JP3073068B2 - Method for producing in-mold cured product and in-mold cured product obtained by the production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an in-mold cured product and a cured in-mold product obtained by the 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 excellent in dimensional accuracy, surface properties and water resistance by curing a specific polymerizable composition in a mold, and a molded article obtained by the method. is there.

[0002]

2. Description of the Related Art Heretofore, radically polymerizable unsaturated (poly) ol having a radically polymerizable group and a hydroxyl group in a molecule, and radically polymerizable unsaturated (poly) isocyanate having a radically polymerizable group and an isocyanate group in a molecule have been known. There are the following proposals for in-mold cured products using polymerizable compositions containing vinyl monomers and vinyl monomers. 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;
Using polymerizable composition containing vinyl and vinyl monomer (JP-A-58-91719)

However, in the above-mentioned conventional proposals using a polymerizable composition containing an unsaturated polyester having a hydroxyl group as a terminal group, a polyisocyanate, and a vinyl monomer, curing shrinkage occurs due to the structure of the unsaturated polyester. Therefore, only a molded article having poor surface characteristics with poor dimensional accuracy and remarkable occurrence of cracks and embossing of reinforcing fibers can be obtained. Even when a conventionally known low-shrinking agent composed of a thermoplastic polymer compound is used in combination to reduce the curing shrinkage, the effect is hardly obtained. Further, in the above conventional proposal using a polymerizable composition containing an oligomeric unsaturated polyester having a hydroxyl group at one end and a vinyl group at the other end, a polyurethane polyisocyanate, and a vinyl monomer, a polyisocyanate is used. Although the curing shrinkage is smaller than that of the above-mentioned conventional proposals, a molded article with somewhat improved dimensional accuracy and surface characteristics can be obtained, but the degree of the improvement is still insufficient, and a low-shrinking agent is used in combination. However, curing shrinkage cannot be further improved.

[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, curing shrinkage is large, and therefore, dimensional accuracy and surface characteristics are reduced. Only bad moldings can be obtained, and the combined use of a low shrinkage agent has almost no effect.

[0005]

Means for Solving the Problems Thus, the present inventors have
For a molded product obtained by in-mold curing of a polymerizable composition containing a hydroxyl compound, an isocyanate compound, and a vinyl monomer copolymerizable therewith, the chemical structure of the hydroxyl compound and the isocyanate compound and the resulting mold As a result of studying the relationship with the properties of the inner hardened molded product,
It has been found that the use of an ethylenically unsaturated esterol having a specific structure as a hydroxyl compound and the use of an ethylenically unsaturated urethane isocyanate having a specific structure as an isocyanate compound at a predetermined ratio is properly preferred.

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
The present invention relates to a method for producing an in-mold cured product, wherein the in-mold curing is performed at 0.9 (weight ratio) in the presence of a catalyst, and an in-mold cured product obtained by the production method.

A: One or more of ethylenically unsaturated esterols of the following formula 1 B: One or more of ethylenically unsaturated urethane isocyanates of the following formula 2 or 3 C: One or two vinyl monomers copolymerizable with A and B
More than species

[0008]

(Equation 1)

[0009]

(Equation 2)

[0010]

(Equation 3)

[Equation 1, 2 and 3]¹, X^TwoA residue obtained by removing a hydroxyl group from a divalent to tetravalent polyol;
Group X^ThreeA residue Y obtained by removing a hydroxyl group from a tri- or tetravalent polyol;¹From divalent to tetravalent polyisocyanate to isocyanate;
Residue Y excluding the^TwoA divalent polyisocyanate to an isocyanate group
Residue R excluding¹, R^Three, R^FiveAn aliphatic hydrocarbon group R having 5 to 21 carbon atoms^Two, R^Four, R⁶H or CH_Three  d, e, f; d = 0 an integer of 0 to 2, e, f = 1 to 3
A number that satisfies d + e + f = 2 to 4 p, q; p = 0 to 2; q = 1 to 3;
R, s; an integer of 1 to 3, and 2 ≦ r + s ≦ 4
T, u, v; t = 0 or 1, u = 1 or 2, v = 2 or
3, and satisfy t + u + v = 3 or 4. However, d and p do not simultaneously become 0, and d and t also become
It does not become 0 at the same time]

The ethylenically unsaturated esterol represented by the formula 1 includes a (meth) acrylic acid partial ester of a polyol (hereinafter referred to as an esterol) and a polyol (meth) acrylic acid / long chain fatty acid mixed partial ester ( Hereinafter, this is referred to as a mixed esterol).

