JPH0668067B2 - Unsaturated polyester resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a technique of using a specific curing aid as a curing aid in a room temperature curable unsaturated polyester resin composition.

2. Description of the Related Art An unsaturated polyester resin composition prepared by mixing an unsaturated polybasic acid (or a saturated polybasic acid with it) with a polyhydric alcohol, a crosslinkable monomer and a curing agent is added to the unsaturated polyester resin is Paints, castings, premixes,
Used in large quantities for applications such as FRP.

The curing method of the unsaturated polyester resin composition includes a room temperature curing type, a medium temperature curing type, and a high temperature curing type. As the curing agent, in the room temperature curing type, an initiator and a curing aid (accelerator alone or as an accelerator Auxiliary accelerator), the medium temperature curing type, an initiator alone or an initiator and a curing aid, and the high temperature curing type, an initiator, respectively. There is also a photo-curable type, but the description is omitted here.

The curing agent in the case of the room temperature curing type is represented as follows.

The initiator may be referred to as a curing agent or a catalyst, and the accelerator may be referred to as a curing auxiliary agent, but in the present specification, they are referred to as described above.

As the curing agent in the room temperature curing type, the following combinations of and are generally adopted.

Radical Polymerization Initiator-Metal Soap System A radical polymerization initiator (particularly ketone peroxide) is used as an initiator, and a metal soap (particularly cobalt organic acid salt) is used as an accelerator among curing aids. Examples of co-promoters used as necessary include β-diketones and aromatic tertiary compounds.
Examples include primary amines, mercaptans, and phosphorus compounds.

Radical Polymerization Initiator-Amine System A radical polymerization initiator (especially acylperoxide) is used as an initiator, and an amine (especially dimethylaniline, diethylaniline, dimethyl-p-toluidine) or an amine is used as an accelerator among curing aids. Use salt. Also in this case, a suitable co-promoter can be used.

The component of the unsaturated polyester resin itself in the case of room temperature curing is to co-condense the polyhydric alcohol allyl ether in addition to the above-mentioned unsaturated polybasic acid (or saturated polybasic acid) and polyhydric alcohol. Is preferable, which improves the room temperature curability.

A method of improving dispersibility of carbon black and improving black sharpness by co-condensing mono- or dihydroxyalkylated tertiary amine as a part of the polyhydric alcohol component (JP-A-55- 152752), a method for improving pigment dispersibility by co-condensing using a polyethylene glycol alkylamine-based surfactant as a part of the polyhydric alcohol component (JP-A-61-97325), polyhydric alcohol. A method for improving curability and stability by co-condensing N, N-bis (hydroxyalkyl) arylamine as a part of the component and additionally blending phenothiazine and metal acetylacetonate as a curing aid JP-A-56-74112) is also known.

Problems to be Solved by the Invention Currently, a curing agent used for room temperature curing of a putty or a molding resin using an unsaturated polyester resin uses a radical polymerization initiator as an initiator and is an accelerator among curing assistants. Often, a tertiary amine is used as. The room-temperature-curable unsaturated polyester resin composition using this combination of curing agents has good storage stability.

However, in this curing agent system, it is necessary to use a relatively large amount of a tertiary amine in order to obtain the required room temperature curability, and as a result, a tertiary amine is formed on the surface of the cured coating film. May form problems such as poor surface curing, reduced mechanical strength of the cured product, poor adhesion, and bleeding over time.

A method of co-condensing using a mono- or dihydroxyalkylated tertiary amine (including N, N-bis (hydroxyalkyl) arylamine) and a polyethylene glycol alkylamine-based surfactant as a part of the polyhydric alcohol component. Has the disadvantages that the hue of the resin liquid becomes extremely poor, the curability is insufficient, the curability decreases during storage, or the curing agent composition becomes extremely complicated.

