JPS607663B2 - Low shrinkage allylic unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an allylic unsaturated polyester resin composition.

Specifically, pseudoallylic unsaturated compounds, 'B} have at least one succinic anhydride group in one molecule and have a molecular weight of 100
The present invention relates to an allylic unsaturated polyester resin composition, which is made of polyether having a molecular weight of 0 to 20,000 and a) unsaturated polyester, and is used to obtain a molded article with a small shrinkage rate and excellent surface smoothness by heating and pressure molding. Unsaturated polyester resin molded products reinforced with glass fibers or other fibers are widely used in fields such as bathtubs, septic tanks, toilet tanks, tanks, and boat docks. Such molded products are lighter than metals, have high corrosion resistance, and are highly flexible in design. However, in the hot-press molded products according to the prior art, glass fibers and the like stand out on the surface, making it impossible to obtain a smooth surface. Furthermore, due to the large shrinkage rate, it lacks dimensional stability and has drawbacks such as warping and cracking. To overcome these drawbacks, methods have recently been proposed to reduce curing shrinkage by blending thermoplastic polymers such as polystyrene, polymethyl methacrylate, polyvinyl acetate, or saturated polyester resins into unsaturated polyester resins. has been done. For ordinary unsaturated polyester resins that use copolymerizable monomers with relatively low boiling points, such as styrene, as crosslinking monomers, the curing shrinkage rate decreases due to the addition of these thermoplastic polymers. It is recognized that this decreases. The mechanism of low shrinkage in styrenic unsaturated polyester resin compositions is generally a rapid curing exothermic reaction between the unsaturated groups in the polyester and styrene, and the resulting styrene that dissolves or penetrates into the polymer and swells. It is believed that curing shrinkage is reduced by polymerization heat generation, foaming expansion, and the expansion rate when a compatible thermoplastic polymer precipitates during curing.

[Reinforced Plastics Technology Association, ed. "Reinforced Plastics Handbook" Nikkan Kogyo Shimbun (1975)] However, when a thermoplastic polymer is blended into an allyl unsaturated polyester resin composition using an allyl compound as a crosslinking monomer, The polymerization reaction between unsaturated groups and allyl groups in polyester does not occur as rapidly as in the case of styrene and generates less heat, and the allyl compound itself has a high boiling point and is difficult to foam. It has good compatibility with compounds and is difficult to cause low Z shrinkage due to precipitation during hardening.

Furthermore, if an attempt is made to reduce shrinkage by increasing the amount of thermoplastic polymer added, serious drawbacks such as color unevenness, reduction in gloss, or mold staining will occur. The inventors of the present invention aimed to overcome the drawbacks of conventional methods and provide an allyl unsaturated polyester resin with low pseudo-Z and low shrinkage.
It has succinic anhydride groups and has a molecular weight of 1000 to 20
The present invention was completed based on the discovery that by using a polyether of No. 000, a molded product with small curing shrinkage and excellent surface smoothness could be obtained.

That is, in the low shrinkage allylic unsaturated polyester resin composition of the present invention, (1) the allylic unsaturated compound contains 15 to 6% by weight of the harmful allylic unsaturated compound, (B) at least one in one molecule; It has a succinic anhydride group and a molecular weight of 1000 to 2.
0000 polyether and 39 to 84 weight% of unsaturated polyester.

Furyl compounds that can be used in the present invention include allyl naphtate, allyl octate, monoallyl phthalate, monoallyl compounds such as trimethylolpropane monoallyl ether, diallyl (ortho, iso,
and tele)phthalate, diallyl maleate, diallyl succinate, diallyl malonate, diallyl sebacate, diallyl adibate, diallyl tetrahalogenophthalate, diallyl tetrahydrophthalate, diallyl 3,6-endomethylenetetrahydrophthalate, diallyl 3,6-endo Diallyl compounds such as dichloromethylenetetrahydrophthalate, dimethallyl phthalate, dichlorophthalate, or trimethylolpropane diallyl ether, triallyl compounds such as triallyl cyanurate, triallyl phosphate, or triallyl isocyanurate, and diallyl phthalate prepolymers Examples include polyallyl compounds represented by the following, and one or more of these can be used in an amount ranging from 15 to 6% by weight based on the resin composition.

