JPH0128062B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition that provides a cured product with low shrinkage and excellent air drying properties. Unsaturated polyester resins are widely used as molding materials because they have excellent chemical resistance, heat resistance, mechanical properties, and electrical properties. Among these, unsaturated polyester resins reinforced with glass fibers are molded using various molding methods to provide various molded products such as helmets, chairs, bathtubs, tanks, and ships. Although unsaturated polyester resin has these features, its drawbacks include that when it is cured in the air using peroxide, the surface that comes into contact with the air is not sufficiently cured, resulting in poor air drying properties. It has been pointed out that dimensional accuracy is poor due to large shrinkage during heating, and adhesion with glass fibers is impaired, causing glass fibers to stand out on the surface, resulting in poor gloss and surface smoothness. Various methods have been developed to improve these drawbacks. Regarding air drying properties, for example, chemical methods such as blending petroleum resins or allyl ether compounds modified with unsaturated acids, or adding film-forming agents such as wax to form a film on the surface of the unsaturated polyester resin during curing can be used. There are physical methods to form and block air. However, petroleum resins have a disadvantage that they are not compatible with unsaturated polyester resins and tend to cause turbidity on the surface, and when wax is used, it takes time and effort to grind the film afterwards. On the other hand, to improve shrinkage, a common method is to add a thermoplastic polymer and use its thermal expansion to create voids around the dispersed thermoplastic resin after curing and cooling, thereby lowering the apparent shrinkage rate. has been adopted. This method has the disadvantage that not only mechanical properties deteriorate due to the generation of a large number of voids, but also color unevenness occurs. Although the conventional techniques can improve air drying properties or shrinkability, other problems arise. In order to improve these drawbacks, it is desirable to impart low shrinkage and air drying properties to the unsaturated polyester itself. As a result of intensive research from this point of view, the inventors discovered that the composition for unsaturated polyester resin described below provides a cured product with low shrinkage and excellent air drying properties, leading to the present invention. . That is, the present invention combines a polyhydric alcohol component (a) containing a polyhydric alcohol having an aliphatic polycyclic skeleton represented by the following formula () and/or formula () and the following formula () and/or formula ( ) and an unsaturated polyester (A) obtained from a saturated polybasic acid component (b) containing a saturated polybasic acid having an aliphatic polycyclic skeleton and an unsaturated polybasic acid component (c) shown in The present invention provides a composition for unsaturated polyester resin comprising a polymerizable α,β-ethylenically unsaturated monomer (B). formula() (R ₁ to _{R 4} are hydrogen or alkyl groups, n is 1 or 2) Formula () ( _R5-10 are hydrogen or alkyl groups, m is 0 or 1) Formula () (R _{11 to 14} are hydrogen or an alkyl group, R' and R'' may be the same or different and are hydrogen or an alkyl group that can be transesterified, k is 1 or 2) Formula () (R _{15 to 20} are hydrogen or an alkyl group, R' and R'' may be the same or different and are hydrogen or an alkyl group capable of transesterification, l is 0 or 1) The above formula () or formula ( ) The following compounds are preferably used. dihydroxymethyltricyclo[5,2,1,
0 ^2,6 ] Decane dihydroxymethylpentacyclo[6,5,
1, 1 ^3,6 , 0 ^2,7 , 0 ^9,13 ] Pentadecane dihydroxymethyltetracyclo[6,5,
1,0 ^2,7 , 0 ^9,13 ] Tetradecane The polyhydric alcohol component (a) of the present invention may be entirely a compound represented by the formula () and/or the formula (), or may be a compound represented by the formula () and/or the formula (), or may be a compound represented by the formula () and/or the formula (). It can also be used in combination with a polyhydric alcohol. Expression () and /