The present inventors have conducted extensive research on curing agents for room-temperature-curable unsaturated polyester resin compositions, and have found an excellent curing aid that replaces conventional tertiary amines, and have completed the present invention. It was

Means for Solving the Problems The unsaturated polyester resin composition of the present invention comprises an unsaturated polyester resin (A) containing a polyhydric alcohol allyl ether component as an air-drying imparting component, a crosslinkable monomer (B) and an initiator. A room-temperature-curable unsaturated polyester resin composition comprising (C) and a curing aid (D), wherein the curing aid (D) is a mono- or dihydroxyalkylated first aromatic ring having N directly attached thereto. The molar ratio of the tertiary aromatic amine (d1) and maleic anhydride (d2) is 1: 2 to 2: 1.
Of the ester compound (d), which comprises a total of 3 or more units (d1) units and (d2) units in one molecule.

The present invention will be described in detail below.

Unsaturated Polyester Resin (A) The unsaturated polyester resin (A) is composed of unsaturated polybasic acid (or saturated polybasic acid) and polyhydric alcohol as constituent components, and is a component which imparts room temperature curability (air drying property). It contains a polyhydric alcohol allyl ether.

Examples of the unsaturated polybasic acid include maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, fumaric acid and the like.

As the saturated polybasic acid, phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride,
Endomethylenetetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 2,5-norbornanedicarboxylic acid, citraconic acid,
Examples thereof include het acid, adipic acid, sebacic acid, succinic acid, azelaic acid, trimellitic acid, pyromellitic acid, and methylcyclohexentricarboxylic acid.

As the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2- or 1,3-propylene glycol, dipropylene glycol, polypropylene glycol, neopentine glycol, 1,3-, 1,4 -Or 2,
3-butylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,
Examples thereof include 4-cyclohexanedimethanol, polytetramethylene glycol, trimethylolethane, trimethylolpropane, glycerin, 1,3,6-hexanetriol, pentaerythritol, sorbitol and bisphenoldioxypropyl ether.

As the polyhydric alcohol allyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, penta Erythritol diallyl ether, pentaerythritol triallyl ether, 1,2,6-hexanetriol monoallyl ether, 1,2,6-hexanetriol diallyl ether, sorbitan monoallyl ether, sorbitan diallyl ether, tetramethylol cyclohexanol diallyl monochlorotyl ether , Hexamethylol melamine diallyl dicrotyl ether, hexanetriol diallyl ether , Pentaerythritol diallyl crotyl ether, tetramethylol cyclohexanol triallyl ether, tetramethylol cyclohexanone dilyl ether, hexamethylol melamine tetraallyl ether and the like.

The unsaturated polyester resin (A) is produced by condensing each of the above components in an inert gas atmosphere at a temperature of about 150 to 250 ° C. according to a conventional method.

The reaction ratio of unsaturated polybasic acid, saturated polybasic acid, polyhydric alcohol and polyhydric alcohol allyl ether is 20% of the total amount of unsaturated polybasic acid and saturated polybasic acid. Mol% or more, especially 50 to 100 mol%,
The ratio of polyhydric alcohol to 1 mol of total amount of unsaturated polybasic acid and saturated polybasic acid is about 1 to 1.5 mol, and polyhydric alcohol allyl ether to 1 mol of total amount of unsaturated polybasic acid and saturated polybasic acid. The ratio of is often 0.4 or less.

Crosslinkable Monomer (B) As the crosslinkable monomer (B), styrene, vinyltoluene, monochlorostyrene, α-methylstyrene, t-
Butyl styrene, diallyl phthalate, triallyl cyanurate, diallyl malate, diallyl fumarate, dibutyl fumarate, alkyl acrylate, alkyl methacrylate, glycidyl methacrylate, 2-hydroxymethacrylate glycidyl ether, vinyl acetate,
Vinyl chloride, methylenebisacrylamide, acrylonitrile, methacrylonitrile, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, Examples thereof include 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and vinylcyclohexene monooxide.