Among these allyl compounds, diallyl phthalate is particularly preferred. In addition, these crosslinking monomers
Up to 3% by weight of the compound used can be replaced by allylic unsaturated compounds and other monomers copolymerizable with the unsaturated polyester {C}. Such monomers include, for example, styrene, halogenated styrene, Q-methylstyrene, vinyltoluene, dipinylbenzene, pinyl acetate, acrylic or methacrylic acid with methyl alcohol/ethyl alcohol, propyl alcohol, octyl alcohol, ethylene glycol or propylene glycol. Examples include esters with aliphatic coals such as esters, etc., and one or a mixture of two or more of these monomers can be used. The additive polymer for low shrinkage used in the present invention has at least one succinic anhydride group in one molecule and has a molecular weight of 1000 to 200.
00 polyether tune, 1 to 3 for the resin composition
% by weight, preferably from 3 to 1% by weight. If the amount used is less than 1% by weight, the effect of addition cannot be expected. Further, if the amount exceeds 3% by weight, the physical properties of the cured unsaturated polyester resin will deteriorate, which is not preferable. Polyether 'B} having a succinic anhydride group used in the present invention can be obtained by ring-opening polymerization of a monoepoxide compound in the presence of allyl glycidyl ether or allyl halide.
It is obtained by preparing a polyether having an allyl group at the end and further reacting it with maleic anhydride.

Examples of monoepoxide compounds include ethylene oxide,
Examples include propylene oxide, 1-butene oxide, and inbutylene oxide. One kind or a mixture of two or more kinds of these monoepoxide compounds can be used. The number of succinic anhydride groups varies depending on the reaction conditions, but is at least 1 or more in one molecule, preferably 1 to 10. Polyether having a molecular weight of 1000 to 2000 is particularly effective. The unsaturated polyester [q, which is another component constituting the present invention, is not particularly limited, but is usually used for heat-pressing molding and has relatively high reactivity, that is, the double bond density in the molecule. A highly unsaturated polyester is desirable and can be used in a range of 39 to 84% by weight based on the resin composition.

