JPS6015658B2 - Unsaturated polyester resin composition - Google Patents

Description

[Detailed Description of the Invention] This invention has excellent compatibility with unsaturated polyester resin liquids, low shrinkage during curing, and excellent bending elasticity, bending strength, chemical resistance, processability, surface smoothness, etc. The present invention relates to an unsaturated polyester resin composition suitable for producing unsaturated polyester resin products.

More specifically, the present invention relates to a composition in which a liquid butadiene-acrylonitrile copolymer having a pinyl 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 generally known Q.8-unsaturated 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 substituted are used. An unsaturated polyester resin liquid obtained by dissolving an unsaturated polyester, which is a condensation product with a substituted alcohol compound, in a polymerizable monomer that can be copolymerized with an unsaturated polyester such as styrene, is molded and cured. It has the disadvantage that it undergoes significant shrinkage during the process, causing cracks and corrugations on the surface, impairing the surface smoothness.

Therefore, when dimensional stability and surface smoothness are particularly required for the product, such as when a molded and cured product is used as an automobile body, gel coating or polishing may be necessary. Such processing was necessary.

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 plastic resin separates and separates 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.

Other methods include, for example,
57, 48 - Madara 73 and Mochikai Shoryaku - Satoshi 2, 48 - Gishi 9
Examples include a method of adding polybutadienes to an unsaturated polyester resin liquid as disclosed in .

Among these, the polybutadiene used in the invention disclosed in Mochiko Sho 47-16657 has an intrinsic viscosity of 0.5 or more, so its molecular weight is at least 10,000 or more, and it is presumed to be a solid polybutadiene. However, because it is difficult to dissolve in polymerizable monomers such as styrene,
There is a problem with the dispersibility of polybutadiene within the compound. Tokuko Sho 48-18873 and Tsubaki Seki Sho 48-98
The invention disclosed by No. 2 uses terminal-modified polybutadiene and polybutadiene, but the surface of the plate formed according to these inventions has adhesiveness (stickiness).
However, there is a problem that the mold remains, and contamination of the mold also occurs, which are disadvantages. On the other hand, the invention of JP-A-48-Gifu-9 prevents residual stickiness by adding a third component (unsaturated dicarboxylic acid and/or alkyl ester thereof) in addition to polybutadiene. Addition of the three components is undesirable for work and practical reasons. 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 after molding, chemical resistance, and As a result of research aimed at developing an unsaturated polyester resin composition suitable for manufacturing unsaturated polyester resin products that have excellent cracking resistance, bending strength, and bending elasticity and do not leave any sticky residue on the product, we found that: Q.3 in acid components
- An unsaturated polyester resin liquid obtained by dissolving an unsaturated polyester containing 60 to 100 mol% of unsaturated polybasic acid in a polymerizable monomer copolymerizable with the unsaturated polyester, The purpose can be achieved with an unsaturated polyester resin composition to which a liquid butadiene-acrylonitrile copolymer having a group is added. This invention was developed based on the knowledge that the drawbacks of the present invention can also be improved.

The liquid butadiene-acrylonitrile copolymer having a vinyl group at the end used in this invention was developed in the Hakama Kaisho 4th century.
According to the method described in 9-96090, for example, Japanese Patent Publication No. 43-28471 (USP. 3285949)
It can be easily obtained by reacting glycidyl acrylate with a liquid ptadiene-acrylonitrile copolymer having a carpoxyl group at the terminal obtained by the method described in 1, and can be represented by the following structural formula.

[In this formula, A is Z, R in Z is an alkyl group having 1 to 3 carbon atoms, n is an integer of 1 to 6, and B represents a butadiene-acrylonitrile copolymer as the main polymer chain.

] The amount of acrylonitrile bound in the copolymer used in this invention is 5 to 5% by weight, preferably 1% by weight.
5 to 2% by weight is preferred, and the molecular weight of the copolymer is 50%.
0 to loo0, preferably 1000 to 5000 is suitable.

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

The mechanism behind the various excellent effects achieved in this invention is not yet clear, but the pinyl group at the terminal of the liquid Z-butadiene-acrylonitrile copolymer has a pinyl group at the terminal. Because it is very active, the vinyl group is easily crosslinked by the organic peroxide that is the curing catalyst for the unsaturated polyester resin liquid, and the pinyl group at the end and the nitrile group in the main chain are It is considered that this invention exhibits excellent compatibility with the saturated polyester and the copolymerizable polymerizable monomer, and as a whole exhibits the excellent effects of the present invention.