Initiator (C) Examples of the initiator (C) include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl. Examples include perbenzoate and cyclohexanone peroxide.

Curing aid (D) As the curing aid (D), in the present invention, a mono- or dihydroxyalkylated third group in which N is directly attached to an aromatic ring is used.
An esterification product of a primary aromatic amine (d1) and maleic anhydride (d2) in a molar ratio of 1: 2 to 2: 1 in one molecule (d1)
An esterified product (d) containing a total of 3 units or more of units and (d2) units is used. Instead of mono- or dihydroxyalkylated tertiary aromatic amine (d1) having N directly on the aromatic ring, hydroxylated secondary amine, monohydroxyalkylated tertiary aliphatic amine and (meth) acrylic acid Even if an esterification product of and an esterification product containing one dihydroxyalkylated tertiary aromatic amine (d1) unit and one maleic anhydride (d2) unit in one molecule is used, I can't achieve it.

The above-mentioned mono- or dihydroxyalkylated tertiary aromatic amine (d1) is represented by the following formula.

Monohydroxyalkylated tertiary aromatic amine Dihydroxyalkylated tertiary aromatic amine In the formula, at least one of R ₁ and R ₂ and R ₄ is an aromatic ring (including a derivative) such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, or a phenanthryl group.
Is. When both R ₁ and R ₂ are not such an aromatic ring, R ₁ or R ₂ which is not the aromatic ring is a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group or a hexyl group. , Hydrocarbon groups such as cyclohexyl group and benzyl group (including derivatives). R ₃ , R ₅ and R ₆ are methylene groups,
Ethylene group, propylene group, butylene group, amylene group,
An alkylene group or an arylene group (including a derivative) such as a hexylene group, a phenylene group, a tolylene group, a xylene group, or a derivative thereof.

Specific examples of the mono- or dihydroxyalkylated tertiary aromatic amine (d1) having N directly attached to the aromatic ring include N-
Ethyl-N-β-hydroxyethylaniline, N-methyl-N-β-hydroxyethylaniline, N-butyl-
N-β-hydroxyethylaniline, N-methyl-N-
β-hydroxyethyl-m-toluidine, N-ethyl-
Monohydroxyalkylated tertiary aromatic amines such as N-β-hydroxyethyl-m-toluidine and N-butyl-N-β-hydroxyethyl-m-toluidine, N, N-
Di (β-hydroxyethyl) aniline, N, N-di (γ-
Hydroxypropyl) aniline, N, N-di (β-hydroxypropyl) aniline, N, N-di (β-hydroxyethyl) -m-toluidine, N, N-di (γ-hydroxypropyl) -m-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, N, N-di (β-hydroxypropyl) -p-toluidine, N, N-di (β-hydroxyethyl) -2,5-dimethoxyaniline , N, N-di (β-
Hydroxyethyl) -2,5-diethoxyaniline, N, N-
Di (β-hydroxyethyl) -p-cresidine, N, N-
Di (β-hydroxyethyl) -o-anisidine, N, N-
Di (β-hydroxyethyl) -o-phenetidine, N, N
-Di (β-hydroxyethyl) -amino-m-acetanilide, 3- (N, N-di-β-hydroxyethyl) -amino-4-methoxyacetanilide, N-butyldiethanolamine, N-benzyldiethanolamine, N-
Examples include dihydroxyalkylated tertiary aromatic amines such as butyl-bis (γ-hydroxypropyl) amine.

An esterified product (d) is obtained by subjecting the above-mentioned mono- or dihydroxyalkylated tertiary aromatic amine (d1) and maleic anhydride (d2) to an esterification reaction.

In the reaction, both components are usually used in a molar ratio of 1: 2 to 2: 1 and preferably 2 to 6 at a temperature of about 90 to 160 ° C. under an inert gas atmosphere, in the absence of a catalyst or in the presence of a catalyst. It is carried out by heating and stirring for about an hour.