Similar to this unsaturated polyester, a conventional method, for example, a Q, B-unsaturated dibasic acid or a mixture of this and a saturated dibasic acid, and a polyhydric alcohol, carbon dioxide gas, nitrogen In an inert gas Z flow such as gas, 140~
A method of heating to 250o0 to cause a condensation reaction, and gradually increasing the temperature depending on the degree of reaction progress while discharging the produced water out of the reaction system, Q.8 Monounsaturated dibasic acid anhydride or it and saturated dibasic acid The mixture with the anhydride and the oxide were heated at 50 to 250oC in an inert gas stream without or in the presence of a catalyst.
A method of reacting by heating to and/or by replacing part or all of the polyhydric alcohol with an ester of a polyhydric alcohol with a lower fatty acid such as acetic acid, propionic acid, etc., in the presence of a transesterification catalyst in an inert gas stream. An acid value of 60 or less obtained by heating to 140 to 250 CO to cause a condensation reaction, and distilling the produced dihydroalcohol, acid, etc. out of the reaction system. ,
It is an unsaturated polyester with a molecular weight of 1000 or more. At this time, the Q.8-unsaturated dibasic acids used are maleic acid, halogenated maleic acid, fumaric acid, citraconic acid,
Examples include itaconic acid, halogenated itaconic acid, and their saddle anhydrides; examples of saturated dibasic acids include phthalic acid,
Halogenated phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, succinic acid , azelaic acid, sebacic acid and the like. In addition, if necessary, monobasic acids such as acrylic acid, methacrylic acid, propionic acid, butyric acid, cyanobic acid, higher fatty acids, benzoic acid, octylic acid, etc., and tetracarboxylic acids such as trimellitic acid, hemimellitic acid, trimesic acid, and benzene may be used. It is also possible to use a polybasic acid such as the above-mentioned Q.P-unsaturated dibasic acid or a mixture thereof with a saturated dibasic acid as a modifying agent. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, tetramethylene glycol, 116-hexanediol, and neobentyl. Glycol, hydrogenated bisphenol A, ethylene oxide and/or propylene oxide adducts of bisphenol A, etc. can be mentioned, and in an excess amount of approximately equivalent to 5 to 20 mol% relative to the brewing ingredients. used. In addition, if necessary, higher aliphatic alcohols such as amyl alcohol, hexyl alcohol, bentyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, monohydric alcohols such as tetrahydrofuric alcohol, glycerin, bentaerythritol, trimethylol, etc. ethane,
Polyhydric alcohols such as trimethylolpropane, trimethylol phthane, sorbitol, erythritol, mesoerythritol, etc. can also be used in combination with the above-mentioned polyhydric alcohols as a denaturing agent. Examples of oxides include alkylene oxides such as ethylene oxide, 1,2-propylene oxide, and epichlorohydrin, and glycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, and allyl glycidyl ether. can. In preparing the unsaturated polyester, when a method is adopted in which a Q/B-unsaturated dibasic acid anhydride or a mixture of this and a saturated dibasic acid anhydride is reacted with an oxide, the catalyst used is are lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, thallium, lead,
Examples include organic or inorganic salts of metals such as titanium, zirconium, antimony, zinc, cadmium, tin, mercury, etc., and esters of these metal acids with alcohols. .0
It can be effectively used in amounts of ~0.01%, preferably 1.0-0.03%.

In addition, when a method of carrying out a transesterification reaction is adopted, the transesterification catalyst used can be the same as the catalyst used in the above method, and in particular compounds of zinc, tin, antimony, lead, and titanium are used as catalysts. Highly active and preferred. The low shrinkage allylic unsaturated polyester resin composition of the present invention is an allylic unsaturated compound of 'B', a polyether having at least one succinic anhydride group in one molecule and having a molecular weight of 1,000 to 20,000. , and}
Although it is made of unsaturated polyester, it can be manufactured by various methods.

For example, it can be produced by adding a previously prepared allyl compound solution of a succinic anhydride group-containing polyether to a resin liquid or mixture obtained by dissolving or blending an unsaturated polyester and a furyl compound. Alternatively, polyether can be directly added to a resin solution or mixture obtained by dissolving or blending an unsaturated polyester with an allyl compound, and if necessary, it can be produced by heating to about 100 qo to dissolve or melt the polyether. However, the scope of the present invention is not limited only by these manufacturing methods. The curing of the low-shrinkage allylic unsaturated polyester resin composition of the present invention produced in this way is performed using penzoyl peroxide, methyl ethyl ketone peroxide, t-butyl beroxybenzoate, t-butyl peroxy octocoat, dicumyl ber A polymerization catalyst such as an organic peroxide such as oxide, cumene hydroperoxide, cyclohexanone peroxide, lauroyl peroxide, or a nitrile capable of generating a radical such as azopisisobutyronitrile is added to the resin composition. If necessary, organic metals such as cobalt naphthenate, cobalt octenoate, manganese naphthenate, etc., aliphatic amines, aromatic amines, or mercaptans are added. The polymerization accelerator,
Blended in a range of 0.1 to 5% by weight with respect to the resin composition,
This can be carried out according to conventionally known procedures.