The esterol includes (meth) acrylic acid and a di- or tetrahydric alcohol as a polyol or a 2- to 4-hydric alcohol.
(Meth) acrylic ester monools, (meth) acrylic ester diols, and (meth) acrylic ester triols derived from polyvalent polyether polyols and having from 1 to 3 free hydroxyl groups in the molecule. You. When such an esterol is derived, the polyol 1 is so prepared that one to three free hydroxyl groups remain.
The molar ratio of (meth) acrylic acid used to mole is determined.

(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 dihydric alcohols, 2) glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, 5-methyl-1,2,4-heptanetriol dimethacrylate, 1,2,6-hexanetriol Di (meth) acrylates of trihydric alcohols such as dimethacrylate;
3) tri (meth) acrylates of tetrahydric alcohols such as pentaerythritol triacrylate and pentaerythritol trimethacrylate; 4) ethylene glycol monoglyceryl ether dimethacrylate; (poly)
Ethoxylated trimethylolpropane dimethacrylate, (poly) propoxylated trimethylolpropane diacrylate, (poly) ethoxylated glycerin, etc.
(Poly) ether triol di (meth) acrylates, 5) diglycerin triacrylate, (poly) ethoxylated pentaerythritol trimethacrylate, ethylene glycol diglyceryl ether trimethacrylate, etc. A) acrylates;

(Meth) acrylic ester diols include: 1) glycerin monoacrylate, glycerin monomethacrylate, trimethylolpropane monomethacrylate, 5-methyl-1,2,4-heptanetriol monomethacrylate, 1,2,6-hexane Tri (alcohol) mono (meth) acrylates such as triol monomethacrylate, 2) dihydric alcohol di (meth) acrylates such as pentaerythritol diacrylate and pentaerythritol dimethacrylate, 3)
Mono (poly) ether triols such as ethylene glycol monoglyceryl ether monomethacrylate, (poly) ethoxylated trimethylolpropane monomethacrylate, (poly) propoxylated trimethylolpropane monoacrylate, (poly) ethoxylated glycerin monomethacrylate, etc. (Meth) acrylates, and 4) di (meth) acrylates of (poly) ethertetraol such as diglycerin diacrylate, (poly) ethoxylated pentaerythritol dimethacrylate, and ethylene glycol diglyceryl ether dimethacrylate.

The (meth) acrylic ester triols include: 1) mono (meth) acrylates of tetrahydric alcohols such as pentaerythritol monoacrylate and pentaerythritol monomethacrylate; 2) diglycerin monoacrylate; and (poly) ethoxylated pentane. (Poly) such as erythritol monomethacrylate, ethylene glycol diglyceryl ether monomethacrylate, etc.
Mono (meth) acrylates of ether tetraol may be mentioned.

The mixed esterol is derived from (meth) acrylic acid, a long-chain fatty acid having 6 to 22 carbon atoms and a trihydric or tetrahydric polyhydric alcohol or a trihydric or tetrahydric polyether polyol, Mixed ester monols and mixed ester diols having one or two free hydroxyl groups therein are included. When such mixed esterols are derived, the molar ratio of (meth) acrylic acid and long chain fatty acid to 1 mol of polyol is determined so that one or two free hydroxyl groups remain.

The mixed ester monools include: 1) glycerin monomethacrylate / monooctanoate, trimethylolpropane monoacrylate / monoisononanoate, 5-methyl-1,2,4-heptanetriol monomethacrylate / monooleate, , 2,6-
Mixed ester monools derived from trihydric alcohols such as hexanetriol monomethacrylate / mono-2-ethylhexoate, 2) pentaerythritol dimethacrylate / monoisostearate, pentaerythritol monomethacrylate / diisooctanoate ,
Mixed ester monols derived from tetrahydric alcohols such as pentaerythritol dimethacrylate / monooctanoate, 3) ethylene glycol monoglyceryl ether monomethacrylate / monoisononanoate, (poly) ethoxylated trimethylolpropane mono Acrylate monoisostearate, (poly) propoxylated trimethylolpropane monomethacrylate
Mixed ester monools derived from (poly) ether triol such as monolaurate, (poly) ethoxylated glycerin monomethacrylate / monooctanoate, 4) ethoxylated pentaerythritol dimethacrylate / monoisostearate, ethylene Mixed ester monools derived from (poly) ether tetraol, such as glycol diglyceryl ether monomethacrylate / dideanoate.