If the reaction temperature is too low, the esterification will not proceed easily, while if the reaction temperature is too high, for example 180 ° C or higher, gelation or adduct formation between (d1) and (d2) will occur and the curing aid will When used as, there is a possibility that curing failure may occur. The esterified product (d) obtained by reacting at about 90 to 160 ° C. minimizes amine adduct formation,
The change in hue is small, and the activity when used as a curing aid is high.

The number average molecular weight of the obtained esterified product (d) is 396 in the case where the molecular weight is the smallest (the case where 1 mol of maleic acid having no small amount is reacted with 2 mol of N-methyl-N-β-hydroxyethylaniline). Therefore, it becomes the lower limit, and when it is smaller than that, poor surface curing and deterioration of mechanical strength of the cured product are caused. The upper limit of the number average molecular weight is preferably 2000. If it exceeds 2000, no disadvantage occurs in the initiation of curing, but the complete curability is deteriorated.

Blending Ratio The blending ratio of the unsaturated polyester resin (A), the crosslinkable monomer (B), the initiator (C), and the esterification product (d) as the curing aid (D) is 100% of the unsaturated polyester resin (A). 20 parts by weight of crosslinkable monomer (B)
.About.50 parts by weight, initiator (C) 0.5 to 4 parts by weight, and esterified product (d) 0.5 to 10 parts by weight are suitable, but not limited to this range.

Other Additives In addition to the unsaturated polyester resin composition of the present invention comprising the above components, other additives such as a filler, a leveling agent, a diluent, a thermoplastic resin, and an anti-greening agent may be appropriately blended. it can.

Uses The unsaturated polyester resin composition of the present invention is a coating composition, putty, cast product by itself, or further mixed with a room temperature curable unsaturated polyester resin, a urethane-modified unsaturated polyester resin, an epoxy acrylate resin, or the like. , Molded articles, premixes, FRPs, copper clad laminates, bolt fixing agents, and various other applications.

Effects and Effects of the Invention The present invention relates to a mono- or dihydroxyalkylated tertiary aromatic amine (d1) having N attached directly to an aromatic ring as a curing aid (D) in a room temperature curable unsaturated polyester resin composition. It is an esterified product with a molar ratio of maleic anhydride (d2) of 1: 2 to 2: 1 and has (d1) units and (d
2) It is characterized by using an esterified product (d) containing 3 units or more in total. This esterified product (d) is
The coloring is small, the curing promoting action is excellent, and the problems of mechanical strength reduction, poor adhesion, and bleeding with time do not occur.

EXAMPLES Next, the present invention will be further described with reference to examples. Hereinafter, "part" and "%" are expressed on a weight basis.

<Production of Resin Liquid> Production Example 1 of Resin Liquid In a reaction vessel equipped with a stirrer, a nitrogen introducing tube and a thermometer,
0.6 mol of maleic anhydride, 0.4 mol of phthalic anhydride, 1.05 mol of diethylene glycol, 0.1 mol of trimethylolpropane diallyl ether and a small amount of hydroquinone were charged and reacted at 200 ° C. for 7 hours in a nitrogen stream. The acid value of the obtained unsaturated polyester resin was 16.2 KOHmg / g.

After cooling the above reaction liquid to 80 ° C., styrene was added to dilute it to obtain a resin liquid having a heating residue of 70%, a viscosity of 950 cps / 20 ° C., and a hue (Gardner Helige) of 1 or less.

Resin Liquid Production Example 2 In a reaction vessel, maleic anhydride 0.6 mol, tetrahydrophthalic anhydride 0.4 mol, diethylene glycol 1.06 mol,
0.05 mol of pentaerythritol triallyl ether and a small amount of hydroquinone were charged and reacted at 200 ° C. for 7 hours in a nitrogen stream. The acid value of the obtained unsaturated polyester resin was 15.8 KOHmg / g.

