JPS5850650B2 - thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin assembly that can be cured at room temperature, and more specifically, the present invention relates to a thermosetting resin assembly that can be cured at room temperature. The present invention relates to a thermosetting resin composition which can be cured at room temperature by introducing a tricyclodecenyl α,β unsaturated group having the following and utilizing a copolymerization reaction between the tricyclodecenyl α,β unsaturated group and a polymerizable monomer.

Polybutadiene oligomers having hydroxyl groups with a number average molecular weight of about 1,000 to 6,000 are relatively easy-to-handle elastomers that flow at room temperature.
It is expected to be used in a wide range of applications such as adhesives and potting materials.

However, even though it has fluidity, it has a viscosity of 50 to 600 poise (at 25°C), making it less workable than unsaturated polyester resins, which are said to be the representative solvent-free type. Although it has excellent properties, it has not yet been widely used.

On the other hand, as shown in Japanese Patent Publication No. 47-16195, acrylic or methacrylic groups are mainly introduced into polybutadiene containing active hydrogen using incyanate, and vinyl monomer is added to this to create a thermosetting resin with excellent workability. Many attempts have been made in the past.

However, in general, acrylic or methacrylic groups have inferior copolymerizability to styrene, which is the most commonly used solvent-free monomer, so they do not cure quickly and sufficiently at room temperature like unsaturated polyester resins. Furthermore, the properties of the cured product cannot be said to be sufficient.

Therefore, those skilled in the art have strongly desired the emergence of a polybutadiene oligomer that does not lose the excellent performance of polybutadiene as an elastomer, has good workability, and has a fast curing rate even at room temperature, that is, is easy to handle.

In view of the above-mentioned circumstances, the inventors of the present invention have conducted extensive studies on the modification of polybutadiene oligomers, and as a result have completed a thermosetting resin composition that has improved the above-mentioned drawbacks.

That is, the present invention provides (1) a compound (4) having an active hydrogen represented by the general formula (X is an α, β unsaturated dicarboxylic acid residue having 2 or 3 carbon atoms, and R is a glycol residue) , butadiene constituting the polymer chain consists of 1,2- and 1°4-bonds, and contains a hydroxyl group as a functional group, and has a number average molecular weight of 1,
000-5,000 butadiene homo- or copolymer (B
) and diisocyanate (C), each with an equivalent ratio of functional groups (A)/(B)/(C) = 0.6 to 1.0/1
．． 50 to 90 parts by weight of a polybutadiene derivative obtained by blending and reacting so that O/1.2 to 2.0 (2) Polymerizable monomer having one or more polymerizable double bonds in the molecule 10 to It relates to a thermosetting resin composition containing 50 parts by weight.

In the present invention, the compound (4) having active hydrogen represented by the general formula (Tazoshi X is an α, β unsaturated dicarboxylic acid residue having 2 or 3 carbon atoms, and R is a glycol residue) is The carboxyl group of tricyclodecenyl monocarboxylic acid obtained by half-esterifying dicyclopentadiene and α, β unsaturated dicarboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, and citraconic acid by a known method. Glycols having 2 equivalents of hydroxyl groups can be subjected to an ester reaction at 200 to 220°C.

The glycol used here is ethylene glycol,
Diethylene glycol, fluoropylene glycol, dipropylene glycol, ■, 3 or 1,4 butanediol,
(2), 6-hexanediol, neopentyl glycol, caro-isomer of bisphenol A with 2 moles of ethylene or propylene oxide, etc., and these are used alone.

The butadiene homo- or copolymer (B) used in the present invention has a hydroxyl group as described above and has a number average molecular weight of 1,000 to 5,000.
-11.4- The bonding ratio may be arbitrary, and it does not matter whether the polymer is a homopolymer or a copolymer.

These include N15so PBG grade (manufactured by Nippon Soda), Polybd R-45, C8-15°CN-15 grades (ARCO, Chem 1cal
(manufactured by).

The diisocyanate (C) used in the present invention is aliphatic diisocyanate such as ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-4lylene diisocyanate, 4,4'-diphenylmethane. diisocyanate,
Aromatic diisocyanates such as P- or m-phenylene diisocyanate, alicyclic diisocyanates such as cyclohexylene diisocyanate, mixtures thereof, and the like are used.

The equivalent ratio of (B) and (C) having these functional groups is (A)/(B)/(C) = 0.6 to 1.0
/ 1. O/1.2 to 2, O is mixed and reacted to obtain a polybutadiene derivative, but the equivalent ratio of 4) and (C) to 1 equivalent of (B) is less than 0.6 equivalent, 1.2, respectively. If the amount is less than 1.0 equivalent, the composition will have slow curability and poor properties of the cured product.
If the amount exceeds 0 equivalents, there will be a large amount of reactants that do not bind to the backbone polybutadiene, and the properties of the composition will deteriorate.

They are blended in the above equivalent ratio, and the reaction is carried out without a catalyst or with a catalyst such as organic tin at 150°C or lower, preferably 50 to 100°C.

In this case, if desired, the reaction may be carried out using a polymerizable monomer having one or more polymerizable double bonds in the molecule as a solvent.

Examples of the polymerizable monomer having one or more polymerizable double bonds in the molecule, which is the second component of the resin composition of the present invention, include styrene, divinylbenzene, vinyltoluene, methyl (
meth)acrylate (the meanings of methyl acrylate and methyl methacrylate are the same hereinafter), ethyl (meth)acrylate, carpitol (meth)acrylate, diallyl phthalate, as well as ethylene glycol, 1,3 or 1,4 butanediol, ■, 6-hexanediol , di(meth)acrylate such as neopentyl glycol, etc. are used.