The mixed ester diols include 1) mixed ester diols derived from tetrahydric alcohols such as pentaerythritol monomethacrylate / monoisostearate and pentaerythritol monomethacrylate / monoisooctanoate; 2) ethoxyl And mixed ester diols derived from (poly) ether tetraols, such as pentaerythritol monomethacrylate / monoisostearate and ethylene glycol diglyceryl ether monomethacrylate / monodecanoate.

As the polyol used to derive the esterols and mixed esterols exemplified above, those having a molecular weight of 100 or less per hydroxyl group contained in the molecule can be advantageously used. Can be used particularly advantageously.

The ethylenically unsaturated urethane isocyanate represented by the formula 2 is a urethanization product of the above-mentioned (meth) acrylic ester monool and polyisocyanate or a urethanization product of the above-mentioned mixed ester monool and polyisocyanate. It is. These all have 1 to 3 free isocyanate groups in the molecule.

The polyisocyanate used in the synthesis of the ethylenically unsaturated urethane isocyanate includes
1) Diisocyanates such as various tolylene diisocyanates, methylene-bis- (4-phenylisocyanate), and hexamethylene diisocyanate; 2) Hexamethylene diisocyanate cyclic trimer (Nippon Polyurethane Co., Coronate EH); Triisocyanates such as a reaction product (manufactured by Nippon Polyurethane Co., Coronate HL) having 3/1 (molar ratio) of trimethylolpropane; Examples include polyisocyanates containing an average of three or more groups in the molecule.

When deriving such a urethanized product,
So that 1 to 3 free isocyanate groups remain (meth)
OH / NCO in reaction of acrylic ester monool or mixed ester monool with polyisocyanate
Is determined.

As the ethylenically unsaturated urethane isocyanate represented by the formula 2, 1) 2-hydroxyethyl methacrylate / tolylene diisocyanate = 1/1 (molar ratio), glycerin dimethacrylate / tolylene diisocyanate = 1/1 (Mole ratio) Reactant, glycerin dimethacrylate / polymethylene polyphenyl polyisocyanate (average of isocyanate groups in one molecule: 3.
5) = 2.5 / 1 (molar ratio) ethylenically unsaturated urethane monoisocyanates obtained from a (meth) acrylic ester monol and a polyisocyanate, such as a reactant; 2) glycerin monomethacrylate / monoocta Noate / tolylene diisocyanate = 1/1 (molar ratio) reaction product, glycerin monomethacrylate / monooctanoate / polymethylene polyphenyl polyisocyanate (containing an average of 3.5 isocyanate groups in one molecule) = 2. 5/1 (molar ratio) ethylenically unsaturated urethane monoisocyanates obtained from mixed ester monools and polyisocyanates such as reactants, 3) glycerin dimethacrylate / polymethylene polyphenyl polyisocyanate (isocyanate in one molecule) Average of 3.5 groups) = 1. / 1 (molar ratio) reaction product, (average of 3.5 amino-containing isocyanate groups per molecule) of ethylene glycol mono-glyceryl ether dimethacrylate / polymethylene polyphenyl polyisocyanate = 1.5
/ 1 (molar ratio), such as reactants, ethylenically unsaturated urethane diisocyanates obtained from (meth) acrylic ester monool and polyisocyanate, 4) glycerin monomethacrylate / monooctanoate / polymethylene polyphenyl polyisocyanate (Containing an average of 3.5 isocyanate groups in one molecule) = 1.5 / 1 (molar ratio) Ethylenically unsaturated urethane diisocyanates obtained from a mixed ester monool and a polyisocyanate, such as a reactant; ) Glycerin diacrylate / polymethylene polyphenyl polyisocyanate (containing an average of 4 isocyanate groups per molecule) = 1/1 (molar ratio)
Reactant, glycerin monomethacrylate / monooctanoate / polymethylene polyphenyl polyisocyanate (containing an average of 4 isocyanate groups per molecule) = 1 /
Ethylenically unsaturated urethane triisocyanates, such as 1 (molar ratio) reactants.

