JP3106578B2 - Unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition having excellent flexibility and thixotropic properties and suitable for FRP and paints.

[0002]

2. Description of the Related Art As a method for producing an unsaturated polyester,
There is known a method for producing a polyester by substituting an oxide compound for glycol required for performing a polyesterification reaction.
The reaction initiator which is an active hydrogen atom-containing compound in an amount for initiating the reaction and controlling the molecular weight is water;
Monoalcohols such as ethanol, propanol or butanol; ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol or dipropylene glycol. Diol, or monobasic acid such as acetic acid, propionic acid, butyric acid and dibasic acid such as maleic acid, adipic acid, sebacic acid or fumaric acid; and as an initiator for obtaining a branched reactant It is well known that polyfunctional components such as trimethylolpropane and pentaerythritol may be used alone or in combination with glycol, or a tribasic or higher polycarboxylic acid such as pyromellitic acid may be used. Have been. (For example, JP-B-55-44767 and JP-B-53-7471)

[0003] However, there are some examples of using polyfunctional polyols and polybasic acids as initiators as described above, but there is no clear description of their purpose of use and their effects.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an unsaturated polyester resin composition having flexibility and thixotropic properties.

The present inventors have used generally known polyfunctional polyols or polybasic acids, from which branched reactants can be obtained, as reaction initiators in order to obtain such unsaturated polyester resin compositions. An unsaturated polyester resin having flexibility and thixotropic properties could not be obtained.

The inventors of the present invention have made intensive studies and have found that an unsaturated polyester resin is obtained by reacting an oxide compound with 4-carboxy-1,8-octanediacid as an initiator in the presence of a polybasic acid anhydride. As a result, it has been found that a resin having excellent hardness while having an appropriate hardness, excellent thixotropy, and a very high thixotropy can be obtained, and the present invention has been completed.

[0007]

That is, according to the present invention, there is provided an unsaturated polyester resin composition comprising an unsaturated polyester and a polymerizable monomer, wherein the unsaturated polyester comprises 4-
An unsaturated polyester resin composition comprising, as an alcohol component, a compound obtained by reacting an oxide compound with carboxy-1,8-octanediacid as an initiator; It is intended to provide an unsaturated polyester resin composition which is performed in the presence of an anhydride.

(Constitution) The present invention relates to 4-carboxy-1,
Unsaturated polyester resin composition containing, as an alcohol component, a compound obtained by reacting an oxide compound with 8-octanedioic acid as an initiator, preferably a polycarboxylic anhydride in which the reaction is at least partly maleic anhydride The unsaturated polyester is produced from the reaction between the product and the oxide compound.

Further, 4-carboxy-1,8-octanediacid and a known compound having a carboxyl group and a hydroxyl group can be used in combination as an initiator. Examples of such a reaction initiator include water; methanol, ethanol,
Monoalcohols such as propanol or butanol
Ethylene glycol, propylene glycol, 1,
Diols such as 4-butanediol, diethylene glycol or dipropylene glycol; monobasic acids such as acetic acid, propionic acid and butyric acid; and maleic acid, adipic acid, sebacic acid or fumaric acid. Dibasic acid such as above; trimethylolpropane or pentaerythritol multifunctional component alone or in combination with glycol as an initiator for obtaining a branched reactant; or trimellitic acid or pyromellitic acid And the like are used. The higher the desired molecular mass, the lower the amount of chain limiting agent. 4-carboxy-
The 1,8 octane diacid is preferably 2 to 15% by weight in the unsaturated polyester.

The polycarboxylic anhydrides used in the present invention include, for example, α, β-unsaturated polycarboxylic anhydrides such as maleic anhydride, citraconic anhydride and itaconic anhydride, and phthalic acid. Saturated aliphatic polycarboxylic acids such as anhydride, succinic anhydride, tetrahydrophthalic anhydride, 3,6-endmethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride Acid anhydrides, aromatic polycarboxylic anhydrides and their aliphatic groups, aromatic substituents, and halogen-substituted derivatives of the above-mentioned acid anhydrides, either alone or as a mixture of two or more.

On the other hand, those which can be used as an oxide compound have the general formula

[0012]

Embedded image

Wherein R is hydrogen, an alkyl group, an alkoxide group, an aryl group, an allyl group or a derivative thereof, for example, ethylene oxide,
Propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether, aryl glycidyl ether, epihalohydrin and the like are used, and these alone or a mixture of two or more kinds are used. Preferably, it is an alkylene oxide.