Other polyhydric alcohols that can be used in combination with the compound represented by formula () include propylene glycol, ethylene glycol, neopentyl glycol, 2,2,4-trimethylpentanediol-1,3, butanediol-1 ,3,butanediol-1,4,hexanediol-1,
6. Hydrogenated bisphenol A, bisphenol A
propylene oxide adducts, trimethylolpropane, epoxy compounds, etc., and combinations of these are also possible. The polyhydric alcohol component (a) used in the present invention contains 50% of the compound represented by formula () and/or formula ().
It is preferable that the content is mol% or more. Furthermore, in the compound represented by the above formula () or formula (), when R' and R'' take an alkyl group,
They may be any alkyl group that can be transesterified in polyester synthesis, preferably an alkyl group having 1 to 3 carbon atoms. The following compounds are preferably used as the compound represented by formula () or formula (). Dicarboxytricyclo[5,2,1,0 ^2,6 ]
decan dimethoxycarbonyltricyclo[5,2,
1,0 ^2,6 ] Decane Dicarboxypentacyclo[6,5,1,1 ^3,6 ,
0 ^2,7 , 0 ^9,13 ] Pentadecane dimethoxycarbonylpentacyclo[6,5,
1, 1 ^3,6 , 0 ^2,7 , 0 ^9,13 ] Pentadecane Dicarboxytetracyclo[6,5,1,0 ^2,7 ,
0 ^9,13 ] Tetradecane dimethoxycarbonyltetracyclo[6,5,
1,0 ^2,7 , 0 ^9,13 ] Tetradecane The saturated polybasic acid component (b) of the present invention may be entirely a compound represented by the formula () and/or the formula (), or may be a compound represented by the formula () and/or the formula (). It can also be used in combination with other saturated polybasic acids. Other saturated polybasic acids that can be used in combination with the compound represented by formula () and/or formula () include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydro Examples include phthalic anhydride, endomethylenetetrahydrophthalic anhydride, hettic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, succinic acid, adipic acid, sebacic acid, trimellitic anhydride, and combinations of these are also possible. The saturated polybasic acid component (b) used in the present invention is a compound represented by formula () and/or formula ().
It is preferable that the content is mol% or more. As the unsaturated polybasic acid component (c), maleic acid,
Fumaric acid or anhydride thereof is used. The ratio of the polyhydric alcohol component (a), the saturated polybasic acid component (b), and the unsaturated polybasic acid component (c) is not particularly limited, and may be within the conventionally generally used range. For example, the molar ratio of polyhydric alcohol component (a)/saturated polybasic acid component (b)/unsaturated polybasic acid component (c) is 1/
A range of 0.5-0.3/0.5-0.7 is appropriate. By polycondensing these three components, unsaturated polyester (A) can be easily obtained. The α,β-ethylenically unsaturated monomer (B) copolymerizable with this unsaturated polyester (A) includes styrene, chloro-substituted styrene, bromine-substituted styrene, α-methylstyrene, vinyltoluene, divinyl benzene,
Vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, diallyl phthalate, etc., and combinations of these are also possible. Unsaturated polyester (A) and α,β-ethylenically unsaturated monomer (B)
The mixing ratio by weight is (A)/(B)=30/70~80/
A range of 20 is appropriate. The thus obtained composition for unsaturated polyester resin contains fillers, glass fibers, boron fibers,
Inorganic fibers such as carbon fibers, organic fibers such as vinyl fibers and polyester fibers, thermoplastic polymers, mold release agents, flame retardants, ultraviolet absorbers, blowing agents, pigments, etc., are used in combination as necessary to produce a conventional catalyst. It is used in the production of various molded products by being cured in the presence of the resin. Examples of the present invention are shown below, but these are for specifically explaining the present invention and are not intended to limit the scope of the present invention. Example 1 Equipped with a stirrer, thermometer, and fractionation condenser
0.5 flask,