The ethylenically unsaturated urethane isocyanate represented by the formula (3) is a urethanization product of 1 mol of the above-mentioned (meth) acrylic ester diol or mixed ester diol and 2 mol of diisocyanate or the above-mentioned (meth)
It is a urethane product of 1 mole of acrylic ester triol and 3 moles of diisocyanate. Each of these has two or three free isocyanate groups in the molecule.

Examples of the diisocyanate used for synthesizing the ethylenically unsaturated urethane isocyanate include the above-mentioned diisocyanates.

As the ethylenically unsaturated urethane isocyanate represented by the formula 3, 1) glycerin monomethacrylate / tolylene diisocyanate = 1/2 (molar ratio)
Reactant, pentaerythritol dimethacrylate / tolylene diisocyanate = 1/2 (molar ratio) Reactant, ethylene glycol diglyceryl ether dimethacrylate / hexamethylene diisocyanate = 1/2 (molar ratio)
Reactants such as ethylenically unsaturated urethane diisocyanates obtained from (meth) acrylic ester diol and diisocyanate, 2) pentaerythritol monomethacrylate / monooctanoate / tolylene diisocyanate = 1/2 (molar ratio) , Ethylenically unsaturated urethane diisocyanates obtained from mixed ester diols such as diglycerin monomethacrylate / monolaurate / hexamethylene diisocyanate = 1/2 (molar ratio) and diisocyanate; 3) pentaerythritol monoacrylate / triacrylate (Meth) acrylic ester such as diisocyanate = 1/3 (molar ratio), ethylene glycol diglyceryl ether monomethacrylate / tolylene diisocyanate = 1/3 (molar ratio) Ethylenically unsaturated urethanes triisocyanates obtained from an all and diisocyanate.

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

Examples of the vinyl monomer copolymerizable with the ethylenically unsaturated esterol A and the ethylenically unsaturated urethane isocyanate B include: 1) methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, etc. (Meth) acrylic acid alkyl esters,
2) vinyl aromatic hydrocarbons such as styrene, methyl styrene, and divinyl benzene; 3) diallyl phthalate; one or more of these can be used as appropriate; From the viewpoint of physical properties, methyl methacrylate, styrene, or a mixture thereof is preferable.

In the present invention, when the ethylenically unsaturated esterol of A, the ethylenically unsaturated urethane isocyanate of B and the vinyl monomer of C are cured in a mold in the presence of a catalyst, the ratio of A and B is functionalized. OH / NC in base molar ratio
O = 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) = 0.1 by weight ratio.
To 0.9, preferably OH / NCO =
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.

In the method for producing a cured molded product according to the present invention,
A ethylenically unsaturated esterol of A, an ethylenically unsaturated urethane isocyanate of B and a vinyl monomer of C are used. In this case, the ethylenically unsaturated esterol or the ethylenically unsaturated urethaneisocyanate has 5 carbon atoms. It is extremely important to use the one in which ２１21 hydrocarbon groups are introduced, in order to impart dimensional accuracy, surface characteristics and water resistance to the obtained in-mold cured molded product. In order to more effectively impart the above-mentioned properties to the obtained in-mold cured molded product, as the hydrocarbon group, an alkyl group having 7 to 17 carbon atoms, an isoalkyl group having 7 to 17 carbon atoms, and 15 carbon atoms.
~ 21 alkenyl groups are preferred. Further, the content of the hydrocarbon group is preferably from 7 to 35% by weight, more preferably from 10 to 30% by weight, based on the total amount of the ethylenically unsaturated esterol and the ethylenically unsaturated urethane isocyanate. .

The ethylenically unsaturated ester ol of A and B
Various combinations having different functional groups are possible for the combination with the ethylenically unsaturated urethane isocyanate, but the combination of the ethylenically unsaturated ester monool or the ethylenically unsaturated ester diol with the ethylenically unsaturated urethane diisocyanate is preferred. preferable. Such preferred combinations include 1) a combination of an ethylenically unsaturated urethane diisocyanate obtained from a (meth) acrylic ester diol / mixed ester monool and a polyisocyanate, 2) a mixed ester diol / (meth) acrylic ester monol and a polyisocyanate. Combination of ethylenically unsaturated urethane diisocyanate obtained from isocyanate; 3) Combination of ethylenically unsaturated urethane diisocyanate obtained from mixed ester diol / mixed ester monol and polyisocyanate; 4) (meth)
Combination of ethylenically unsaturated diisocyanate obtained from 1 mol of acrylic ester diol / mixed ester diol and 2 mol of diisocyanate, 5) ethylenic unsaturated diisocyanate obtained from 1 mol of mixed ester diol / (meth) acrylic ester diol and 2 mol of diisocyanate Combinations of saturated diisocyanates, 6) combinations of ethylenically unsaturated diisocyanates obtained from 1 mole of mixed ester diol / mixed ester diol and 2 moles of diisocyanate, among which 1)
A combination of 3), 4) or 6) is preferred.