The low-shrinkage allylic unsaturated polyester resin composition of the present invention can be effectively used as it is, but it can also be used with fillers such as calcium carbonate, cinnabar sand, barium sulfate, clay, glass powder, glass fiber, asbestos, hemp, etc. , vinylon fiber, carbon fiber, etc., and thickeners such as magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium oxide, etc., bulk molding compound (BMC), sheet molding compound (S
As MC), it can be used for various electrical parts, industrial parts, automobile parts, etc. by taking advantage of its heat resistance, electrical insulation properties, and corrosion resistance.

For example, in the case of BMC, the low shrinkage allylic unsaturated polyester resin composition of the present invention is mixed with calcium carbonate and zinc stearate in a kneader 0. chopped strands,
Add curing catalyst, colorant and thickener if necessary,
Mix thoroughly to form a mass.

A calculated amount of this lump is placed in a mold and heated and pressurized to polymerize and harden it into a molded product. Also, in the case of SMC,
The low shrinkage allylic unsaturated polyester resin composition of the present invention is thoroughly mixed with a thickener, a mold release agent, a polymerization catalyst, and a filler to obtain a relatively viscous liquid mixture.

A pre-formed glass fiber sheet is impregnated with an appropriate amount of this liquid mixture, the resin mixture is thickened to the extent that it loses its sulfur properties, and the calculated amount of bread-like sheets are placed in a mold, heated and pressurized. Polymerize and harden to form a molded product. The molded product thus obtained has excellent surface smoothness and shrinkage during molding is extremely low, so that no distortion or cracks occur. The present invention will be explained in more detail with reference to Examples below.

Note that parts in the examples mean parts by weight. Example 1 A four-necked flask equipped with a reflux condenser, a thermometer, and a Nada Azusa machine was charged with 10 anchors of polypropylene oxide (molecular weight approximately 8,000) having allyl groups at both ends and 10 anchors of benzene, and further anhydrous maleic acid. Acid 4. $ part and 0.05 part of azobisisobutyronitrile were added, and the mixture was reacted at 80 qo for 3 hours.

After the reaction, the solvent benzene was removed under reduced pressure to obtain polypropylene oxide (hereinafter referred to as polyether "A") having about three succinic anhydride groups in one molecule. Reference Example 2 The same operation as in Reference Example 1 was carried out except that polypropylene oxide having an allyl group at both ends with a molecular weight of 6000 was used to obtain a reaction product (hereinafter referred to as polyether "B").
”.

) was obtained. Reference Example 3 592 parts of phthalic anhydride, 588 parts of maleic anhydride, and 836 parts of propylene glycol were charged into a four-necked flask equipped with a rope strainer, a thermometer, a partial condenser, a gas inlet pipe, and a heating device, and the mixture was heated. The mixture was heated to a maximum temperature of 220° C. to cause a dehydration condensation reaction, and when the reaction product reached an acid value of 30, the reaction was stopped and cooled to obtain an unsaturated polyester.

8 parts of this unsaturated polyester were mutually dissolved in a ratio of 20 parts of orthodiallyl phthalate and 0.020 parts of hydroquinone to obtain resin "1". Reference Example 4 The acid value was set to 33 using the same procedure as Reference Example 3 except that maleic anhydride and 1,3-butylene glycol 85 were used.
An unsaturated polyester was obtained.

7 parts of this unsaturated polyester were mutually dissolved with 3 parts of ortho diallyl phthalate and 0.02 parts of hydroquinone to form resin "0". Example 1 8 parts of resin "1", 2 parts of polyether "A" 30% orthodiaryl phthalate solution, 1.0 part of t-butylberoxybenzoate, 3 parts of zinc stearate. Ikari county,
7 parts of toner color for polyester (blue), 18 parts of calcium carbonate base and 7 parts of 1/4 inch chopped strands were intimately mixed in a Banbury mixer to obtain a soft bread-like mass (BMC).

