unsaturated group include 1) various isocyanates such as tolylene diisocyanate, methylene-bis- (4-phenylisocyanate), and hexamethylene diisocyanate; Triisocyanates such as trimers (Nippon Polyurethane Co., Coronate EH), and reaction products of hexamethylene diisocyanate / trimethylolpropane in a 3/1 (molar ratio) (Nihon Polyurethane Co., Coronate HL) 3)
Polyisocyanates containing an average of three or more isocyanate groups in the molecule, such as polymethylene polyphenyl polyisocyanate (Millionate MR, manufactured by Nippon Polyurethane Inc.) are exemplified.

When deriving such a urethanized product,
So that 1 to 3 free isocyanate groups remain (meth)
The OH / NCO functional group molar ratio in the reaction between the acrylic ester monol and the polyisocyanate is determined.

As the isocyanate compound having an ethylenically unsaturated group represented by the formula 2, 1) 2-hydroxyethyl methacrylate / tolylene diisocyanate =
1/1 (molar ratio) reactant, glycerin dimethacrylate / tolylene diisocyanate = 1/1 (molar ratio) reactant, glycerin dimethacrylate / polymethylene polyphenyl polyisocyanate (an average of 3.5 isocyanate groups per molecule) Monoisocyanates having an ethylenically unsaturated group, obtained from a (meth) acrylic ester monol and a polyisocyanate, such as a reactant; 2.5 / 1 (molar ratio); 2) glycerin dimethacrylate / Polymethylene polyphenyl polyisocyanate (containing an average of 3.5 isocyanate groups in one molecule) =
1.5 / 1 (molar ratio) reactant, ethylene glycol monoglyceryl ether dimethacrylate / polymethylene polyphenyl polyisocyanate (containing an average of 3.5 isocyanate groups in one molecule) = 1.5 / 1 (molar ratio) 3) diisocyanates having an ethylenically unsaturated group obtained from a (meth) acrylic ester monol and a polyisocyanate such as a reactant; 3) glycerin diacrylate / polymethylene polyphenyl polyisocyanate (an isocyanate group per molecule) = 4 on average) = 1 /
1 (molar ratio) reactant, glycerin dimethacrylate / polymethylene polyphenyl polyisocyanate (containing an average of 4 isocyanate groups in one molecule) = 1/1 (molar ratio) Having triisocyanates.

The isocyanate compound having an ethylenically unsaturated group represented by the formula 3 is a urethanization product of 1 mol of the above-mentioned (meth) acrylic ester diol and 2 mol of a diisocyanate having no ethylenically unsaturated group, or Is a urethanization product of 1 mol of (meth) acrylic ester triol and 3 mol of diisocyanate having no ethylenically unsaturated group. Each of these has two or three free isocyanate groups in the molecule.

Examples of the diisocyanate having no ethylenically unsaturated group used in the synthesis of the isocyanate compound having an ethylenically unsaturated group include the above-mentioned diisocyanates.

As the isocyanate compound having an ethylenically unsaturated group represented by the formula 3, 1) glycerin monoacrylate / tolylene diisocyanate = 1/2
(Mole ratio) Reactant, ethylene glycol monoglyceryl ether monomethacrylate / tolylene diisocyanate = 1/2 (molar ratio) Reactant, pentaerythritol dimethacrylate / hexamethylene diisocyanate = 1
/ (Molar ratio) reactant, propylene glycol diglyceryl ether dimethacrylate / tolylene diisocyanate = 1/2 (molar ratio), etc., obtained from (meth) acrylic ester diol and diisocyanate,
Diisocyanates having an ethylenically unsaturated group, 2)
Pentaerythritol monoacrylate / tolylene diisocyanate = 1/3 (molar ratio), ethylene glycol diglyceryl ether monomethacrylate / tolylene diisocyanate = 1/3 (molar ratio)
Examples include triisocyanates having an ethylenically unsaturated group, which are obtained from (meth) acrylic ester triol and diisocyanate.