In this invention, the amount of the liquid butadiene-acrylonitrile copolymer having a pinyl group at the end to be added to the unsaturated polyester resin liquid 2 is 3% by weight or more, preferably 5% by weight based on the unsaturated polyester resin liquid. ~25% by weight is preferred. If the amount added is small, there is no particular disadvantage, but the effect of addition is not sufficient.If it is too large, the butadiene-acrylonitrile copolymer may 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 since the amount may be affected. 3 The quantitative ratio of the unsaturated polyester of the unsaturated polyester resin liquid to the polymerizable monomer capable of copolymerizing the unsaturated polyester is 100:30.
It is preferable that it is 100:200 (weight ratio). In this invention, the unsaturated polyester used as the unsaturated polyester resin liquid (3) is not particularly limited as long as the proportion of Q.8 monounsaturated polybasic acid in the brewing component is 60 to 100 mol%. .

Q.8-Unsaturated polybasic acids or their acid anhydrides, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid,
Mesaconic acid, 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 acids, adipic acid, azelaic acid,
Acid components substituted with sebacic acid, het acid, benzoic acid, etc. and polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, neobentyl glycol, 1,3-butylene glycol, 1,3-propanediol, 1. 4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,2,4-trimethyl-1.
3-bentanediol, hydrogenated bisphenol A, 2.
2-di(4-hydroxypropoxyphenyl)propane, 2.2-di(4-hydroxyethoxyphenyl)
A polyester obtained by an esterification reaction from propane or a mixture thereof, or a polyhydric alcohol partially substituted with a monohydric alcohol is used. If the proportion of the Q.8 monounsaturated polybasic acid in the acid component is less than 60 mol %, the desired shrinkage reduction effect will be insufficient. Examples of polymerizable monomers that can be copolymerized with unsaturated polyesters include styrene, Q-chlorostyrene, vinyltoluene, pinyl acetate, methyl methacrylate, diallyl phthalate, triacyl cyanurate, triallyl isocyanurate, and the like. 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 an unsaturated polyester to obtain an unsaturated polyester resin liquid, and adding liquid butadiene having a vinyl group at the end to the unsaturated polyester resin liquid. By adding and mixing a n-acrylonitrile copolymer, or by adding and mixing a liquid butadiene-acrylonitrile copolymer having a vinyl group at the end with a polymerizable monomer that can be copolymerized with an unsaturated polyester, By mixing with a saturated polyester, and after adding and mixing a liquid butadiene-acrylonitrile copolymer having a pinyl group at the end to an unsaturated polyester, a polymerizable monomer that can be copolymerized with the unsaturated polyester is mixed. By doing so, it can be easily manufactured.

However, from the viewpoint of workability, it is not very suitable to first mix a liquid butadiene-acrylonitrile copolymer having a terminal pinyl group and an 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 curing catalysts include diacyl peroxide, aldehyde peroxide, ketone/gu oxide, alkyl/gu oxide, hydro/gu oxide,
There are alkyl/gu esters, azonitrile, etc., and these are appropriately selected and added to the unsaturated polyester resin liquid in advance for use. Further, in the unsaturated polyester resin composition of the present invention, commonly used additives such as fillers, reinforcing materials, thickeners, verticalizing agents, and coloring agents can be added and used.

Examples of fillers include calcium carbonate, talc, clay, barium sulfate, calcium sulfate, shirasu balloon,
Fillers such as inorganic fillers such as glass micro/silune, greenite, and asbestos, or organic fillers such as wood flour can be used. As a reinforcing material,
For example, vinylon fiber, polyester fiber, vegetable fiber,
Examples include organic or inorganic reinforcing materials such as glass fiber, carbon fiber, and metal fiber. As a thickener,
Examples include oxides or hydroxides of alkali metals such as magnesium oxide, magnesium hydroxide, and calcium hydroxide. Examples of the mold release agent include stearic acid, its metal salts, and phosphates. Next, the present invention will be explained with reference to Examples and Comparative Examples.

In each example, when determining the surface smoothness, 0 indicates excellent surface smoothness with no warpage, sink marks, or undulations, and × indicates poor surface smoothness with warpage, sink marks, or undulations. Represents something that indicates. In the evaluation of surface tackiness, 0 indicates no "stickiness" and x indicates "stickiness". Examples 1 to 5 Composition of the bulk molding compound used Unsaturated polyester resin liquid * 1 Zero Sanjiji Re * Total 3 flies Amount % Calcium carbonate (Nitto Funka; NS #200) 55% by weight 6 side chopped strand (manufactured by Nittobo; CS-Han-22
1) 15% by weight Zinc Stearate 7.0PHR Magnesium Oxide 1. Fertilizer HRt-Butyl peroxybenzoate (Perbutyl Z: NOF Corporation) 0. Rudder HR t-Butyl peroxy-2-ethyl hexa/ate (Perbutyl 0: NOF Corporation) 0.1 PHR*1; Type of unsaturated polyester resin liquid used (all parts are parts by weight) Resin liquid (1): Fumaric acid 1.0 mol, propylene glycol 1
．． This product was obtained by adding 0.01 part of hydroquinone to 100 parts of an unsaturated polyester with an acid value of 29 obtained by condensation reaction using 0.05 moles, and then dissolving this in 55 parts of styrene.