One or more of these polymerizable monomers can be used depending on the curing method of the composition, workability, etc., depending on the desired properties.

Furthermore, when the amount of the polybutadiene derivative in the resin composition of the present invention is less than 50 parts by weight and the amount of the polymerizable monomer having one or more polymerizable double bonds in the molecule exceeds 50 parts by weight, Unreacted polymerizable monomers may remain in the cured product, or the cured product may have insufficient crosslinking density.Also, if the amount of polybutadiene derivative exceeds 90 parts by weight, there may be one or more polymerizable double bonds in the molecule. If the amount of the polymerizable monomer with This results in an inferior cured product.

The thermosetting resin composition of the present invention can be cured by heat using peroxide, redox curing using a combination of peroxide and a curing accelerator, ultraviolet curing, far infrared curing, etc. Known photosensitizers must be added to the composition.

Examples of peroxides that can be used include benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, and tert-butyl peroxide, and examples of curing accelerators include cobalt, copper, manganese,
Metal soaps such as lead, tertiary amines, β-diketones, etc. are used, and there are no particular restrictions on the amount or method of use.

It should be noted that the resin composition of the present invention may be used without any problem by adding desired amounts of pigments, fillers such as calcium carbonate, silica sand, curcum, kaolin, dyes, etc., as required, and carbon fibers. It may also be used in combination with fibrous reinforcing agents such as glass fibers, polyvinyl alcohol fibers, and polyester fibers.

Further, the thermosetting resin composition of the present invention may be mixed with other polymers such as unsaturated polyesters, alkyd resins, etc. without any problem as long as it does not contradict the purpose of the present invention.

The thermosetting resin composition of the present invention can be used for casting for electrical insulation,
Coil impregnated varnish, FRP pipe for electrical insulation, corrosion-resistant FR
It can be widely used for industrial materials such as P and corrugated plates.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Hereinafter, "parts" and "%" mean parts by weight and % by weight, respectively.

Example 1 Synthesis of compound (4) 2 equipped with a condenser, nitrogen inlet tube, thermometer, and stirrer
71! 1200 parts (8.0 mol) of hydroxylated dicyclopentadiene, 78 parts of maleic anhydride in a four-bottle flask
4 parts (8.0 mol) were charged and reacted at 145° C. for 3 hours while introducing nitrogen to obtain a tricyclodecenyl monomale compound having an acid value of 224.

To this was added 848 parts (8.0 mol) of diethylene glycol, and the esterification reaction was further carried out at 210°C for 4 hours in a nitrogen stream to obtain a compound (4
) was obtained.

2 Synthesis of polybutadiene derivative (1) Using the same equipment as in 1, Polyb with a hydroxyl value of 46.6
d R-45HT (ARCOChem 1cal O
(Hated polybutadiene) to 1000 parts of (4
), 264 parts, hexamethylene diisocyanate, 1
39 parts were charged and reacted at 80° C. for 8 hours under a nitrogen stream to obtain a polybutadiene derivative (FBI).

This product was a yellow viscous liquid, and it was confirmed that there was no absorption of free isocyanate by IR.

3 Synthesis of polybutadiene derivative Using the same equipment as in ff1 (II) ■, Nl5SO-PB with a hydroxyl value of 54.3
G2000 (OH polybutadiene manufactured by Nippon Soda) 100
0 parts to 168 parts of 2,4-tolylene diisocyanate, 1
311 parts of (4) obtained in step 2 were added, 1-0.5 parts of dibutyltin dilaure were added thereto, and the mixture was reacted at 80° C. for 3 hours to obtain a polybutadiene derivative (PB2).

This product was a yellow viscous liquid, and it was confirmed by IR that there was no absorption of free isocyanate.

Polybd with a hydroxyl value of 46.6 was prepared using the same equipment as in Comparative Example ■.
R-45HT (manufactured by CARCO Chemical) 2-hydroxyethyl alcohol per 1000 parts
216 parts of methyl methacrylate and 286 parts of 2,4-tolylene diisocyanate were charged and reacted at 80° C. for 3 hours with stirring under a nitrogen stream to obtain a pale yellow viscous liquid (Rfl).

This product was a pale yellow viscous liquid, and it was confirmed by IR that there was no absorption of free isocyanate.

Various compositions were prepared using polybutadiene derivatives of PBI, PB2, and Rf 1, and their properties were compared.

The results are shown in Table 1.

The numbers indicating the composition amounts in Table 1 are parts by weight.

As shown in Table 1, the thermosetting resin composition of the present invention has a fast curing speed, excellent properties of the cured product, and excellent adhesive properties, so it can be applied to a wider range of applications than conventional polybutadiene. It is a solvent-free thermosetting composition that can be

Claims (1)

[Claims] 1(1) A compound having active hydrogen represented by the general formula (Tazoshi X is an α, β unsaturated dicarboxylic acid residue having 2 or 3 carbon atoms, R is a glycol residue) (4) The butadiene constituting the polymer chain consists of 1,2- and 1゜4-bonds and has a hydroxyl group as a functional group, and has a number average molecular weight of 1,00.
0 to 5,000 of butadiene homo- or copolymer (B) and diisocyanate (C), respectively, in equivalent ratio of functional groups (
A)/(B)/(C)=0.6-1, 0/1.
50 to 90 parts by weight of a polybutadiene derivative obtained by blending and reacting so that O/1.2 to 2.0 (2) Polymerizable monomer having one or more polymerizable double bonds in the molecule 10 to A thermosetting resin composition containing 50 parts by weight.