As the polyisocyanate having no ethylenically unsaturated group used for deriving the isocyanate compound having an ethylenically unsaturated group represented by the formula 2 or 3, the polyisocyanate having no ethylenically unsaturated group per one isocyanate group contained in the molecule is used. Having a molecular weight of 100 or less can be advantageously used.
The following can be used particularly advantageously:

When synthesizing an isocyanate compound having an ethylenically unsaturated group represented by the formula 2 or 3, an inert solvent is added to the esterol, and a catalyst such as a tertiary amine well known in the synthesis of polyurethane is used. A method of adding a metal salt, preferably di-n-butyltin dilaurate, and gradually adding polyisocyanate while maintaining the temperature at 30 to 80 ° C. is employed. In this case, a vinyl monomer such as alkyl (meth) acrylate or styrene can be used as the inert solvent.

Examples of vinyl monomers copolymerizable with the ethylenically unsaturated ester ol of A and the isocyanate compound having an ethylenically unsaturated group of B include: 1) methyl methacrylate, methyl acrylate, ethyl methacrylate, acrylic (Meth) acrylic acid alkyl esters such as ethyl acrylate, 2) vinyl aromatic hydrocarbons such as styrene, methyl styrene and divinylbenzene, 3) diallyl phthalate and the like. One or more of these may be used as appropriate. However, methyl methacrylate, styrene, or a mixture thereof is preferred in view of the physical properties of a molded product obtained by curing.

In the present invention, when the in-mold curing of the ethylenically unsaturated ester ol of A, the isocyanate compound having an ethylenically unsaturated group of B and the vinyl monomer of C is carried out in the presence of a catalyst, The ratio is O
H / NCO = 0.8 to 1.2, and the ratio of C to the total amount of A, B and C is expressed as C / (A + B + C) by weight ratio.
= 0.1 to 0.9, preferably the above OH / N
CO = 0.95 to 1.05, and the above C / (A +
B + C) = 0.2 to 0.6. This is in order to obtain an in-mold cured product having desired excellent properties under a smooth molding operation.

The ethylenically unsaturated ester ol of A and B
The combination with the isocyanate compound having an ethylenically unsaturated group can be various combinations having different numbers of functional groups, and the number of the ethylenically unsaturated groups contained in the ethylenically unsaturated esterol and the isocyanate compound The total sum of the number of ethylenically unsaturated groups contained is 1.
It is preferable to combine them in a range of 0 to 3.0, and more preferably a combination of (meth) acrylic ester monol or (meth) acrylic ester diol and an isocyanate compound having an average of two isocyanate groups. . Such combinations include: 1) diol mono (meth) as (meth) acrylic ester monol
A combination of an acrylate and a diisocyanate having one or two ethylenically unsaturated groups, 2) a combination of a triol di (meth) acrylate as a (meth) acrylic ester monol and a diisocyanate having one ethylenically unsaturated group, 3) Combination of triol mono (meth) acrylate as (meth) acrylic ester diol and diisocyanate having one or two ethylenically unsaturated groups, 4) tetraol di (meth) acrylate as (meth) acrylic ester diol Examples thereof include a combination with a diisocyanate having one ethylenically unsaturated group.

In the present invention, the above-mentioned combination is preferable because the crosslinking density in the cured molded product is optimized in order to improve the thermal properties of the cured molded product obtained by the radical polymerization and the polyurethane forming reaction. Is to do. In order to optimize the crosslink density, the content ratio of the (meth) acryloyl group and the urethane-forming group contained in the ethylenically unsaturated esterol A and the isocyanate compound B is important. As an index of these content ratios, the average molecular weight (methacryloyl group equivalent) per one (meth) acryloyl group and the molecular weight (urethane group equivalent) per urethane-forming group contained in the reaction system of A and B are as follows. Available. In the present invention, the (meth) acryloyl group equivalent is preferably from 80 to 400, and the urethane group equivalent is preferably from 400 to 600. The average value of (meth) acryloyl group equivalent and urethane group equivalent is 250 to 450.
Is preferable, and 300 to 400 are more preferable.

