JPS5947708B2 - Unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unsaturated polyester resin composition having excellent chemical resistance such as alkali resistance and water resistance.

IQ - In general, unsaturated polyester resins contain ester bonds in their prepolymer main chains, so they have extremely poor chemical resistance such as alkali resistance and water resistance, and therefore cannot be used in the presence of alkalis, acids, etc. It has the disadvantage that it cannot be used.

Various studies have been made in the past as methods for improving such alkali resistance and water resistance.

For example, improvements have been made using unsaturated polyester resins made from bisphenol A and unsaturated polyester resins made from isophthalic acid. However, these methods have drawbacks such as expensive raw materials and long production time of the unsaturated polyester prepolymer.

In addition, in order to improve chemical resistance, the use of a thermoplastic resin as a third component in addition to the unsaturated polyester prepolymer and the crosslinkable unsaturated monomer was considered, but the compatibility of the three components is generally Unfortunately, when molding general liquid unsaturated polyester resins such as pan lay-up molding, spray-up molding, and cast molding, the unsaturated polyester component and thermoplastic resin phase separate, leaving uncured materials. An excellent molded product cannot be obtained. For this reason, there is currently a need for a liquid unsaturated polyester resin composition that can be molded by any method and has excellent chemical resistance.
The inventors of the present invention have arrived at the present invention as a result of intensive studies in consideration of the above points.

That is, the present invention includes (1) 15 to 45% by weight of an unsaturated polyester prepolymer, 45 to 80% by weight of a crosslinkable unsaturated monomer, and a styrene thermoplastic polymer soluble in the crosslinkable unsaturated monomer. Combine 5-30
100 parts by weight of an unsaturated polyester resin consisting of % by weight.

(2) 0.01 to 5.0 parts by weight of a nonionic surfactant having an HLB value of 6.5 to 16.5.

(3) By adding it to the composition consisting of (1) and (2) above, the viscosity can be increased from 300 to 50,000 cps (20
Powdered inorganic filler.

(4) An organic peroxide and an accelerator for curing the unsaturated polyester resin at room temperature and pressure.

The present invention relates to an unsaturated polyester resin composition.

Further, a resin concrete with excellent compressive strength, which is made by adding sand in a volume content of 10 to 70% to the unsaturated polyester resin composition, and 100 parts by weight of the unsaturated polyester resin composition are added to the unsaturated polyester resin composition in a chopped or continuous form. The present invention relates to a glass fiber-reinforced unsaturated polyester resin composition containing 10 to 400 parts by weight of glass fibers and having excellent mechanical strength. The unsaturated polyester resin composition according to the present invention contains an excess of crosslinkable unsaturated monomers relative to the unsaturated groups of the unsaturated polyester prepolymer, and further has excellent alkali resistance, water resistance, and acid resistance. Because the styrenic thermoplastic resin is uniformly dispersed with a nonionic surfactant, it exhibits chemical resistance not found in conventional unsaturated polyester resins.

More surprisingly, the unsaturated polyester resin composition according to the present invention can be cured and molded by uniformly dispersing the styrenic thermoplastic resin dissolved in the crosslinkable unsaturated monomer in the composition. The body exhibits excellent impact resistance.

Moreover, it is possible to provide a molded article that not only has improved elongation but also has excellent mechanical strength such as tensile strength and bending strength. The unsaturated polyester prepolymer in the present invention is
It is a polymer with a molecular weight of about 700 to 5,000 obtained by polycondensing a saturated acid, an unsaturated acid, and a dihydric alcohol. Saturated acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, etc.; unsaturated acids include fumaric acid, maleic acid or their anhydrides, and citraconic acid; and dihydric alcohols. Examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and the like. In addition, examples of the crosslinkable unsaturated monomer used in the present invention include styrene, chlorostyrene,
Styrene derivatives such as α-methylstyrene, tertiarybutylstyrene, vinyltoluene, divinylbenzene,
Examples include methyl methacrylate, methyl acrylate, diallyl phthalate, etc., which can be used alone or in combination. Examples of the styrenic thermoplastic polymer used in the present invention include polymers that are soluble in the crosslinkable unsaturated monomers, such as polystyrene, high-impact polystyrene, acrylonitrile-styrene copolymer, butadiene-styrene copolymer, etc. It will be done.