The process for the preparation of the unsaturated polyesters of the present invention comprises the steps of placing the reactor under vacuum if the reactor contains oxygen and / or passing an inert gas through the reactor under the reaction conditions. Is removed. The inert gas is carbon dioxide, nitrogen, argon, helium or a mixture of two or more of these gases. Under normal or pressurized conditions under substantially anhydrous conditions, maleic anhydride alone or one or more acid anhydrides other than maleic anhydride and one or two or more mixtures of oxide compounds It is performed by heating at 120 to 220 ° C. The oxide compound may be added in several portions as the reaction proceeds. The reaction is continued until a suitable acid number or / and a suitable viscosity is obtained. Since the reaction between the oxide compound and the carboxylic anhydride is exothermic, it is necessary to control the temperature by cooling the mixture. The use of a catalyst is not necessarily required, but a tertiary amine, a quaternary ammonium compound, a hydroxide, an oxide and a salt of an alkali metal and an alkaline earth metal, an organic metal compound, and other usual esterification or A ring opening polymerization catalyst is used. The amount of the catalyst used is suitably 0.01 to 2% based on the reactants.

The unsaturated polyester obtained by the present invention is a semi-solid or solid at room temperature and is usually colorless and transparent. The obtained unsaturated polyester can be copolymerized with a vinyl group-containing polymerizable monomer such as styrene by an ordinary method. The resulting unsaturated polyester is
It dissolves in the vinyl group-containing polymerizable monomer maintained at a temperature in the range of 40 ° C to 80 ° C. The dissolution of the unsaturated polyester is carried out in the presence of a polymerization inhibitor incorporated in the monomer and / or the polyester.

The vinyl group-containing polymerizable monomers are those usually used in unsaturated polyesters. These are in particular styrene, chlorostyrene, vinyltoluene, divinylbenzene, alkyl acrylates and methacrylates having less than 6 carbon atoms, vinyl acetate, vinyl propionate and vinyl pivalate, allyl phthalate, triaryl Lucianurate, 1,3-butanegio
Such as rudimethacrylate and alkyl vinyl ether. The proportion of the vinyl group-containing polymerizable monomer is preferably
20 to 6 to 40 to 80% by weight of unsaturated polyester
Use in the range of 0% by weight.

The polymerization inhibitor acting to preserve the unsaturated polyester resin composition is para-tert-butyl catechol, hydroquinone monomethyl or monoethyl ether, benzoquinone, hydroquinone 2,5.
-Choose among common inhibitors such as t-thiobutyl, copper naphthenate and especially hydroquinone. It is preferably used in a proportion of from 30 to 2000 ppm by weight, based on the unsaturated polyester resin composition.

To the obtained unsaturated polyester resin composition, a curing catalyst, a curing accelerator, a thickener, a filler, a fiber reinforcing material, a colorant, an internal mold release agent, and a low shrinkage agent can be added.

The curing catalyst acts on an unsaturated polyester resin, and may be, for example, an azo compound such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide, dimethyl peroxide, Organic peroxides such as mill peroxide can be mentioned, and it can be used usually in the range of 0.3 to 3 parts by weight based on 100 parts by weight of the unsaturated polyester resin composition.

As the curing accelerator, metal salts of organic acids, particularly cobalt salts, for example, cobalt naphthenate, cobalt octylate, cobalt acetylacetone and the like are used.

As the filler, calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose thread, silica sand, river sand, cold water stone, Known materials such as marble chips and crushed stones may be mentioned. Among them, glass powder, aluminum hydroxide, barium sulfate and the like are preferable because they impart translucency when cured.

The thickener is chemically bonded to a hydroxyl group, a carboxyl group, an ester bond, or the like of the unsaturated polyester to form a linear or partial cross-link, thereby increasing the molecular weight and increasing the viscosity of the unsaturated polyester resin. For example, diisocyanates such as toluene diisocyanate, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, oxides of divalent metals such as magnesium oxide, calcium oxide and beryllium oxide, and calcium hydroxide And hydroxides of such divalent metals. The amount of the thickener used is usually from 0.2 to 10 based on 100 parts by weight of the unsaturated polyester resin.
Parts by weight, preferably 0.5 to 4 parts by weight. If necessary, a small amount of a highly polar substance such as water can be used as a thickening aid.

The fiber reinforcing material used in the present invention is, for example, an organic fiber such as glass fiber, amide, aramid, vinylon, polyester, phenol, etc., carbon fiber, metal fiber, ceramic fiber or a combination thereof.
In consideration of workability and economy, glass fibers and organic fibers are preferable. The form of the fiber includes plain weave, satin weave, mat shape, and the like, but a mat shape is preferable. It is also possible to cut the glass roving into 20 to 100 mm and use it as a chopped strand.