After cooling the above reaction liquid to 80 ° C., styrene was added to dilute it to obtain a resin liquid having a heating residue of 70%, a viscosity of 820 cps / 20 ° C. and a hue (Gardner Helige) of 1 or less.

Resin Liquid Production Example 3 A reaction vessel was charged with 0.6 mol of maleic anhydride and 0.4 mol of phthalic anhydride.
Mol, diethylene glycol 1.05 mol, trimethylolpropane diallyl ether 0.1 mol, N, N-di (β-hydroxyethyl) -p-toluidine 0.03 mol, and a small amount of hydroquinone were charged and reacted at 200 ° C. for 6 hours in a nitrogen stream. . The acid value of the obtained unsaturated polyester resin is
It was 15.3 KOHmg / g.

After cooling the above reaction liquid to 80 ° C., styrene was added to dilute it to obtain a resin liquid having a heating residue of 70%, a viscosity of 920 cps / 20 ° C., and a hue (Gardner Helige) of 10 or more.

<Synthesis of Ester Compound (d)> Ester Compound Synthesis Example 1 In a reaction vessel equipped with a stirrer, a nitrogen introducing tube and a thermometer,
1.0 mol of maleic anhydride and 1.67 mol of N, N-di (β-hydroxyethyl) -p-toluidine were charged and reacted at 140 to 160 ° C. for 3 hours in a nitrogen stream. As a result, an esterified product having a number average molecular weight of 600 and an acid value of 5.0 KOHmg / g was obtained.

Esterified Compound Synthesis Example 2 In a reaction vessel, 1.0 mol of maleic anhydride and N, N-di (β
-Hydroxypropyl) aniline (1.67 mol) was charged and reacted in a nitrogen stream at 140 to 160 ° C for 3 hours. This allows
An esterified product having a number average molecular weight of 670 and an acid value of 5.0 KOHmg / g was obtained.

Esterified Compound Synthesis Example 3 A reaction vessel was charged with 1.0 mol of maleic anhydride and 2.0 mol of N-ethyl-N-β-hydroxypropyl-p-toluidine and reacted in a nitrogen stream at 140 to 160 ° C. for 3 hours. This gives a number average molecular weight of 460 and an acid value of 5.0 KOHmg / g
An esterified product of was obtained.

Esterified Compound Synthesis Example 4 A reaction vessel was charged with 1.0 mol of maleic anhydride and 2.0 mol of N-ethyl-N-β-hydroxyethylaniline and reacted at 140 to 160 ° C. for 3 hours in a nitrogen stream. As a result, an esterified product having a number average molecular weight of 410 and an acid value of 5.0 KOHmg / g was obtained.

<Preparation of Composition> Example 1 313.6 parts of the resin solution obtained in Production Example 1 of resin solution, 6.4 parts of the esterified product obtained in Synthesis Example 1 of esterified product, 65 parts of styrene, 55 parts of titanium dioxide, 546 parts of talc, synthetic iron 2 parts black and silicon dioxide ("Nipseal" manufactured by Nippon Silica Industry Co., Ltd.)
4 parts were placed in a kneader and kneaded for 1 hour to obtain a putty.

To 100 parts of this putty, 4.0 parts of 2% benzoyl peroxide (“Nyper BO” manufactured by NOF CORPORATION) was added and mixed, and then cold rolled steel sheet JIS G3141 having a thickness of 0.6 mm.
(SPCC-SB) was coated with a spatula so that the coating amount was 400 g / m ² .

Example 2 313.6 parts of resin solution obtained in Production Example 1 of resin solution, 6.4 parts of esterified product obtained in Synthesis Example 2 of esterified product, 65 parts of styrene, 55 parts of titanium dioxide, 546 parts of talc, 2 parts of synthetic iron black and silicon dioxide 4 parts were placed in a kneader and kneaded for 1 hour to obtain a putty.