The unsaturated polyester resin used in the present invention includes 15 to 45% by weight of the unsaturated polyester prepolymer and 45 to 80% by weight of the crosslinkable unsaturated monomer. , 5 to 30% by weight of a styrenic thermoplastic polymer.

If the amount of the unsaturated polyester prepolymer is less than 15% by weight, the mechanical strength and thermal strength of the unsaturated polyester resin will decrease, making it unusable for practical use. If the unsaturated polyester prepolymer exceeds 45% by weight, or if the thermoplastic polymer exceeds 30% by weight? or when the crosslinkable unsaturated monomer is less than 45% by weight, the viscosity of the unsaturated polyester resin composition becomes high, making it impossible to mold at room temperature and pressure, and molding by cast molding, spray-up, and panning. Tray-up molding is not possible. If the content of the crosslinkable unsaturated monomer exceeds 80% by weight, curing shrinkage will be large and cracks will occur. Furthermore, if the amount of the styrene thermoplastic resin added is less than 5% by weight, no improvement in alkali resistance or water resistance is observed, and mechanical properties such as impact strength deteriorate. The surfactant used in the present invention has an HLB value (hydrophilic-lipophilic balance value) of 6.5 to 1.
Among the nonionic surfactants listed in 6.5, are the alkyl allyl ether type, alkyl ether type, alkyl ester type, and I2? Seed--? There are various products such as (Nippon Nyuka).

In particular, as a surfactant, a nonionic surfactant having the structure (R represents an alkyl group or an alkenyl group) improves the adhesion of unsaturated polyester resin to difficult fillers, sand, and glass fiber. Furthermore, by imparting superior elongation, strength can be exhibited despite the presence of large amounts of inorganic filler and sand.

The alkyl group and alkenyl group of the surfactant include:
A lauryl group, stearyl group, oleyl group, and linoleyl group are preferred. The amount of nonionic surfactant used in the present invention is 0 parts by weight per 100 parts by weight of the unsaturated polyester resin.
．． 01 to 5.0 parts by weight.

If the amount added is less than 0.01 parts by weight, the unsaturated polyester and the styrene thermoplastic polymer will separate into two layers, making molding impossible. Further, if the amount added exceeds 5.0 parts by weight, phase separation occurs and molding becomes impossible. Also, the HLB value is 6.5
If the HLB value is less than 16.5, the unsaturated polyester and the styrenic thermoplastic polymer will separate, and if the HLB value exceeds 16.5, the compatibility will be resolved, but the resulting molded product will have a disadvantage of poor water resistance. . Examples of the powdered inorganic filler used in the present invention include calcium carbonate, aluminum hydroxide, clay, talc, mica, fly ash, basic magnesium carbonate, etc., and the viscosity of the unsaturated polyester resin composition is 300 to 50,000 cps ( 20°C) is required.

If the viscosity of the composition is less than 300 cps, the resin composition tends to undergo phase separation during curing, and the powdered inorganic filler tends to settle, resulting in variations in the physical properties of the cured resin.
Even if the speed exceeds 00 cps, air bubbles will be introduced during molding.
A product with excellent mechanical strength cannot be obtained by molding at room temperature and pressure. 10% of sand is added to the unsaturated polyester resin composition of the present invention.
It can contain up to 70% by volume, and can be used as resin concrete to provide a molding material with excellent compressive strength by molding methods such as cast molding and centrifugal molding.