In the present invention, a radical initiator and a urethanization catalyst are used for in-mold curing of the three components A, B and C as described above. As the radical initiator,
1) diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and substituted benzoyl peroxide having a substituent such as a methyl group or a methoxy group on an aromatic group; 2) t-butyl peroxyoctoate;
Alkyl peroxycarboxylates such as -butyl peroxybenzoate, 3) dicumyl peroxide,
Diallyl peroxides and dialkyl peroxides such as di-t-butyl peroxide and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane; 4) t-butylperoxy- Peroxycarbonates such as 2-ethylhexyl carbonate are exemplified. Examples of the urethanization catalyst include tertiary amines and metal salts that are well known in the synthesis of polyurethane, and di-n-butyltin dilaurate can be advantageously used. Further, in the present invention, a curing accelerator can be used in combination with the radical initiator. Examples of such a curing accelerator include aromatic tertiary amines such as dimethylaniline and dimethylparatoluidine, and cobalt naphthenate.

The amounts of the radical initiator, the urethanization catalyst, and the curing accelerator are not particularly limited. The amount of the radical initiator used is usually 0.2 to 2 parts by weight per 100 parts by weight of the total of A, B and C. The amount of the urethanization catalyst is usually 0.00.0 parts by weight per 100 parts by weight of the total of A and B.
1 to 1 part by weight. Further, the amount of the curing accelerator used depends on the molding temperature and the type of radical initiator, but is usually 1 part by weight or less per 100 parts by weight of the total of A, B and C. When the in-mold curing is performed at an initial mold temperature of 50 ° C. or less, it is advantageous to use a curing accelerator in combination to increase the curing speed.

In the present invention, an inorganic powdery filler is contained in an in-mold curing reaction system using an ethylenically unsaturated ester ol of A, an isocyanate compound having an ethylenically unsaturated group of B and a vinyl monomer of C. be able to. The content of the inorganic powdery filler is not particularly limited, but is usually 250 parts by weight or less per 100 parts by weight of the total of A, B and C. As the inorganic powdery filler, alumina trihydrate (Al ₂ O
₃ · 3H ₂ O), calcium carbonate, silica, calcium sulfate 2
Water salts (CaSO ₄ .2H ₂ O) and the like can be mentioned, but when a material containing water of crystallization, particularly alumina trihydrate, is used, it is possible to impart flame retardancy to the obtained in-mold cured product.

The molding method to which the present invention is applied is not particularly limited as long as it is an in-mold molding method. In particular, a reaction injection molding method (R
IM) are preferred. As one method of applying the reaction injection molding method, a solution in which predetermined amounts of A and C are mixed and dissolved, and a solution in which predetermined amounts of B and C are mixed and dissolved,
Using a radical initiator solution, these are transferred by a metering pump so as to have a predetermined ratio and injected into the mold, and the respective liquids are impact-mixed and cured in the mold to obtain a molded product. . At this time, it is also effective to load reinforcing fibers in the mold in advance. Urethanization catalyst, curing accelerator,
A predetermined amount of the inorganic powdery filler can be mixed with one or both of the solution of A and C or the solution of B and C.

[0035]

【Example】

Test section 1 (Synthesis of ethylenically unsaturated esterol) Synthesis of glycerin dimethacrylate (A-1) Take 86 parts (1.0 mol) of methacrylic acid and 3 parts of triethylamine as a catalyst, and maintain at 60 ° C. And 142 parts (1.0 mol) of glycidyl methacrylate were added to 30 parts.
Dropped over minutes. Thereafter, the reaction system was maintained at 70 ° C. for 5 hours to complete the synthesis. Oxirane oxygen was quantified in the product, but hardly detected. The product obtained here was glycerin dimethacrylate (A-1), and had a hydroxyl value of 245, an acid value of 0.7 and a saponification value of 493.

