JP2938162B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition having excellent hydrolysis resistance, corrosion resistance and hot water resistance and suitable for the field of gel coating.

[Conventional technology]

Conventionally, urethane-modified resins have been widely used for coating applications because of their excellent toughness and abrasion resistance.

A molded article using an unsaturated polyester resin is often subjected to gel coating for the purpose of imparting performance such as appearance and scratch resistance and crack resistance. Molded products for gel coating include housing equipment such as bathtubs and wash basins, benches,
Examples include FRP and cast products such as outdoor goods such as ships.

Conventionally used resins for gel coating include unsaturated polyester resins, vinyl ester resins, and the like.Japanese Patent Publication No. 47-19880 discloses a method of improving scratch resistance by blending a vinyl ester resin with an unsaturated polyester resin. Have been reported. In general, the amount of gel coat resin used is very small, only a few percent of the molded product, so that expensive special resins can be used. Japanese Patent Application Laid-Open No. 62-297308 discloses that the acrylic urethane resin is used for scratch resistance and abrasion resistance. It is reported about the improvement of sex. These acrylic urethane resins use aromatic diisocyanates or alicyclic diisocyanates, but have disadvantages inferior in hot water resistance and hydrolysis resistance.

[Problems to be solved by the invention]

As described above, conventional gel coat resins have drawbacks of being inferior in hot water resistance and hydrolysis resistance, and in order to solve these, for example, an attempt has been made to blend a vinyl ester resin in the resin or to add a polyfunctional monomer. However, the above problems, such as a remarkable decrease in weather resistance, have not been sufficiently solved.

An object of the present invention is to solve the above problems and to provide a resin composition having excellent corrosion resistance, heat resistance, hydrolysis resistance, and boiling resistance.

[Means for Solving the Invention]

The present inventors have conducted intensive studies to solve the above problems, and as a result, a glycol component having a bisphenol skeleton, and 2,5- and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane. And a resin composition comprising an acrylic urethane resin modified with an ethylenically unsaturated monomer having a hydroxyl group in the molecule and a reactive diluent, and having excellent heat resistance and hydrolysis resistance. They have found and completed the present invention.

That is, the present invention reacts 1.1 to 2.0 g of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane with respect to 1 g of a glycol component containing a glycol having a bisphenol skeleton. Acrylic urethane resin having ethylenically unsaturated groups at both terminals obtained by reacting 0.5 to 1.5 g equivalent of an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule with respect to 1 g equivalent of the urethane-modified resin obtained by the above method And a reactive diluent having at least one ethylenically unsaturated group in the molecule.

Examples of the compound having a bisphenol skeleton used in the present invention include bisphenol A, a propylene oxide adduct of bisphenol A, and an ethylene oxide adduct. These compounds are
Used alone or as a mixture. Further, it may be used in combination with the glycol component having no bisphenol skeleton. In addition, 2,5- and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane is, for example, 2,5-isomer and / or 2,6-isomer of diaminomethyl-bicyclo [2 [2,1] heptane is subjected to a salt-forming reaction in a mixed solvent of isoamyl acetate and 0-dichlorobenzene by blowing hydrogen chloride gas, followed by phosgene blowing by blowing phosgene and then rectification.

Further, as the glycol component having no bisphenol skeleton, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol , Neopentyl glycol, hexylene glycol and octylene glycol.

The glycol compound having the bisphenol skeleton,
Generally gives a resin that is hard and has excellent chemical resistance, water resistance and corrosion resistance. When a straight-chain glycol having no bisphenol skeleton is used, the strength and hardness of the final molded product may not be obtained.
If it is 0%, it is desirable to contain 50% or more.

When the bisphenol skeleton-containing polyester oligomer or polymer is used as the glycol component, its performance is determined by the acid component contained in the polyester oligomer or polymer. Those which do not adversely affect decomposability and hot water resistance are desirable.

Examples of the carboxylic acid or its anhydride used in the synthesis of the bisphenol skeleton-containing polyester oligomer or polymer include succinic acid, adipic acid,
Examples include setibanic acid, azelaic acid, hexahydrophthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, fumaric acid, itaconic acid, citraconic acid, and maleic anhydride.

When the above polyester oligomer or polymer is used as the glycol component, the acid value is desirably 0, but is preferably at least 5 or less.

In addition, when a polyester polyol is used as a component other than the bisphenol skeleton-containing glycol, it must be taken into consideration that the properties greatly vary depending on the number of methylene groups in the skeleton, the presence or absence of ether bonds, the number of hydroxyl groups contained, and the like. .

Examples of the polyester polyol include, for example, glycerin, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol,
Polyethylene glycol, polypropylene glycol,
Examples include polyethylene propylene glycol and poly (oxytetramethylene) glycol.

Examples of the ethylenically unsaturated monomer having at least one hydroxyl group in the molecule used in the present invention include 2-hydroxyethyl methacrylate and acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate and the like.