The amount added is 10 volumes? If it is less than that, strain will be concentrated and the strength will be lower than that without the addition. Furthermore, if the amount added exceeds 70% by volume, the amount of resin will be insufficient even if the sand is most densely packed, resulting in poor adhesion and cavities, resulting in a decrease in strength. By mixing 10 to 400 parts by weight of chopped or continuous glass fibers into 100 parts by weight of the unsaturated polyester resin composition of the present invention,
A glass fiber reinforced molded product with excellent mechanical strength and thermal strength can be provided.

If the glass fiber content is less than 10 parts by weight, the strength will be lower than that without the addition, and if it exceeds 400 parts by weight, the mechanical strength will be lowered due to insufficient adhesion between the glass fibers. This glass fiber-reinforced unsaturated polyester resin composition can be molded using cast molding, centrifugal molding, pan lay-up molding, spray-up molding, etc., and filament winding molding (FW molding) using continuous glass fibers. It can also be pultruded. The unsaturated polyester resin composition of the present invention can be cured with an organic peroxide, and is characterized by being rapidly cured at room temperature and pressure, particularly with a redox accelerator. Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tertiary butyl perbenzoate, etc., and examples of accelerators include dimethylaniline, diethylaniline, cobalt naphthenate, manganese naphthenate, etc. The amount added can be adjusted depending on the curing time. As a method for preparing the unsaturated polyester resin composition of the present invention, a resin liquid is prepared by mixing an unsaturated polyester prepolymer with a crosslinkable unsaturated monomer, and a styrenic thermoplastic polymer is mixed with a crosslinkable unsaturated monomer. An example of this method is to mix the mixed resin liquids, further add a nonionic surfactant and a powdered inorganic filler, and uniformly mix the mixture by mechanical stirring.

Some common items used in the embodiments of the present invention will be explained below.

1) Production of unsaturated polyester prepolymer stirrer, N
Into a reactor having two gas inlets and a partial condenser, 10 m of phthalic anhydride (I1) 10 m of maleic anhydride was added.
01) Add propylene glycol 22m01), 18
By polymerizing at 0 to 200°C for 8 hours, the acid value is 20.
The following unsaturated polyester prepolymer is obtained.

(2) Add 0.02 parts by weight of hydroquinone to 60 parts by weight of the unsaturated polyester prepolymer obtained by mixing crosslinkable unsaturated monomers, and heat to 80°C.

After uniform melting, 40 parts by weight of a crosslinkable unsaturated monomer is added and dissolved to obtain unsaturated polyester resin liquid A. (3) Preparation of unsaturated polyester resin A crosslinkable unsaturated monomer is added to the styrenic thermoplastic polymer and dissolved to obtain Solution B.

The A liquid and the B liquid in (2) are added and mixed to obtain an unsaturated polyester resin. (4) Chemical resistance test The unsaturated polyester resin composition was cast and molded to a thickness of 3n.
Obtain a molded plate.

A test piece with a width of 25 u) and a length of 80 n was made from this molded plate, and after immersed in the test solution at 60°C for 5 hours, washed with distilled water and wiped thoroughly with a dry cloth, the weight change and bending strength retention were determined. Check chemical resistance. Example 1 30 parts by weight of the unsaturated polyester prepolymer, 56 parts by weight of styrene monomer, polystyrene (Styrono,
66; Asahi Tau Co., Ltd.) Emulgen 90 as a nonionic surfactant to unsaturated polyester resin consisting of 15 heavy grains
After adding 0.5 parts by weight of Kao Atlas HLB value 10.8) and 50 parts by weight of kaolin clay and mixing uniformly, 1.0% by weight of benzoyl peroxide and 0.3% by weight of diethylaniline as curing catalysts. 3m7 by adding and casting! A molded plate having a thickness of L was molded.

Table 1 shows the physical properties and chemical resistance results. Comparative Example 1 An unsaturated polyester resin composition consisting of 60 parts by weight of unsaturated polyester prepolymer, 40 parts by weight of styrene monomer, and 50 parts by weight of kaolin clay was cured by the cast molding method in the same manner as in Example 1.