Synthesis of ethylene glycol monoglyceryl ether dimethacrylate (A-2) Take 132.6 parts (1.02 mol) of 2-hydroxyethyl methacrylate and 1.5 parts of a boron trifluoride ether complex as a catalyst. The mixture was stirred at 50 ° C., and 142 parts (1.0 mol) of glycidyl methacrylate was added dropwise over 30 minutes. Thereafter, the reaction system was maintained at 80 ° C. for 4 hours to complete the synthesis. Oxirane oxygen was quantified in the product, but hardly detected. The product obtained here was ethylene glycol monoglyceryl ether dimethacrylate (A-2), and had a hydroxyl value of 210, an acid value of 0 and a saponification value of 421.

Synthesis of dipropylene glycol diglyceryl ether dimethacrylate (A-3) 246 parts (1.0 mol) of dipropylene glycol diglycidyl ether, 172 parts (2.0 mol) of methacrylic acid
And using 3 parts of triethylamine as a catalyst, operating in the same manner as in the case of glycerin dimethacrylate (A-1),
Dipropylene glycol diglyceryl ether dimethacrylate (A-3) was synthesized. The product obtained here had a hydroxyl value of 271, an acid value of 0.9, and a saponification value of 267.

Test Category 2 (Synthesis of isocyanate compound having an ethylenically unsaturated group) Synthesis of isocyanate compound (B-1) 39 parts (0.3 mol) of 2-hydroxyethyl methacrylate, di-n-butyl 0.5 parts of tin dilaurate and 89 parts of mylionate MR-100 (polymethylene polyphenyl isocyanate containing an average of 3.5 isocyanate groups in one molecule, manufactured by Nippon Polyurethane) (0.2 mol)
Was dropped into the flask over 30 minutes. At this time, heat of reaction was generated, but the temperature in the flask was kept at 60 ° C. or lower. Thereafter, the temperature was maintained at 60 ° C. for 1 hour to complete the synthesis. An isocyanate compound (B-1) having an average of two isocyanate groups and an average of 1.5 ethylenically unsaturated groups was obtained.

Synthesis of isocyanate compound (B-2) 80 parts (0.5 mol) of glycerin monomethacrylate,
Using 0.8 parts of di-n-butyltin dilaurate and 174 parts (1.0 mol) of tolylene diisocyanate, the same operation as in the synthesis of the isocyanate compound (B-1) was performed, and two isocyanate groups were used on average. An isocyanate compound (B-2) having an average of one ethylenically unsaturated group was obtained.

Synthesis of isocyanate compound (B-3) 209 parts (0.5 mol) of dipropylene glycol diglyceryl ether dimethacrylate obtained in Test Category 1, 0.8 parts of di-n-butyltin dilaurate and Using 174 parts (1.0 mol) of tolylene diisocyanate,
The same operation as in the case of the synthesis of the isocyanate compound (B-1) was carried out, and the isocyanate compound having an average of two isocyanate groups and an average of two ethylenically unsaturated groups (B-
3) was obtained.

Test Category 3—Reaction Injection Molding (RIM)
Example 1 to 3 and Comparative Examples 1 to 5 The first liquid, the second liquid and the radical initiator solution shown in Table 1 were prepared. These three liquids were separately transported by a metering pump in a fixed amount, and injected into a nickel electroformed flat mold heated to 80 ° C. using a reaction injection molding machine. Five minutes after the end of the injection, the mold was released to obtain a flat molded product having a length of 250 mm, a width of 250 mm and a thickness of 10 mm. The molded product obtained above is 127 mm long x 1 width
The specimen was cut to a size of 2.7 mm × a thickness of 10.0 mm with a diamond cutter to prepare a test piece. The heat distortion temperature (JIS-K6919) of the test piece was measured. The results are shown in Table 1. In Comparative Example 5, the cured product was in a phase-separated state, and only a heterogeneous molded product was obtained.

[0042]

[Table 1]

Examples 4 to 7 and Comparative Examples 6, 7 A first liquid, a second liquid and a radical initiator solution shown in Table 2 were prepared. These three liquids were separately transferred by a metering pump in a fixed amount, and injected into a nickel electroformed flat mold heated to 50 ° C. using a reaction injection molding machine. Into the nickel electroformed flat mold, a glass strand continuous mat (Unifilomat U-750,
Nippon Electric Glass). After 15 minutes from the end of the injection, the mold was released to obtain a flat plate having a length of 250 mm x a width of 250 mm x a thickness of 3 mm. The molded product obtained above was converted to a length of 40.
The test piece was cut by a diamond cutter to a size of 6 mm × width 6 mm × thickness 3 mm. The temperature at which the maximum value of Tan δ was measured for the test piece with a dynamic viscoelasticity meter was measured, and this value was used as the glass transition temperature. The results are shown in Table 2.