In the present invention, a radical initiator and a urethanizing 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 can be contained in an in-mold curing reaction system using an ethylenically unsaturated esterol of A, an ethylenically unsaturated urethane isocyanate of B and a vinyl monomer of C. . 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 dihydrate (CaSO
₄ · 2H ₂ O), etc. However, those containing water of crystallization, in particular the use of alumina trihydrate, it is possible to impart flame retardancy to mold cured product obtained.

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.

[0037]

【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 glycerin monomethacrylate monooctanoate (A-2) Take 86 parts (1.0 mol) of methacrylic acid and 3 parts of triethylamine as a catalyst, stir at 60 ° C., 200 parts (1.0 mol) of glycidyl were added dropwise over 30 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 is glycerin monomethacrylate monooctanoate (A-2), and has a hydroxyl value of 195, an acid value of 1.0,
The saponification value was 394.

Synthesis of glycerin monomethacrylate monoisopalmitate (A-3) Using 142 parts (1.0 mol) of glycidyl methacrylate, 256 parts (1.0 mol) of isopalmitic acid and 3 parts of triethylamine as a catalyst. Glycerin monomethacrylate / monooctanoate (A-2), and glycerin monomethacrylate / monoisopalmitate (A-3) was synthesized. The product obtained here had a hydroxyl value of 143, an acid value of 1.3 and a saponification value of 284.

Synthesis of dipropylene glycol diglyceryl ether dimethacrylate (A-4) 246 parts (1.0 mol) of dipropylene glycol diglycidyl ether, 172 parts (2.0 mol) of methacrylic acid
And glycerin monomethacrylate monooctanoate (A-2) using 3 parts of triethylamine as a catalyst.
In the same manner as in the above, dipropylene glycol diglyceryl ether dimethacrylate (A-4) was synthesized. The product obtained here has a hydroxyl value of 271 and an acid value of 0.1.
9, saponification value was 267.

..Ethylene glycol diglyceryl ether monomethacrylate monooctanoate (A-
Synthesis of 5) 174 parts (1.0 mol) of ethylene glycol diglycidyl ether, 86 parts (1.0 mol) of methacrylic acid,
Using 144 parts (1.0 mol) of octanoic acid and 3 parts of triethylamine as a catalyst, operating in the same manner as in the case of glycerin monomethacrylate / monooctanoate (A-2), ethylene glycol diglyceryl ether monomethacrylate / monooctanoate was used. Noate (A-5) was synthesized. The product obtained here has a hydroxyl value of 276 and an acid value of 1.
6, saponification number 271.

Test Category 2 (Synthesis of Ethylenically Unsaturated Urethane Isocyanate) Ethylene Unsaturated Urethane Isocyanate (B-
1) Synthesis of glycerin monomethacrylate obtained in Test Category 1
120 parts (0.3 mol) of monoisopalmitate (A-3), 0.5 part of di-n-butyltin dilaurate, and millionate MR-100 (polyol containing an average of 3.5 isocyanate groups per molecule) 89 parts (0.2 mol) of methylene polyphenyl isocyanate, manufactured by Nippon Polyurethane Co.
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 ethylenically unsaturated urethane isocyanate (B-1) having an average of two isocyanate groups was obtained.

Synthesis of ethylenically unsaturated urethane isocyanate (B-2) 209 parts (0.5 mol) of dipropylene glycol diglyceryl ether dimethacrylate (A-4) obtained in Test Category 1, di-n -Butyl tin dilaurate 0.8
Parts and 174 parts (1.0 mol) of tolylene diisocyanate, the same operation as in the synthesis of the ethylenically unsaturated urethane isocyanate (B-1) was carried out to obtain an ethylenically unsaturated urethane isocyanate having an average of two isocyanate groups. (B-2) was obtained.