Table 1 shows the physical properties and chemical resistance results. Examples 2 to 5
and Comparative Examples 2 to 4 The component weight ratio of the unsaturated polyester resin shown in Example 1, that is, unsaturated polyester prepolymer/styrene monomer/polystyrene = 30/5
Changed 5/15, 10/85/5, 15/70/15
, 15/80/5, 20/50/30) 20/45/3
5, 45/45/10) Emulgen 902 was added to 100 parts by weight of an unsaturated polyester resin consisting of 50/45/5.
,．． 5 parts by weight and 50 parts by weight of kaolin clay,
It was cast and molded in the same manner as in Example 1, and the physical properties and chemical resistance were examined. Table 1 shows the results.

Examples 6 to 7 and Comparative Examples 5 to 6 100 parts by weight of an unsaturated polyester resin obtained in the same manner as in Example 1 was added with HLB values of 4.7, 6, 7, 16, 3.
, 17.2, and 50 parts by weight of kaolin clay were added, cast molding was performed in the same manner as in Example 1, and the chemical resistance was examined.

The results are shown in Table 2. As a result, in those with an HLB value of 4.7, the polystyrene component phase-separated from the unsaturated polyester resin composition, and uncured materials adhered to the surface of the cured molded product, making it impossible to measure physical properties. When the HLB value was 17.2, the surface became white due to alkali resistance, and the mechanical strength also decreased. Also, those with HLB values of 6.7 and 16.3 showed good results similar to the HLB value of 10.8 used in Example 1. Comparative Example 7 50 parts by weight of kaolin clay was added to 100 parts by weight of an unsaturated polyester resin obtained in the same manner as in Example 1, and cured in the same manner as in Example 1, but the polystyrene component was an unsaturated polyester resin. It was separated from the composition and bled onto the surface of the molded plate as an uncured product.

Examples 8 to 10 and Comparative Example 8 To 100 parts by weight of an unsaturated polyester resin obtained in the same manner as in Example 1, 50 parts by weight of kaolin clay and Emulgen 906 were added at 0.01, 3.0, 5.0, 7.0 parts by weight was added and cast molding was carried out in the same manner as in Example 1.

The results are shown in Table 3. As a result, the added weight of surfactant was 7
．． In the case of 0 parts by weight, one component of the unsaturated polyester prepolymer phase-separated due to the high affinity between the clay and polystyrene components. Compared to Comparative Example 1, no uncured material was observed, but a molded plate with non-uniform composition was obtained, and the mechanical strength was also reduced. Examples 11 to 13 and Comparative Examples 9 to 10 Unsaturated polyester resin 10 obtained in the same manner as Example 1
Emulgen 90^.0 parts by weight. 5 parts by weight, and further 25 parts by weight of calcium carbonate as a powdered inorganic filler.
0 parts by weight, clay NK-SP (Chuo Kaolin Co., Ltd.) 100
200 parts by weight were added.

The viscosity at 20° C. was measured using a BL viscometer, and the sedimentation phenomenon and moldability of the inorganic filler were also investigated, and the results are shown in Table 4. As a result, if the viscosity is less than 300 cps, the inorganic filler will settle, making it impossible to obtain a good molded plate. 50 again
If it exceeded 000 cps, defoaming was difficult and a good molded product could not be obtained. As Comparative Example 10, a composition without an inorganic filler was studied.

The results are shown in Table 4. Examples 14 to 18 and comparative examples
11-13 35 parts by weight of the unsaturated polyester prepolymer, 30 parts by weight of styrene monomer, divinylben;
Ninibon-''.', Masanobu τ: Trunk = ;゛?: Shin'!': W to Y; Content rate: 5%, 1
0? , 50%, 60%, 70%, 80% 32-150
Mesh sand was added, cast molding was performed in the same manner as in Example 1, and the physical properties were measured.

The results are shown in Table 5. In addition, as Comparative Example 11, a composition without sand was studied and compared with Examples 14-18.