As the coloring agent, any of conventionally known organic and inorganic dyes and pigments can be used.
Those which are excellent in transparency and which do not significantly hinder the curing of the unsaturated polyester resin are preferred.

Examples of the internal release agent include higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters. Usually, it can be used at a ratio of 0.5 to 5 parts by weight.

The low-shrinkage agent is a thermoplastic resin. Specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate,
Lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, homopolymers or copolymers of monomers such as styrene, vinyl chloride and vinyl acetate, at least one of the vinyl monomers, and lauryl methacrylate , Isovinyl methacrylate, acrylamide,
In addition to methacrylamide, hydroxylalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, at least one copolymer of a monomer composed of cetylstearyl methacrylate, etc., cellulose acetate butyrate and cellulose acetate propioate Nate, polyethylene, polypropylene and the like.

The unsaturated polyester resin composition of the present invention is used for FRP, paints, gel coats and the like.

Next, the present invention will be described with reference to examples.
In the description, “parts” and “%” are based on weight.

[0029]

【Example】

Example 1 A 3-liter capacity cylindrical separable flask having a four-necked lid was equipped with a rectification tower, a nitrogen gas inlet tube and a thermometer, and 65.4 g of 4-carboxy-1,8-octanediacid (0 0.3 mol), 98 g (1 mol) of maleic anhydride, and 252 g (1.7 mol) of phthalic anhydride are present in the reactor. After replacing the air with nitrogen and raising the temperature to 120 ° C., the mixture was stirred at 900 rpm with a stirrer equipped with a turbine-type stirring blade, and 197 g of propylene oxide was fed from the bottom of the reaction vessel.
(3.4 mol) were introduced over 3 hours. First, the heat generated by the reaction between the carboxylic acid and propylene oxide was suppressed by cooling such that the temperature reached 210 ° C. in 2 hours. Next, 210
The remaining propylene oxide was introduced at 1 ° C for 1 hour, and the mixture was held for another hour. The reaction was completed after a total reaction time of 4 hours. After cooling to 150 ° C. and adding 100 ppm of hydroquinone, a resin solution was prepared with a resin content of 66% and styrene monomer of 34%. The viscosity by a bubble viscometer is U, and the acid value is 2
6. The color tone of the resin was 8 in Gardner color. Aerosil # 200 (manufactured by Nippon Aerosil Co., Ltd.)
One part was added and kneaded and dispersed using three rolls. 25
The degree of thixotropicity (TI) was measured at ° C. Further, 0.1 part of cobalt naphthenate (containing 6% metal) was added, and after stirring for about 1 minute, 2 parts of methyl ethyl ketone peroxide was added and stirred, and after defoaming, a plate having a thickness of 3 mm was prepared. I cast it into a mold. After standing at room temperature for 24 hours, after-curing was performed at 120 ° C. for 2 hours, and various physical property tests according to JIS were performed. The results are shown in Table 1.

Example 2 32.7 g of 4-carboxy-1,8-octanedioic acid
(0.15 mol), 98 g (1 mol) of maleic anhydride,
274 g (1.85 mol) of phthalic anhydride was charged, and 197 g of propylene oxide (3.
4 mol). The obtained resin has a resin content of 66.
%, Styrene monomer-34%, bubble viscosity was W, acid value was 21, and color by Gardner colorimeter was 6. The same test as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that 4-carboxy-1,8-octanediacid was replaced by trimellitic acid. That is, trimellitic acid 5
7.6 g (0.3 mol), 98 g (1 mol) of maleic anhydride, and 252 g (1.7 mol) of phthalic anhydride were charged.
The reaction was carried out under the same conditions as in Example 1. The obtained resin was 66% in resin content and 34% in styrene monomer, the bubble viscosity was S, the acid value was 30, and the number of Gardner colors of the resin was 2. The same test as in Example 1 was performed, and the results are shown in Table 1.

[0033]

[Table 1]

[0034]

The composition of the present invention can be made flexible by using 4-carboxy-1,8-octanediacid as a reaction initiator for an unsaturated polyester obtained from a polycarboxylic anhydride and an oxide compound. It has excellent properties and thixotropic properties. Utilizing such properties, it is used for FRP or paint.

Claims (2)

(57) [Claims] 1. An unsaturated polyester resin composition comprising an unsaturated polyester and a polymerizable monomer, wherein the unsaturated polyester reacts with an oxide compound using 4-carboxy-1,8-octanediacid as an initiator. An unsaturated polyester resin composition comprising the obtained compound as an alcohol component. 2. The unsaturated polyester resin composition according to claim 1, wherein the reaction is carried out in the presence of a polycarboxylic anhydride.