Test Category 3—Reaction Injection Molding (RIM)
Production of Molded Articles and Its Evaluation} The first liquid, the second liquid and the radical initiator solution shown in Table 1 or Table 2 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. A glass fiber for reinforcement was previously loaded in the nickel electroformed flat mold. After 5 minutes from the end of the injection, the mold was released to obtain a flat molded product having a length of 25 cm × a width of 25 cm × a thickness of 0.3 cm. With respect to the appearance of the molded product obtained above, the presence or absence of the emergence of the glass fiber and the occurrence of cracks were visually observed.

The molded product obtained above is 80 mm long × 25 mm wide.
× Cut to a thickness of 3 mm with a diamond cutter to prepare a test piece. After the test piece was accurately weighed, it was immersed in warm water at 80 ° C. for 30 hours. Then, the test piece was taken out, the weight of the test piece before and after the test was measured, the water absorption was calculated by the following equation, and the bending strength (JIS-K6911) was measured, and the bending strength reduction rate was calculated by the following equation. .

Water absorption (%) = {(weight after test−weight before test) / (weight before test)} × 100 Flexural strength reduction rate (%) = ｛(bending strength before test−bending strength after test) / test Pre-bending strength｝ × 100 The results are shown in Table 1 or Table 2. In addition, the water absorption rate and the bending strength reduction rate were shown by the average value of n = 3.

[0047]

[Table 1]

[0048]

[Table 2]

Note) In Tables 1 and 2, 1st liquid, 2nd liquid, radical initiator solution: numerical values are parts by weight ethylenically unsaturated esterol, ethylenically unsaturated urethane isocyanate, hydroxyl compound, isocyanate compound: upper row Is the type, and the lower part is parts by weight. A-1 to A-5, B-1, B-2: those obtained in test category 1 or test category 2 a-1: 2-hydroxyethyl methacrylate b-1: 2-hydroxy Ethyl methacrylate / tolylene diisocyanate = 1/1 (molar ratio) reactant (average of one isocyanate group) b-2: Dipropylene glycol / tolylene diisocyanate = 1/2 (molar ratio) reactant (average of two isocyanate groups) B-3) Tolylene diisocyanate * 1: 50% solution of dibenzoyl peroxide

[0050]

As is clear from the above, the present invention described above has an effect that an in-mold cured product excellent in dimensional accuracy, surface characteristics and water resistance can be produced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI // B29K 75:00 105: 08 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-4-306214 (JP, A) (58) Fields investigated (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)
In-mold curing characterized by in-mold curing in the presence of a catalyst
Manufacturing method of molded product. A: Ethylenically unsaturated ester represented by the following formula 1
B: one or more kinds of ethylenically unsaturated cellulose represented by the following formula 2 or 3
One or more kinds of urethane isocyanates C: One or two kinds of 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 residue obtained by removing a hydroxyl group from a divalent to tetravalent polyol;
Group X^ThreeA residue Y obtained by removing a hydroxyl group from a tri- or tetravalent polyol;¹From divalent to tetravalent polyisocyanate to isocyanate;
Residue Y excluding the^TwoA divalent polyisocyanate to an isocyanate group
Residue R excluding¹, R^Three, R^FiveAn aliphatic hydrocarbon group R having 5 to 21 carbon atoms^Two, R^Four, R⁶H or CH_Three  d, e, f; d = 0 an integer of 0 to 2, e, f = 1 to 3
A number that satisfies d + e + f = 2 to 4 p, q; p = 0 to 2; q = 1 to 3;
R, s; an integer of 1 to 3, and 2 ≦ r + s ≦ 4
T, u, v; t = 0 or 1, u = 1 or 2, v = 2 or
3, and satisfy t + u + v = 3 or 4. However, d and p do not simultaneously become 0, and d and t also become
It does not become 0 at the same time] 2. The method according to claim 1, wherein A is an ethylenically unsaturated ester monool or an ethylenically unsaturated ester diol, and B is an ethylenically unsaturated urethane diisocyanate. 3. The method for producing an in-mold cured product according to claim 1, wherein the in-mold curing is carried out in a system containing an inorganic powdery filler. 4. The method for producing an in-mold cured product according to claim 1, wherein the in-mold curing is performed using a mold loaded with reinforcing fibers. 5. An in-mold cured product obtained by the production method according to claim 1.