[Formula] 1.0 mol,

[Formula] 0.5 mol and 1.0 g of zinc acetate and 0.5 g of antimony trioxide as transesterification catalysts were charged, and the
After reacting at ℃ until the theoretical amount of methanol was distilled out, 0.5 mol of maleic anhydride was added and the mixture was heated to 180-195℃.
The condensation reaction was carried out at °C, and when the acid value reached 20, the reaction was stopped and 200 mg of hydroquinone was added. 60 parts by weight of the unsaturated polyester synthesized in this way was dissolved in 40 parts by weight of styrene to prepare a composition for unsaturated polyester resin (a). Example 2 Equipped with a stirrer, thermometer, and fractionation condenser
0.5 flask,

[Formula] 0.5 mol and propylene glycol 0.5 mol and

[Formula] 0.3 mol, 0.2 mol of isophthalic acid, and 0.61 g of zinc acetate and 0.30 g of antimony trioxide as transesterification catalysts were reacted at 170 to 200°C under a nitrogen stream until the theoretical amount of methanol was distilled out. maleic anhydride
Add 0.5 mol and conduct a condensation reaction at 180-190℃,
When the acid value reached 20, the reaction was stopped and 200 mg of hydroquinone was added. A composition (b) for unsaturated polyester resin was prepared by dissolving 60 parts by weight of the unsaturated polyester synthesized in this manner in 40 parts by weight of styrene. Comparative Example 1 In Example 1

A composition (c) for unsaturated polyester resin was obtained in the same manner except that propylene glycol was used in place of [Formula]. Comparative Example 2 In Example 1

A composition (d) for unsaturated polyester resin was obtained in the same manner except that isophthalic acid was used in place of [Formula] and the reaction was carried out without using a transesterification catalyst. Comparative Example 3 In Example 1

Using propylene glycol in place of [formula], or

A composition (e) for unsaturated polyester resin was obtained in the same manner except that isophthalic acid was used in place of [Formula] and the reaction was carried out without using a transesterification catalyst. Compositions (a) obtained in Examples 1 and 2 and Comparative Examples 1 to 3
-(e) 100 parts by weight of each, 0.16 parts by weight of accelerator PT-42 [hardening accelerator manufactured by Hitachi Chemical Co., Ltd.], and accelerator PT-24
Add in this order 0.24 parts by weight of curing accelerator (manufactured by Hitachi Chemical Co., Ltd.) and 0.48 parts by weight of Mepotx "55" (55% solution of methyl ethyl ketone peroxide, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), cure at room temperature, and form a cast plate. Created. Volumetric shrinkage, boiling water absorption, alkali resistance, and heat distortion temperature were measured using these cast plates. In addition, PT-42 was added to 100 parts by weight of each of resin compositions (a) to (e).
A mixture containing 0.5 parts by weight of PT-24, 1.0 parts by weight of PT-24, and 2.0 parts by weight of Mepotx "55" was coated on an aluminum plate to a thickness of 0.1 mm, and air drying properties were evaluated. The results are shown in the table below.

[Table] From the results in the above table, it is clear that the unsaturated polyester resin obtained from the composition of the present invention has low shrinkage and excellent air drying properties. It can also be seen that it exhibits excellent properties in terms of chemical resistance and heat resistance.

Claims (1)

[Scope of Claims] 1. A polyhydric alcohol component (a) containing at least one compound selected from the following formula () or a compound represented by the formula (); an unsaturated polyester (A) obtained from a saturated polybasic acid component (b) containing at least one compound selected from the compounds selected from the above, and an unsaturated polybasic acid component (c), and α copolymerizable therewith; A composition for unsaturated polyester resin comprising a β-ethylenically unsaturated monomer (B). formula() (R ₁ to _{R 4} are hydrogen or alkyl groups, n is 1 or 2) Formula () (R ₅ to _{R 10} are hydrogen or alkyl groups, m is 0 or 1) Formula () (R ₁₁ to _{R 14} are hydrogen or an alkyl group, R' and R'' may be the same or different and are hydrogen or an alkyl group that can be transesterified, k is 1 or 2) Formula () (R ₁₅ to _{R 20} are hydrogen or an alkyl group, R' and R'' may be the same or different and are hydrogen or an alkyl group that can be transesterified, l is 0 or 1) 2 Formula () or Formula ( ) 50
The composition according to claim 1, characterized in that the polyhydric alcohol component (a) is used in an amount of mol % or more. 3 The compound represented by formula () or formula () is 60
Claim 1 or 2, characterized in that a saturated polybasic acid component (b) containing mol% or more is used.
Compositions as described in Section.