To 100 parts of this putty, 4.0 parts of 2% benzoyl peroxide was added to the putty and mixed, and then applied to a cold-rolled steel sheet having a thickness of 0.6 mm with a spatula so that the application amount was 400 g / m ² .

Example 3 313.6 parts of the resin solution obtained in Production Example 2 of resin solution, 6.4 parts of the esterified product obtained in Synthesis Example 3 of esterified product, 65 parts of styrene, 55 parts of titanium dioxide, 546 parts of talc, 2 parts of synthetic iron black and silicon dioxide. 4 parts were placed in a kneader and kneaded for 1 hour to obtain a putty.

To 100 parts of this putty, 4.0 parts of 2% benzoyl peroxide was added to the putty and mixed, and then applied to a cold-rolled steel sheet having a thickness of 0.6 mm with a spatula so that the coating amount was 400 g / m ² . .

Example 4 313.6 parts of resin solution obtained in Production Example 1 of resin solution, 6.4 parts of esterified product obtained in Synthesis Example 4 of esterified product, 65 parts of styrene, 55 parts of titanium dioxide, 546 parts of talc, 2 parts of synthetic iron black and silicon dioxide 4 parts were placed in a kneader and kneaded for 1 hour to obtain a putty.

To 100 parts of this putty, 6.4 parts of 2% benzoyl peroxide was added to the putty and mixed, and then applied to a cold-rolled steel sheet having a thickness of 0.6 mm with a spatula so that the application amount was 500 g / m ² .

Comparative Example 1 Example 1 was repeated except that 6.4 parts of diethylaniline was used instead of 6.4 parts of the esterified product obtained in Synthesis Example 1 of esterified product. The hue (Gardner Helige) of the resin liquid after addition of diethylaniline is 6 to 7.

Comparative Example 2 Example 1 was repeated except that 6.4 parts of dimethylaniline was used instead of 6.4 parts of the esterified product obtained in Synthesis Example 1 of esterified product. The hue (Gardner Helige) of the resin liquid after addition of dimethylaniline is 7 to 8.

Comparative Example 3 320 parts of the resin liquid obtained in the resin liquid production example 3 was used in place of 313.6 parts of the resin liquid obtained in the resin liquid production example 1, and 6.4 parts of the esterified product obtained in the esterification product synthesis example 1 was omitted. Other than that,
Example 1 was repeated.

<Evaluation Test and Results> For the putties obtained in Examples 1 to 4 and Comparative Examples 1 to 25, 25
The pot life at ℃, the dry time to the touch after application to the rolled steel plate, the time until the start of polishing after application to the rolled steel plate, the adhesion of the dried coating film, and the presence or absence of amine odor were examined.

Adhesion was measured by applying a 180 ° bending test 24 hours after the putty was applied to the rolled steel sheet and observing the peeling state of the coating film at that time, ○ for no peeling, △ for partial peeling, and for complete peeling. It was evaluated as x.

Regarding the presence or absence of amine odor, 24 hours after the putty was applied to the rolled steel plate, the applied plate was placed in a 500 ml glass bottle, sealed, and after 2 days, the amine odor was examined.

The bleeding with time is that after 48 hours have passed after the putty was applied to the rolled steel sheet, a 180 ° bending test and an amine odor test are performed in the same manner as above, and the adhesion with the one after 24 hours has passed. The difference and the difference in amine odor were compared and judged.

The results are shown in Table 1.

Claims (1)

[Claims] 1. An unsaturated polyester resin (A) containing a polyhydric alcohol allyl ether component as an air-drying imparting component.
In a room temperature curable unsaturated polyester resin composition obtained by blending a crosslinking monomer (B), an initiator (C) and a curing aid (D) with an aromatic ring as the curing aid (D). An esterified product having a molar ratio of a mono- or dihydroxyalkylated tertiary aromatic amine (d1) directly attached to N and maleic anhydride (d2) in a ratio of 1: 2 to 2: 1 (d1 And an esterified product (d) containing 3 or more units in total (d2) units.