The results are shown in Table 5. As Comparative Example 12, the unsaturated polyester resin composition not containing the styrene thermoplastic resin used in Comparative Example 1 was studied and compared with Example 15. As a result, the unsaturated polyester resin composition containing the styrenic thermoplastic resin showed excellent mechanical strength because it had sufficient elongation as a sand-and-sand adhesive. Example 1
9 to 21 and Comparative Example 14 Resin composition 100 consisting of the unsaturated polyester resin, clay, surfactant, and curing catalyst used in Examples 14 to 18
To 1 part by weight, 5, 10, 50, and 100 parts by weight of chopped strand-shaped glass fibers having a length of 251 s were added, and a molded plate was created while defoaming by the Pantray up method.
hardened.

The results are shown in Table 6. Examples 22 to 24 and comparative examples
15 Using the unsaturated polyester resin composition used in Examples 14 to 18 and glass roping, moldings with different glass contents of 146φ were fabricated by filament winding molding method.
The ring was molded and tested according to the Norring Test Method ASTM
2290-64T1D-2291-67).

The results are shown in Table 7. Moreover, the glass content was measured by firing in an electric furnace after measuring the strength. As a result of Examples 19 to 24, molded products with excellent mechanical strength can be obtained by containing 10 to 400 parts by weight of glass fiber. Examples 25, 26 Same as Example 1 (100 parts by weight of the unsaturated polyester resin obtained by straining, 0.1 part by weight of a nonionic surfactant represented by or, 100 parts by weight of talc, and Chopped strand glass fiber used in Example 21 50
Parts by weight were added and cured once in the same manner as in Example 21 to obtain a molded body.

The results are shown in Table 81. As a result, a nonionic surfactant having a structure of V45z (R represents an alkyl group or an alkenyl group) exhibits excellent mechanical properties and also has excellent chemical resistance.

Claims (1)

[Claims] 1 (1) 15 to 45% by weight of an unsaturated polyester prepolymer, 45 to 80% by weight of a crosslinkable unsaturated monomer, and a styrenic thermoplastic polymer soluble in the crosslinkable unsaturated monomer. Combine 5-30
100 parts by weight of an unsaturated polyester resin consisting of % by weight. (2) 0.01 to 5.0 parts by weight of a nonionic surfactant having an HLB value of 6.5 to 16.5. (3) By adding it to the composition consisting of (1) and (2) above, the viscosity can be increased from 300 to 50,000 cps (20
Powdered inorganic filler. (4) An unsaturated polyester resin composition comprising a curing catalyst. 2(1) 15 to 45% by weight of unsaturated polyester prepolymer, 45 to 80% by weight of crosslinkable unsaturated monomer, 5 to 30% of styrenic thermoplastic polymer soluble in crosslinkable unsaturated monomer
100 parts by weight of an unsaturated polyester resin consisting of % by weight. (2) 0.01 to 5.0 parts by weight of a nonionic surfactant having an HLB value of 6.5 to 16.5. (3) By adding it to the composition consisting of (1) and (2) above, the viscosity can be increased from 300 to 50,000 cps (20
Powdered inorganic filler. (4) Curing catalyst. 1. A resin concrete composition comprising an unsaturated polyester resin composition containing 10 to 70% sand in terms of body type content. 3(1) 15 to 45% by weight of unsaturated polyester prepolymer, 45 to 80% by weight of crosslinkable unsaturated monomer, 5 to 30% of styrenic thermoplastic polymer soluble in crosslinkable unsaturated monomer
100 parts by weight of an unsaturated polyester resin consisting of % by weight. (2) 0.01 to 5.0 parts by weight of a nonionic surfactant having an HLB value of 6.5 to 16.5. (3) By adding it to the composition consisting of (1) and (2) above, the viscosity can be increased from 300 to 50,000 cps (20
Powdered inorganic filler. (4) A glass fiber-reinforced unsaturated polyester resin composition characterized by containing 10 to 400 parts by weight of chopped or continuous glass fibers in 100 parts by weight of an unsaturated polyester resin composition comprising a curing catalyst. .