JPS6357623A - Urethane-modified resin composition - Google Patents

Abstract

PURPOSE:To obtain the title rapid-curing composition excellent in rubber elasticity, tearing strength and durability, by mixing a urethane polyester resin obtained by an addition reaction of a polyisocyanate with a specified adduct with a copolymerizable vinyl monomer. CONSTITUTION:An adduct between a carboxy compound (a) of MW<=4,000, having at least one terminal carboxyl group in the molecule, obtained by condensation and addition between an alcohol compound (e.g., neopentyl glycol) and a carboxylic acid compound (e.g., adipic acid) and an epoxy group-containing polymerizable monomer (b) [e.g., glycidyl (meth)acrylate] is further reacted by an addition reaction with a polyisocyanate (c) (e.g., toluene diisocyanate) to obtain an isocyanate group-free urethane polyester resin (A). 30-70wt% component A is mixed with 70-30wt% vinyl monomer (B) copolymerizable with component A (e.g., styrene).

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a waterproof material having high elasticity and high strength;
The present invention relates to curable resin compositions used for various linings such as flooring materials, paints, putty, adhesives, etc. [Conventional technology and its problems] Unsaturated polyester resin has mechanical, electrical, chemical resistance,
Because it has excellent properties such as heat resistance and weather resistance, and is easy to handle, it is used in paints, putties, adhesives, various linings, and F.
It is widely used for applications such as RP. However, unsaturated polyester resin is hard and brittle, in other words, has a low elongation rate and low impact strength.When used for rooftop waterproofing, balconies, and corridor ring linings, it is difficult to prevent vibrations in buildings and cracks in the underlying concrete or mortar. It is especially desirable to have rubber elasticity with high elongation and waterproof properties, but it has not yet been possible to improve the flexibility of unsaturated polyester resins and have rubber elasticity with high elongation. Although methods have been used to make the saturated polyester resin itself flexible or to make it flexible by adding plasticizers, etc., these methods impair chemical resistance and mechanical strength, but do not provide sufficient toughness. In addition, methods to obtain elasticity through the blending effects of chipped strands and inorganic fillers are being considered, but these methods have limitations in use such as lack of stability of the resin composition and uneven coloring of the cured product. However, when used as FRP in combination with reinforcing base materials such as glass fibers and vinylon woven fabrics, there are virtually no materials that provide toughness effects. For painting,
As described in JP-A No. 51-28826, an oligoester obtained by adding an acid anhydride to an alcohol compound and adding a polymerizable monomer having an epoxy group to the product is added with a vinyl monomer, Curable resin compositions containing polyvalent isocyanate compounds have been proposed, but
When the coating film becomes thick, it tends to foam and contain bubbles, making it difficult to obtain a uniform and strong coating film. [Means for Solving the Problems] As a result of various studies aimed at solving the drawbacks of unsaturated polyester resins, the present inventors discovered the toughness imparting effect of urethane-modified resin compositions and arrived at the present invention. did. According to the present invention, polyisocyanate is added to the addition reaction product of a carboxy compound having a molecular weight of 4000 or less and having at least one terminal carboxyl group in one molecule and a polymerizable monomer having an epoxy group. The urethane-modified resin composition, which is characterized by containing a urethane-modified resin in which no isocyanate groups remain and a copolymerizable vinyl monomer, exhibits fast curing, high elongation of the cured product, and rubber elasticity. It is possible to provide a highly durable material that has a high tear strength and a high tear strength. The carboxy compound having at least one terminal carboxyl group in one molecule used in the present invention can be obtained by a condensation or addition reaction of an alcohol compound and a carboxylic acid compound (including acid anhydrides and carboxylic acid alkyl ester compounds). Among them, those derived from a diol component and a dicarboxylic acid component are particularly preferred.The chain of the terminal carboxy compound does not contain an unsaturated bond, or even if it does contain an unsaturated carboxylic acid relative to the total dicarboxylic acid. The proportion of is preferably 8.0 mol% or less, 8.0
If the amount is more than mol%, the elongation of the cured product will be significantly reduced and the rubber elasticity will be impaired. Carboxylic acids used as acid components constituting carboxy compounds include adipic acid, cepatic acid, phthalic acid,
Phthalic anhydride, isophthalic acid, terephthalic acid, 3.6-
