JPS5936661B2 - Unsaturated polyester resin composition - Google Patents

Description

Detailed Description of the Invention This invention has excellent compatibility with unsaturated polyester resin liquid, has a small shrinkage rate during curing, does not adhere to molds, and has excellent processability, surface smoothness, etc. The present invention relates to an unsaturated polyester resin composition suitable for producing unsaturated polyester resin products with excellent gloss.

More specifically, the present invention relates to a resin composition in which a liquid butadiene-acrylonitrile copolymer having an amino group at the terminal is added as a component of the unsaturated polyester resin composition.

Bulk molding compounds (BMC) and sheet molding compounds (S) based on unsaturated polyester resins
Fiber-reinforced molding resin compositions such as MC) or prepreg mats are widely used in many applications such as automobile body parts, furniture, and appliance housings.

However, conventionally known α/β monounsaturated polybasic acids or acid mixtures in which part of the polybasic acid is replaced with saturated polybasic acids, polyhydric alcohols, or monohydric alcohols in which part of the alcohols are replaced An unsaturated polyester resin liquid obtained by dissolving an unsaturated polyester, which is a condensation product with a substituted alcohol mixture, in a polymerizable monomer that can be copolymerized with an unsaturated polyester such as styrene, is It has the drawback that it sometimes undergoes significant shrinkage, causing cracks and corrugations on the surface, impairing surface smoothness.

Therefore, it is important that the product has particularly high dimensional stability, surface gloss, and
When surface smoothness is required, conventionally,
Treatments such as gel coating and polishing were required.

Adding such processing steps, such as polishing or other mechanical prefinishing operations, to the normal manufacturing process has obvious disadvantages. In recent years, unsaturated polyester resin compositions made by adding various additives to unsaturated polyester resin liquids have been developed as a way to improve the drawbacks of unsaturated polyester resin liquids, such as shrinkage that occurs during curing and deterioration of planar smoothness. Many have been proposed.

Typical examples thereof include a method in which a thermoplastic resin such as polystyrene, polyethylene, polymethyl methacrylate, etc. is added to an unsaturated polyester resin liquid. However, unsaturated polyester resin compositions containing thermoplastic resins such as polystyrene, polyethylene, and polymethyl methacrylate have poor dispersion stability, and if left for a long time, the resin composition will lose heat. Since the plasticizing resin separates and oozes out to cause phase separation, there is a drawback that once an unsaturated polyester resin composition is prepared, it must be used as soon as possible, and the surface gloss of the molded product also deteriorates.

The inventors have developed an unsaturated polyester resin composition that has excellent compatibility with an unsaturated polyester resin liquid and has good dispersion stability, in particular has a low shrinkage rate during curing, and has excellent surface smoothness and gloss after molding. As a result of research aimed at developing an unsaturated polyester resin composition suitable for manufacturing unsaturated polyester resin products that have excellent adhesive properties and do not leave any sticky residue on the product, we found that unsaturated polyester is An unsaturated polyester resin composition in which a liquid butadiene-acrylonitrile copolymer having an amino group at the terminal is added to an unsaturated polyester resin liquid obtained by dissolving it in a copolymerizable polymerizable monomer. This invention was achieved based on the knowledge that the objective could be achieved and that beautiful floor surfaces could be created by using this resin composition as a floor coating, resin mortar, or concrete.

The liquid butadiene-acrylonitrile copolymer having an amino group at the end used in this invention can be easily obtained by, for example, reacting a liquid butadiene-acrylonitrile copolymer having a carboxyl group at the end with aminoethylbiperazine. It can be shown by the following structural formula.

[In this formula, X is -CH. , -CH,, -d ゝone-one, B is the main polymer chain butadiene-acrylonitrile copolymer HCH2-CH-CH-CH2)1( CH
2-CH)m)n, where 1, m and n are numbers greater than or equal to 1. ] The bonding amount of acrylonitrile is 5 to 50% by weight, preferably 15 to 27% by weight, and the molecular weight of the copolymer is 500 to 10,000, preferably 100% by weight.
0 to 5000 is suitable.

Acrylonite. If there is a large amount of lyle or if the molecular weight is too large, the viscosity will increase and workability will decrease, so those having the above-mentioned acrylonitrile bond amount and molecular weight are suitable. The effects of this invention cannot be achieved with a solid butadiene-acrylonitrile copolymer. In the present invention, the liquid butadiene-acrylonitrile copolymer having an amino group at the terminal may have an amino group at only one end, but as shown in the above structural formula, the liquid butadiene-acrylonitrile copolymer has an amino group at both ends. The most preferred is

In this invention, the amount of the liquid butadiene-acrylonitrile copolymer having an amino group at the end to be added to the unsaturated polyester resin liquid is 3% by weight or more, preferably 5 to 25% by weight based on the unsaturated polyester resin liquid. weight%
is suitable.