[0044]

[Table 2]

Note) In Tables 1 and 2, 1st liquid, 2nd liquid, radical initiator solution: Numerical parts are by weight, ethylenically unsaturated esterol, vinyl monomer, isocyanate compound: The upper part is the kind, and the lower part is Parts by weight A-1 to A-3, B-1 to B-3: those obtained in test category 1 or test category 2 A-4: 2-hydroxyethyl methacrylate A-5: ethylene glycol monoglyceryl ether monomethacrylate A -6: tetrapropylene glycol monomethacrylate a-1: hydroxyl group type polypropylene maleate at both ends (average molecular weight: about 1000) a-2: methacryloylated poly (propylene maleate) at one end (average molecular weight: about 1000) b-1: tri Diisocyanate * 1: 50% solution of dibenzoyl peroxide * 2: Unsaturated esterol and Isocyanate (meth) acryloyl group equivalent in the reaction system of the compound * 3: urethane group equivalent in the reaction system of the unsaturated ester-ol and isocyanate compound * 4: * average of 2 and * 3

[0046]

As is clear from the above, the present invention described above has an effect that an in-mold cured molded article having excellent mechanical properties can be produced even at high temperatures.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI // B29K 75:00 105: 06 C08L 75:04 (72) Inventor Hirotaka Wada 20-12 Matsubara-cho, Gamagori-shi, Aichi (72) Inventor Iwao Komiya 288 Hamaike, Nishiyuki-cho, Toyohashi-shi, Aichi Prefecture Yamani Nishiyuki Heights 106 (56) References JP-A-2-137784 (JP, A) JP-A-4-277511 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. The following A, B and C are defined as the reaction ratio between A and B.
OH / NCO = 0.8 to 1.2 in terms of functional group molar ratio, and
C / (A + B + C) = 0.1-0.9 (weight ratio)
High galling characterized by in-mold curing in the presence of a catalyst
A method for producing an in-mold cured product having a transition temperature. A: Ethylenically unsaturated ester represented by the following formula 1
B: ethylenically unsaturated represented by the following formula 2 or 3
One or more isocyanate compounds having a group C: One or two vinyl monomers copolymerizable with A and B
More than kind [Formula 1](Equation 2)(Equation 3)[In the formulas 1, 2, and 3, X¹, X^TwoA divalent to tetravalent port having no ethylenically unsaturated group;
A residue X obtained by removing a hydroxyl group from riol X^ThreeA tri- or tetra-valent poly having no ethylenically unsaturated groups
Residue Y except hydroxyl group from all¹From divalent to tetravalent polyisocyanate to isocyanate;
Residue Y excluding the^TwoA divalent polyisocyanate to an isocyanate group
Residue R excluding¹, R^Two, R^ThreeH or CH_Three  m, n; an integer of 1 to 3 and 2 ≦ m + n ≦ 4
P; an integer of 1 to 3 q, r; q = 1 to 3; r = 1 to 3;
S, t; s = 1 or 2, t = 2 or 3, and s + t = 3.
Or satisfy 4) 2. The method of claim 1, wherein A is an ethylenically unsaturated ester monool or an ethylenically unsaturated ester diol, and B is a diisocyanate compound. . 3. The method for producing an in-mold cured product having a high glass transition temperature according to claim 1, wherein the in-mold curing is performed in a system containing an inorganic powdery filler. 4. The method for producing an in-mold cured product having a high glass transition temperature according to claim 1, wherein the in-mold curing is performed using a mold loaded with reinforcing fibers. 5. An in-mold cured product having a high glass transition temperature obtained by the production method according to claim 1.