This BMC was molded into a flat plate of 30 m x 30 m x 3 skins under conditions of a temperature of 150°C, a pressure of 100 k9', and a pressurizing time of 4 minutes. A flat plate with excellent surface smoothness and no color unevenness or color separation was obtained. Regarding the shrinkage rate, please refer to JISK
-6911, a test piece (hereinafter referred to as ``JIS disk'') was molded and measured, and the shrinkage rate was only 0.
It was 0.6%. Example 2 A BMC was prepared using the same procedure as in Example 1 except that resin “0” was used instead of resin “1”, and then a flat plate and a J
When IS disks were molded, the results were as shown in Table 1.

Examples 3-4 In Example 1, resin “1” and polyether “A” 3
The mixing ratio of the ortho diallyl phthalate solution containing 0% was 9
BMC was prepared using exactly the same formulation and procedure except that the IQ was changed to 70/30, and a flat plate and a JIS disk were molded.

The results were as shown in Table 1. Examples 5 to 6 In Examples 1 and 2, a 30% orthodiallyl phthalate solution of polyether "B" was used instead of polyether "A", and BMC was prepared using the same formulation and procedure as above, and a flat plate and a JIS A disk was formed.

The results were as shown in Table 1. Examples 7-8 Using resin "1", the composition was as shown in Table 1 (however, glass fiber was excluded).

) to form a liquid compound. A glass mat was impregnated with this compound using a roll, both sides of the obtained sheet were sandwiched between polyethylene films, and the sheets were aged at 4000° C. for 48 hours to obtain SMC. Using this SMC, a flat plate and a JIS disk were molded in the same manner as in Example 1. The results were as shown in Table 1. Examples 9-10 Using resin "1", the composition was as shown in Table 1 (however, glass fiber was excluded).

) to obtain a liquid compound. This compound is placed between glass mats (#450) in the mold,
Matched die molding was performed using heat and pressure molding. The surface smoothness and shrinkage rate of the molded product were as shown in Table 1. Example
11 BMC was prepared in the same manner as in Example 1 with the formulation shown in Table 1, using a part of orthodiaryl phthalate prepolymer (''Disodap L'' manufactured by Osaka Soda) as the allyl compound.
was prepared and molded into flat plates and JIS disks.

The results are shown in Table 1. Example 12 In Example 1, Mg◯ #40 was further used as a thickener and aged at 40 qo for 48 hours to obtain BMC, which was molded into flat plates and JIS disks.

The results are shown in Table 1. Comparative Examples 1 to 6 BMC was prepared according to the formulation shown in Table 2 in the same manner as in Example 1, and flat plates and JIS disks were molded.

The results were as shown in Table 2. Comparative Example 7 SMC was prepared according to the formulation shown in Table 2 in the same manner as in Example 7, and a flat plate and a JIS disc were molded.

The results were as shown in Table 2. Comparative Example 8 In the same manner as in Example 9, matched die molding was performed using the formulations shown in Table 2 to mold flat plates and JIS discs.

The results were as shown in Table 2. As is clear from Table 2, in the system not using the polyether according to the present invention and the system using the conventional thermoplastic polymer, it was observed that the surface condition of the molded articles was poor and the shrinkage rate was large. Table 1 (Note-1) 30% of the hollether "A" obtained in Reference Example 1
Ortho diallyl phthalate solution (Note 2) ″ 2
“B” (Note-3) “Daiso Duff.

” Made by Osaka Soda (Note 4) Base pigment for polyester (
Cobalt Blue) Evaluation ◎: Excellent ○: Good △: Fairly bad ×: Poor Table 2 (Note-5) 30% ortho diallyl phthalate solution of polypynylacetate (Note-6) Polystyrene (Yoichi 7) Polymethyl methacrylate ″Evaluation ◎: Excellent ○: Good △: Fairly bad ×: Poor

Claims (1)

[Claims] 1 (A) allylic unsaturated compound 15-60% by weight (B
) having at least one succinic anhydride group in one molecule,
Polyether 1~ having a molecular weight of 1000~20000
30% by weight (C) Unsaturated polyester 39-84% by weight
(However, (A) + (B) + (C) is 100% by weight).