Saturated acids such as nindomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid One or more unsaturated acids such as , acrylic acid, and methacrylic acid are used. The diol component mainly consists of dihydroxy compounds, but may also partially contain, for example, up to 20 mol% of polyhydroxy compounds; in this case, for example, by incorporating the same molar amount of monohydroxy compounds, the average It is appropriate to adjust the number of functional groups. Examples of dihydroxy compounds include aliphatic dialcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1.3-butanediol, 1,4-butanediol, and neopentyl glycol; alicyclic dihydroxy compounds such as 4.4-dihydroxydicyclohexylpropane; Examples include aromatic dihydroxy compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide or propylene oxide. Examples of polyhydroxy compounds include trimethylolbutane, glycerin, pentaerythritol, and the like. Examples of monohydroxy compounds include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-
Examples include aliphatic monoalcohols such as butyl alcohol, 1so-butyl alcohol, and nonyl alcohol, alicyclic monoalcohols such as cyclohexanol, and aromatic monoalcohols such as benzyl alcohol. The carboxy compound is prepared by combining the above-mentioned alcohol compound and carboxylic acid compound with respect to the hydroxyl group of the alcohol compound such that the ratio of unsaturated carboxylic acid to all dicarboxylic acids is 8.0 mol% or less, and the terminal of the resulting compound is a carboxyl group. It can be produced by subjecting the carboxylic acid compound to a condensation or addition reaction using a known method in such an amount that the amount of carboxyl groups in the carboxylic acid compound is equal to or more than the equivalent amount. At this time, the molecular weight can be adjusted by changing the equivalent ratio of all carboxylic acid compounds to all alcohol compounds during the reaction. If the molecular weight of the carboxy compound is greater than 4,000, the addition reaction with the polymerizable monomer having an epoxy group will not proceed, and abnormal reactions will easily occur, resulting in gelation. In the addition reaction product of a carboxyl compound and a polymerizable monomer having an epoxy group, it is not necessary that the polymerizable monomer having an epoxy group is added to all the carboxyl groups30.
It is appropriate to add about 80%. Polymerizable monomers having epoxy groups include allyl glycidyl ether, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, methylglycidyl (meth)acrylate, monovalent monovalent monomers such as diglycidyl ether of polyhydric alcohols, etc. These include those with half an equivalent amount of polymerizable unsaturated acid added. A non-polymerizable monoepoxy compound can be used together with these compounds, examples of which include Cardura E (manufactured by Shell Chemical Co., Ltd.), alkylene oxide, and styrene oxide. In order to promote the addition reaction between these epoxy group-containing compounds and carboxyl groups, imidazoles, ether complexes of boron trifluoride, and the like may be used as ring-opening catalysts. The urethanized polyester resin of the present invention is produced by adding polyisocyanate to an addition reaction product of a carboxy compound and a polymerizable monomer having an epoxy group in a conventional manner. The polyisocyanate does not need to be added to all of the hydroxyl groups of the above-mentioned addition reaction product, but it is necessary to add the polyisocyanate to such an extent that substantially no isocyanate groups remain, preferably 90% or less, more preferably 30% or more and 80% or less. good. If isocyanate remains, it is not preferable because it will thicken and gel over time. Examples of the polyisocyanate include toluene diisocyanate, 4,4-diisocyanate diphenylmethane, xylidene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and their condensates and polyhydric alcohol adducts. The amount of urethanized polyester resin is usually 30% of the total composition.
It is used in a range of 70% by weight. Vinyl monomers copolymerizable with the urethanized polyester resin of the present invention include aromatic vinyl compounds such as threne and vinyltoluene, mimethyl (meth)acrylate, ethyl (meth)butyrate, isopropyl (meth)acrylate, n- Butyl (meth)acrylate-1-1iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (
There are (meth)acrylates such as meth)acrylate, stearyl(meth)acrylate, (methyl)glycidyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, etc., and the amount of these used is 30 to 70% by weight when further improving coating performance such as workability, gloss, flexibility, hardness, weather resistance, drying property, and solvent resistance depending on the intended use.
Used within the range of The curing catalyst added as necessary can be appropriately selected depending on the method of curing the composition of the present invention. A polymerization initiator is not particularly required when using high energy such as an electron beam, but a well-known photosensitizer is required as a polymerization initiator when using light or ultraviolet rays, and when using thermal energy or far infrared rays, a polymerization initiator is not required. Suitable polymerization initiators include peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, butyl peroxide, lauroyl peroxide, and cumene hydroperoxide, and metal soaps such as cobalt naphthenate as polymerization initiation aids. Tertiary amines such as dimethylaniline, alcoholades such as sodium methylate, lauryl mercaptan, N-ethylmethatolyluidine, etc. are suitable. [Example] The present invention will be explained in more detail with reference to Examples below.