Resin liquid (0): phthalic anhydride 4.0 mol, fumaric acid 60
After adding 0.01 part of hydroquinone to 100 parts of unsaturated polyester with an acid value of 25 obtained by condensation reaction using 5.1 moles of propylene glycol and 5.0 moles of 1,6-hexanediol, This was obtained by dissolving this in 55 parts of styrene.

*2: The "liquid ptagene-acrylonitrile copolymer having a pinyl group at the end" used was "HycarV" manufactured by B.F. Godrich.
TBN-1300 x 141 (molecular weight 3400, acrylonitrile bond amount 18% by weight, number of terminal vinyl groups 1.9 viscosity CPS (Bruckfield, 27°C = 20 x 1 pi)
It is.

The above-mentioned components were mixed in a kneader using a conventionally known method to produce an unsaturated polyester resin composition as a bulk molding compound.

This was then compression molded at 130° C. and 100k9/8 minutes to create a 220×220×6 side plate.
The shrinkage rate was determined by a method according to JIS, K-6911, and the surface smoothness was determined visually. Table 1 shows the measured fruits and vegetables. Table 1 Comparative Examples 1 and 2 In Example 1, the liquid butadiene-acrylonitrile copolymer having a vinyl group at the end was not added at all, and the unsaturated polyester resin liquid was used at 3% by weight. An unsaturated polyester resin composition similar to that in Example 1 was manufactured and molded, and the shrinkage rate, surface smoothness, and surface tackiness were measured in the same manner as in Example 1.

The results are shown in Table 2. Table 2 Comparative Examples 3 and 4 In Example 2, liquid polybutadiene having hydrogen groups at both ends [molecular weight 130
0 atactic 1,2-polybutadiene, manufactured by Nippon Soda ■: G-1000], and liquid polybutadiene having carboxyl groups at both ends [molecular weight 130u atactic 1,2-polybutadiene, manufactured by Nippon Soda ■: C-100].
0] was used, but the same unsaturated polyester resin composition as in Example 2 was produced, molded in the same manner as in Example 2,
evaluated.

The results are shown in Table 3. In addition, compared to the copolymers in Examples 1 to 5, it was difficult to uniformly mix liquid polybutadiene in Comparative Examples 3 and 4.

Table 3 Comparative Example 5 In Example 2, resin liquid 0 was used, and instead of the liquid butadiene-acrylonitrile copolymer having vinyl groups at the ends, liquid polybutadiene [molecular weight 4000 acrylonitrile] having vinyl groups at both ends was used. Binding amount: 0% by weight
The same procedure as in Example 2 was used, except that HycarVTB, manufactured by B.F. producing an unsaturated polyester resin composition;
It was molded and evaluated in the same manner as in Example 2.

As a result, the molding shrinkage rate was 0.04%, and the surface smoothness was almost the same as in Example 2.

Furthermore, although the surface tackiness was slightly better than in Comparative Examples 3 and 4, it was quite sticky. In addition, as compared with Examples 1 to 5, the consistency was poor, and when the unsaturated polyester was mixed uniformly, mold contamination occurred when the produced unsaturated polyester was molded after being stored for a long period of time.

Example 6 10 unsaturated polyesters subjected to condensation reaction in the ratio of 1.0 mol of phthalic anhydride, 4.0 mol of fumaric acid and 5.0 mol of propylene glycol 0.0 mol of hydroquinone
After adding 1 part of styrene, 78 parts of styrene was added to melt and dissolve the unsaturated polyester resin liquid. % by weight of a liquid butadiene-acrylonitrile copolymer having a vinyl group at the end was added and mixed as a styrene solution with a cloud weight of 6%.

Next, this copolymer was added and mixed with 3 parts of unsaturated polyester resin, 6 parts of calcium carbonate, and 6 parts of glass fiber (
6 parts pork chop strands) and 3 parts zinc stearate
An unsaturated polyester resin composition is produced by blending the following parts, and compression molding is performed at 40qC and 100k9/me for 5 minutes, and the bending strength and bending elastic modulus of the molded product are determined according to JIS, K-6911.
Measured according to.

As a result, the bending strength was 4.64k9/rail, and the bending elastic modulus was IXXk9/me.

Claims (1)

[Claims] 1. An unsaturated polyester resin obtained by dissolving an unsaturated polyester in which the proportion of α/β-unsaturated polybasic acid in the acid component is 60 to 100 mol% into a polymerizable monomer that can be copolymerized with the unsaturated polyester. An unsaturated polyester resin composition characterized in that a liquid butadiene-acrylonitrile copolymer having a vinyl group at the end is added to the liquid.