If the amount added is small, there is no particular disadvantage, but the addition effect is not sufficient, and if it is too large, the butadiene-acrylonitrile copolymer tends to stand out on the surface or remain sticky on the surface, although it has a low shrinkage effect during molding. Generally, the above range of addition amount is suitable. The quantitative ratio of the unsaturated polyester of the unsaturated polyester resin liquid to the polymerizable monomer copolymerizable with the unsaturated polyester is 100:30.
It is preferable that it is 100:200 (weight ratio).

The unsaturated polyester used as the unsaturated polyester resin liquid in this invention is an α/β monounsaturated polybasic acid or its acid anhydride, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid. or a part of these as saturated acids or their acid anhydrides, such as phthalic anhydride, isophthalic acid, terephthalic acid,
Tetrahydrophthalic acid, succinic acid, hexachloroendomethylenetetrahydrophthalic acid, chlorinated phthalic anhydride,
Acid components substituted with adipic acid, azelaic acid, sebacic acid, head acid, benzoic acid, etc. and polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1'3-butylene glycol, 1,3-propane Diol, 1,4-
butanediol, 1,5-pentanediol, 1,6-
Hexanediol, cyclohexanedimethanol, 2.
2,4-trimethyl-1,3-pentanediol, hydrogenated bisphenol A, 2,2'-di-(4-hydroxypropoxyphenyl)propane, 2,2'-di-(4-
Polyesters obtained by an esterification reaction from polyhydric alcohols such as hydroxyethoxyphenyl) propane alone or in mixtures, or polyhydric alcohols partially substituted with monohydric alcohols are used.

In particular, when the proportion of α/β-unsaturated polybasic acid in the acid component is 60 mol % or more, the shrinkage reduction effect becomes even more remarkable. Examples of polymerizable monomers copolymerizable with unsaturated polyesters include styrene, α-chlorostyrene, vinyltoluene, vinyl acetate, methyl methacrylate, diallylphthalate, triacyl cyanurate,
Examples include triallylisocyanurate,
Among them, styrene is common. The unsaturated polyester resin composition of the present invention is produced by adding a polymerizable monomer copolymerizable with the unsaturated polyester to the unsaturated polyester to obtain an unsaturated polyester resin liquid, and adding liquid butadiene having an amino group at the terminal to the unsaturated polyester resin composition. By adding and mixing an acrylonitrile copolymer, or by adding and mixing a liquid butadiene-acrylonitrile copolymer having an amino group at the terminal to a polymerizable monomer that can be copolymerized with an unsaturated polyester, and then mixing it with an unsaturated polyester. Copolymerizable with unsaturated polyester by mixing with saturated polyester or unsaturated polyester resin liquid, or after adding and mixing a liquid butadiene-acrylonitrile copolymer having an amino group at the end to unsaturated polyester. It can be easily produced by mixing polymerizable monomers.

However, from the viewpoint of workability, it is not very suitable to first mix the liquid butadiene-acrylonitrile copolymer having an amino group at the terminal and the unsaturated polyester. In curing the unsaturated polyester resin composition of the present invention, catalysts generally known as curing catalysts for unsaturated polyester resin liquids are used.

Examples of the curing catalyst include diacyl peroxide, aldehyde peroxide, ketone peroxide, alkyl peroxide, hydroperoxide, alkyl bar ester, and azonitrile, which can be selected as appropriate and added to the unsaturated polyester resin liquid in advance. ,use.

Further, in the unsaturated polyester resin composition of the present invention, commonly used additives such as fillers, reinforcing materials, thickeners, mold release agents, and coloring agents can be added and used. Examples of fillers include inorganic fillers such as calcium carbonate, talc, clay, barium sulfate, calcium sulfate, shirasu balloons, glass microballoons, perlite, and asbestos, and organic fillers such as wood flour. can be used. Examples of the reinforcing material include organic or inorganic reinforcing materials such as vinylon fiber, polyester fiber, vegetable fiber, glass fiber, carbon fiber, and metal fiber. Examples of the thickener include alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, and calcium hydroxide. Examples of the mold release agent include stearic acid, its metal salts, and phosphates. In addition, in the unsaturated polyester resin composition of the present invention, a conventionally known low shrinkage agent,
For example, a small amount of thermoplastic resin such as polyethylene, polystyrene, polymethyl methacrylate, etc. may be added.