This is not intended to limit the invention; hereinafter parts are by weight unless otherwise specified. (Example-1) Neopentyl glycol 1 was placed in a four-loaf flask equipped with a stirrer, a thermometer, a fractionator with a condenser, and a nitrogen inlet tube.
04 parts and 175.2 parts of adipic acid were charged and esterified at 210°C in a nitrogen stream, and the number average molecular weight was determined to be 150 by analysis by gel verminesin chromatography.
0), this was dissolved in 243.2 parts of styrene in which 0.05 part of hydroquinone was dissolved, and the temperature was 110°C.
Glycidyl methacrylate while stirring well.
19.9 parts were added dropwise over 1 hour, and the reaction was continued until the acid value became 5 or less. Thereafter, while maintaining the reaction temperature at 80°C, 17.1 parts of toluene diisocyanate (toluene diisocyanate) was added dropwise over 1 hour, and the reaction was continued for an additional hour to form a transparent pale yellow resin composition (with no active isocyanate groups remaining). A) was obtained. 2 parts of benzyl peroxide and 0.5 parts of aniline were mixed with 100 parts of resin composition (A) to create a sheet with a thickness of 1 m+a at room temperature, and after curing for 1 week,
Dumbbell shapes were punched out and tensile strength, tear strength, and elongation were examined. [Example-2] After reacting 104 parts of neopentyl glycol and 7.1 parts of maleic anhydride at 120°C, 16 parts of adipic acid
4.7 parts were added and esterified at 210° C. in a nitrogen stream to obtain a polyester resin with a number average molecular weight of 1500. Otherwise, a transparent pale yellow resin composition (B) was obtained in the same manner as in Example-1. Example 1 of resin composition (B)
The physical properties of a sheet cured in the same manner as above were investigated. [Example-3] A polyester resin with a number average molecular weight of 1600 was obtained using 13.2 parts of trimethylolpropane, 10 parts of cyclohexanol, and 83.2 parts of neopentyl glycol, and the rest was exactly the same as in Example-1. A transparent pale yellow resin composition (C) was obtained. 0.5 parts of benzyl peroxide and 0.5 parts of methylene dianiline were added to 100 parts of the resin composition (C).
The physical properties of a sheet prepared in the same manner as in Example-1 were evaluated by blending 3 parts. [Example-4] A pale yellow resin composition was prepared in the same manner as in Example-1, except that 13.4 parts of alimeglycidyl ether and 0.4 parts of 2-methylimidazole were used as the ring-opening catalyst. (
D) was obtained, a sheet was prepared in the same manner as in Example-1, and the physical properties were evaluated. [Comparative Example-1] According to Example-1, a polyester resin (E) with a number average molecular weight of 1500 was made of 104 parts of neopentyl glycol, 175.2 parts of adipic acid, 22.7 parts of glycidyl methacrylate, and 174 parts of styrene. was synthesized. Olestar P-49-755 (containing 12% of active incyanate groups based on 100 parts of polyester resin (E))
Mitsui Toatsu Chemical Co., Ltd., 50 parts of ethyl acetate solution of 3 mol trimethylolpropane/toluene diisocyanate adduct, 2 parts of methyl ethyl ketone peroxide, and 0.5 parts of cobalt naphthenate were mixed to make a sheet with a thickness of lIn11 at room temperature. After curing for one week, dumbbell shapes were punched out and their tensile strength, tear strength, and elongation were examined.

[Comparative Example-2] Neopentyl glycol 1 was prepared using the same equipment as in Example-1.
04 parts, adipic acid 146 parts, and 21 parts in a nitrogen stream.
The esterification reaction was carried out at 0°C, and the number average molecular weight was determined to be 6 by analysis by gel verminesin chromatography.
000 polyester resin was obtained. Glycidyl methacrylate 22 at a temperature of 110°C in the same manner as in Example-1.
．． After adding 7 parts, the viscosity rapidly increased during the heating reaction, and the mixture was wrapped around the stirrer and turned into a gel. The above results are shown in Table 1. Table 1 Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] A urethane in which substantially no isocyanate groups remain, which is obtained by adding polyisocyanate to an addition reaction product of a carboxy compound with a molecular weight of 4000 or less and a polymerizable monomer having an epoxy group and having at least one terminal carboxyl group in one molecule. 1. A urethane-modified resin composition comprising a polyester resin and a copolymerizable vinyl monomer.