The above-mentioned reaction between the glycol component and the diisocyanate compound having a specific structure is performed based on 1 g equivalent of the glycol component, 0.5 to 1.5 g equivalent of diisocyanate, preferably 1.1 to 1.5 g equivalent.
2.0 g equivalent was added and reacted at a reaction temperature of 30 to 60 ° C. for 1 to 5 hours, and further 0.5 to 1.5 g equivalent of an ethylenically unsaturated monomer having at least one or more hydroxyl group in a molecule, preferably 0.8 to 1.5 g. The reaction is carried out at 50 to 70 ° C. for 3 to 5 hours, and the reaction is carried out until NCO% = 0. Also NCO
When%> 0, it is more advantageous to add alcohols so that NCO% = 0. In addition, you may add a reaction catalyst as needed.

The obtained urethane acrylate usually has a considerably high viscosity and cannot be used as it is as a gel coat, so dilution is required.

Among the reactive diluents used here, the amount of the ethylenically unsaturated monomer used depends on the obtained acrylic urethane resin.
The amount is 1 to 99 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight based on 100 parts by weight.

However, among the ethylenically unsaturated monomers to be used, compounds such as aromatic amines, which significantly lower the weather resistance, are not used unless otherwise specified.
It is at most 3 parts by weight, preferably at most 3 parts by weight.

The amount of the crosslinkable unsaturated monomer or crosslinkable oligomer having at least two or more double bonds in the molecule is 1 to 99 parts by weight.

The total amount of these reactive diluents is adjusted so as to be 50 to 200 parts by weight based on 100 parts by weight of the acrylic urethane resin.

If the amount of the reactive diluent is less than 50 parts by weight, the resin viscosity is too high, and the coating operation is difficult, and even if it can be applied, the film thickness cannot be adjusted or the surface cannot be smoothed. On the other hand, if the amount of the reactive diluent exceeds 200 parts by weight, the influence thereof is so great that the intended gel coat layer cannot be obtained.

Among the reactive diluents used in the present invention, examples of the ethylenically unsaturated monomer include, for example, methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, propyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, methacrylic acid 3
Methacrylic acid such as hydroxypropyl and methacrylic acid and esters thereof, methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, laurel acrylate, 2-hydroxy acrylate ethyl,
Acrylic acid such as acrylic acid and its esters, other, vinyl acetate, acrylonitrile, acrylamide,
Examples include methacrylamide, styrene, α-methylstyrene and the like.

Further, as the ethylenically unsaturated monomer having a relatively low odor, methoxydiethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate,
β-methacryloxyethyl hydrogen phthalate,
β-methacryloxyethyl hydrogen succinate, nonylphenoxyethyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate,
β-acryloyloxyethyl hydrogen phthalate, β-acryloyloxypropyl hydrogen phthalate, β-acryloyloxyethyl hydrogen succinate, butoxydiethylene glycol acrylate, nonylphenoxyethyl acrylate, and the like.

Examples of the crosslinking unsaturated monomer include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
3-butylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimethacrylate, trimethylolethanetriacrylate, trimethylolethanetrimethacrylate, tetramethylolethanetrimethacrylate, tetramethylolmethanetriacrylate, tetramethylolmethanetrimethacrylate, tetramethylolmethanetetraacrylate, 2,2-bis [4 -(Methacryloxyethoxy) phenyl] propane, pentaerythritol triacrylate, Pentaerythritol hexaacrylate and the like.

Examples of the crosslinkable oligomer include oligoester acrylate, oligoester methacrylate, urethane acrylate oligomer, urethane methacrylate oligomer, acrylic-modified epoxy oligomer, epoxy-modified acrylic urethane oligomer, acrylate oligomer, and methacrylate oligomer.

As described above, the gel coating resin composition obtained in the present invention is:
The combination of acrylic urethane resin and ethylenically unsaturated monomer, crosslinkable unsaturated monomer, and crosslinkable oligomer replaces the basic combination of unsaturated polyester resin and styrene. This gives a molded product having excellent heat resistance and hot water resistance.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 2,5- and 2,6-diisocyanatomethylbicyclo [2,
2,1] Production of heptane (BCHI) Isoamyl acetate (687 g) and 0-dichlorobenzene (2189 g) were mixed as a solvent, and the mixture was prepared as a solvent for salt formation and phosgenation (hereinafter, referred to as a mixed solvent). The mixture was placed in a flask and cooled to 5 ° C. with ice water while stirring. Hydrogen chloride gas was blown into this at a rate of 1.6 Nl / min for 30 minutes, and then about 60% of the 2,5-isomer and about 2,6-isomer
A 40% mixture of diaminomethyl-bicyclo [2,2,
1] Heptane (BHCA) 250.0 g (1.62 mol) mixed solvent 1750
The solution (concentration: 12.5% by weight) dissolved in g was dropped into the liquid in the flask over 2 hours. Continue cooling during the dropping, keep the temperature inside the flask at 10 to 15 ° C, and blow hydrogen chloride gas at 1N.
Continued at l / min.

After completion of the dropwise addition of the starting diamine solution, blowing of hydrogen chloride gas was continued at a rate of 0.4 Nl / min for 2 hours while maintaining the temperature inside the flask at 25 ° C. or lower, to complete the salt formation reaction. In the salt-forming reaction, agglomeration of hydrochloride particles did not occur, and the transition was extremely smooth, and a slurry of white uniform fine particles was obtained.

After completion of the salt-forming reaction, the temperature inside the flask is increased from 25 ° C to 160 ° C by 5
The phosgene reaction was started by gradually blowing phosgene from 100 ° C. while the temperature was raised in 0 minutes. Blowing of phosgene was continued at a rate of 100 g / h to 120 g / h while adjusting the internal temperature to 160 ± 1 ° C. with a mantle heater. After about 6 hours from the start of phosgene blowing, the property of the reaction liquid changed from a slurry (white) to clear (red), and then phosgene gas was blown at a rate of 50 g / h for another 30 minutes, and then the phosgenation reaction was terminated. did.

Thereafter, into the flask the reaction solution, subjected to 80 minutes blown degassed with N ₂ gas at a rate of 1.3Nl / min, while this liquid temperature is 160
± 1 ° C. After cooling and filtration, the filtrate was desolvated and then rectified under vacuum to obtain a main fraction of 110-116 ° C / 0.4-0.6 torr.
06.5 g was obtained.

The main fraction obtained from the results of elemental analysis, IR spectrum, NMR spectrum and the like was confirmed to be the target product.

Example 1 Bisphenol A was added to a flask having a thermometer and a stirrer.
400 g of -3PO adduct was charged, and 412 g of 2,5- and 2,6-diisocyanatomethylbicyclo [2,2,1] heptane obtained in Reference Example was added, and the mixture was reacted at 70 ° C. for 3 hours. Then, 260 g of hydroxymethyl methacrylate was added and reacted at 70 ° C. for 3 hours to obtain an acrylic urethane resin.

Example 2 Bisphenol A was added to a flask having a thermometer and a stirrer.
After adding 390 g of -3EO adduct and further adding 412 g of 2,5- and 2,6-diisocyanatomethylbicyclo [2,2,1] heptane obtained in Reference Example, and reacting at 70 ° C for 3 hours, Then, 260 g of hydroxymethyl methacrylate was added and reacted at 70 ° C. for 3 hours to obtain an acrylic urethane resin.

Example 3 Bisphenol A was added to a flask having a thermometer and a stirrer.
After adding 360 g of -2PO adduct and further adding 412 g of 2,5- and 2,6-diisocyanatomethylbicyclo [2,2,1] heptane obtained in Reference Example, and reacting at 70 ° C for 3 hours, Then, 260 g of hydroxymethyl methacrylate was added and reacted at 70 ° C. for 3 hours to obtain an acrylic urethane resin.

Example 4 Bisphenol A was added to a flask having a thermometer and a stirrer.
After adding 350 g of -2EO adduct and further adding 412 g of 2,5- and 2,6-diisocyanatomethylbicyclo [2,2,1] heptane obtained in Reference Example, and reacting at 70 ° C for 3 hours, Then, 260 g of hydroxymethyl methacrylate was added and reacted at 70 ° C. for 3 hours to obtain an acrylic urethane resin.

Comparative Example 1 Bisphenol A was added to a flask having a thermometer and a stirrer.
After adding 400 g of -3PO adduct and further adding 444 g of isophorone diisocyanate, and reacting at 70 ° C. for 3 hours,
260 g of hydroxymethyl methacrylate was added and reacted at 70 ° C. for 3 hours to obtain an acrylic urethane resin.

All of the obtained resins have a viscosity of 4 to 6 with a reactive diluent.
Adjusted to poise.

After adding 0.5 part by weight of 6% cobalt naphthenate and 1.0 part by weight of NEKPO to 100 parts by weight of the resin and curing at room temperature,
Using a casting plate obtained by post-curing at ℃, JIS-K-691
Physical properties were determined and evaluated according to 1. The results are summarized in the following table.

[Effects of the Invention] The resin composition of the present invention has a bisphenol skeleton in the resin and has excellent boiling resistance, corrosion resistance, and heat resistance, and therefore has sufficient performance not only in the gel coating field but also for lining. And are useful as these coating agents.

Claims (1)

(57) [Claims] (1) 2,5- and / or 2,6-diisocyanatomethylbicyclo [2,2,1] per 1 g equivalent of a glycol component containing a glycol having a bisphenol skeleton
1.1 to 2.0 g of heptane is reacted, and 0.5 g to 1.5 g of an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule is reacted with 1 g of the urethane-modified resin obtained at 1 g equivalent of ethylene. A resin composition comprising an acrylic urethane resin having an unsaturated unsaturated group and a reactive diluent having at least one ethylenically unsaturated group in a molecule.