The unsaturated polyester resin composition of this invention can be used in various molded products, floor coating materials, primers, etc.
Can be used in resin mortar or concrete by adding aggregate such as gravel.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

In each example, "parts" means parts by weight.

In each example, compatibility, molding shrinkage rate, surface smoothness,
Mold adhesion and surface gloss were measured using the following method.

Compatibility: The number of days until a phase separation phenomenon is observed when a mixed solution is left at 25°C.

Mold shrinkage rate: Measured according to JIS-K69ll.

Surface smoothness: When no warping, whiskers, corrugations, pinholes, etc. were observed by visual observation, it was evaluated as ○, and otherwise, it was evaluated as ×.

Mold adhesion: The case where no adhesion to the mold was observed during molding was judged as ○, and the case where it was observed was judged as ×.

Surface gloss: Value (%) at 60° cross measured with a gloss meter (VG-107A: manufactured by Nippon Denshoku Kogyo Co., Ltd.)
.

Example 1 0.01 part of hydroquinone was added to 100 parts of an unsaturated polyester with an acid value of 38 obtained by condensation reaction at a molar ratio of fumaric acid: phthalic anhydride: propylene glycol of 8:2:10. Then, this was dissolved in 80 parts of styrene to prepare an unsaturated polyester resin liquid (hereinafter abbreviated as resin liquid).

Also, a liquid butadiene-acrylonitrile copolymer having an amino group at the terminal [B1. F. Gutsudoritsuchi (B.
F. Hycar manufactured by GOOdrich
)-ATBN-1300×16: Molecular weight 3400, acrylonitrile bond amount 18% by weight, number of terminal amino groups 1.9
, Bruckfield viscosity (27° C.) = 19×10 4 centipoise] was dissolved in 30 parts of styrene to prepare a styrene solution containing 70% by weight of the copolymer (hereinafter abbreviated as copolymer solution). Next, 92.9 parts of the resin liquid and 7.1 parts of the copolymer solution were mixed using a mixer to obtain a mixed solution.

The compatibility of this mixed solution is shown in Table 1. Next, according to a conventionally known method, 100 parts of the mixed solution, 160 parts of calcium carbonate, 48 parts of 6 mm chopped strands.
6 parts, 4 parts zinc stearate. and 1.2 parts of tertiary butyl peroxybenzoate were mixed to produce an unsaturated polyester resin composition as a bulk molding compound. In addition, the unsaturated polyester resin composition was compression molded at 150°C and 100 kg/Cd for 7 minutes.
A molded plate of 20 x 220 x 6n was prepared, and the surface smoothness, surface gloss, mold shrinkage rate during mold curing, and mold adhesion of the molded plate were measured and evaluated.

The results are shown in Table 1. Example 2 Same as Example 1 except that the mixing ratio of the resin liquid and copolymer solution in Example 1 was changed to 85.7 parts of resin liquid and 14.3 parts of copolymer solution. An unsaturated polyester resin composition was manufactured and molded under the following conditions and evaluated.

The results are shown in Table 1. Example 3 Same as Example 1 except that a mixed solution was used in which the mixing ratio of the resin liquid and copolymer solution in Example 1 was changed to 78.6 parts of resin liquid and 21.4 parts of copolymer solution. An unsaturated polyester resin composition was manufactured under similar conditions, molded, and evaluated.

The results are shown in Table 1. Comparative Example 1 An unsaturated polyester resin composition was produced and molded under the same conditions as in Example 1, except that 100 parts of the resin liquid was used as a mixed solution instead of the copolymer solution in Example 1. evaluated.

The results are shown in Table 1. Comparative Example 2 Comparative Example 1 except that 10 parts of powdered polyethylene was added during the production of the unsaturated polyester resin composition in Comparative Example 1.
An unsaturated polyester resin composition was manufactured under the same conditions as above, molded, and evaluated.

The results are shown in Table 1. Comparative Example 3 A styrene solution containing 30% by weight of polystyrene was prepared by dissolving 30 parts of polystyrene in 70 parts of styrene, and instead of the mixed solution of Example 1, 33.3 parts of this styrene solution and 66.6 parts of resin liquid were used. An unsaturated polyester resin composition was manufactured, molded, and evaluated under the same conditions as in Example 1, except that a mixed solution containing the following was used.

Claims (1)

[Claims] 1. A liquid butadiene-acrylonitrile copolymer having an amino group at the end is added to an unsaturated polyester resin liquid obtained by dissolving an unsaturated polyester in a polymerizable monomer that can be copolymerized with the unsaturated polyester. An unsaturated polyester resin composition characterized by: