JPS6365087B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition having excellent heat resistance, corrosion resistance and mechanical properties. Unsaturated polyester resin is used in paints, cast products,
It is widely used as FRP (fiber-reinforced plastic), and as its uses have recently expanded, the required performance has also become more diverse. The demand for quality with excellent heat resistance, corrosion resistance, and mechanical properties is one of the demands that has arisen against this background. It is extremely difficult to realize both performance and performance at the same time. This is because, if heat resistance and corrosion resistance are prioritized, the crosslinking density of the resin must be increased or the molecular structure must be rigid, resulting in a brittle resin with poor mechanical properties. On the other hand, if priority is given to mechanical properties, heat resistance and corrosion resistance will decrease. Therefore, the inventors of the present invention completed the present invention as a result of intensive research in order to obtain an unsaturated polyester resin that has the above-mentioned antinomic properties. That is, the present invention provides an alcohol component (a) containing at least 10 mol% of a glycol having a molecular weight of 150 or more, and an acid component (b) containing at least 60 mol% of an α,β-unsaturated dicarboxylic acid and/or its acid anhydride. ), and 100 parts by weight of an unsaturated polyester (A), which is obtained by esterifying 60 parts by weight of unsaturated polyester (A) and 40 parts by weight of styrene, and has a heat deformation temperature of a cured product of a resin liquid of 100 ° C. or higher, 25 to 200 parts by weight of polymerizable unsaturated monomer (B) and general formula (However, R is an alkylene group having 1 to 5 carbon atoms.) A reaction product obtained by addition reaction of 1 to 5 equivalents of alkylene oxide (2) per 1 equivalent of divalent phenol compound (1) represented by The present invention relates to an unsaturated polyester resin composition comprising 15 to 100 parts by weight of (meth)acrylate (C) in which at least 70% of the alcoholic hydroxyl groups of (3) are esters of acrylic acid and/or methacrylic acid. The unsaturated polyester (A) used in the present invention is
As mentioned above, when the resin liquid is made up of 60 parts by weight of unsaturated polyester (A) and 40 parts by weight of styrene, it is an unsaturated polyester whose cured product has a heat distortion temperature of 100°C or higher. If the unsaturated polyester has a heat distortion temperature of less than 100° C., it is impossible to obtain an unsaturated polyester resin composition that has excellent heat resistance, corrosion resistance, and mechanical properties as the object of the present invention. Such unsaturated polyester (A) is produced by increasing the ratio of α,β-unsaturated dicarboxylic acid in the acid component that is its raw material, or by increasing the ratio of α,β-unsaturated dicarboxylic acid in the acid component that is the raw material, or by using glycol with a relatively large molecular weight and a rigid molecular structure as the alcohol component. It can be obtained by a method such as using Such an unsaturated polyester (A) includes an alcohol component (a) containing at least 10 mol% of a glycol having a molecular weight of 150 or more, more preferably at least 20 mol%, and an α,β-unsaturated dicarboxylic acid and/or its At least 60 mol% acid anhydride
There is an unsaturated polyester obtained by esterifying the acid component (b) contained therein, and when this is used, the resulting unsaturated polyester resin composition has good physical properties and is particularly preferred. Such an unsaturated polyester (A) can be easily produced according to a conventionally known method, and the present invention is not dependent on the production method. The polymerizable unsaturated monomer (B) refers to a compound having a polymerizable unsaturated double bond that is liquid at room temperature, such as styrene, vinyltoluene, halogenated styrene, divinyltoluene, α-methylstyrene, etc. Aromatic vinyl compounds, allyl esters such as diallyl phthalate, glycidyl allyl ether,
Methyl methacrylate, ethyl acrylate, glycidyl methacrylate, 8(9)-methacryloyloxy-tricyclo[5.2.1.0 ^2.6 ]deca-3-
Acrylates and methacrylates such as en, etc. can be mentioned. Among these, aromatic vinyl compounds, particularly styrene, are preferred because of their excellent reactivity and solvent effects. Polymerizable unsaturated monomer
The amount of (B) used is 25 to 200 parts by weight per 100 parts by weight of the unsaturated polyester (A). If the amount used is outside this range, the physical properties of the resulting unsaturated polyester resin composition will deteriorate, which is undesirable. (Meth)acrylate (C) contains 1 to 1 alkylene oxide per equivalent of divalent phenol compound (1).
The reaction product (3) is an acrylate and/or methacrylate obtained by a 5-equivalent addition reaction. The divalent phenol compound (1) refers to a compound having two hydroxy-substituted phenol groups in one molecule, such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4- These include hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, bis(4-hydroxyphenyl)methane, and 1,1'-bis(4-hydroxyphenyl)ethane. Examples of alkylene oxide (2) include ethylene oxide, propylene oxide, etc.
One or more of these can be used. (Meth)acrylate (C) is a reaction product (3) having two alcoholic hydroxyl groups per molecule obtained by adding 1 to 5 equivalents of alkylene oxide to 1 equivalent of dihydric phenol compound (1). ) is an acrylate and/or methacrylate in which at least 70%, preferably 80% or more of the alcoholic hydroxyl groups of the reaction product (3) are esters of acrylic acid and/or methacrylic acid. If the amount of alkylene oxide used is outside the above range, the excellent effects of the present invention cannot be obtained, which is not preferred. In addition, the degree of esterification of the alcoholic hydroxyl group of the reaction product (3) is
If it is less than 70%, the physical properties of the resulting unsaturated polyester resin composition will deteriorate, which is not preferable. Such (meth)acrylate (C) can be easily produced according to a conventionally known method. A typical example thereof is a method in which the reaction follows a two-step process as shown below. First step: hydroxyalkyl etherification step of divalent phenol compound (1) 1 to 5 per equivalent of divalent phenol compound (1)
An equivalent amount of alkylene oxide (2) is added as necessary (1) Amine compounds such as triethylamine, triethanolamine, trimethylbenzylammonium chloride; Lewis acids such as boron trifluoride and tin tetrachloride; sodium, lithium, potassium, etc. Alkali metal compounds: Reaction catalysts such as alkaline earth metal compounds such as calcium and magnesium (2) Acetone, trichlene, dichloromethane,
A step of converting the hydroxyl group of the divalent phenol compound (1) into a hydroxyalkyl ether at room temperature or under heating in the presence of an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, etc. Second step: Esterification step If necessary, (1) para. Reaction catalysts such as toluenesulfonic acid, sulfuric acid, Lewis acids, titanate esters, etc. (2) Organic solvents as exemplified in the first step (3) Tertiary amines such as triethylamine and pyridine: sodium carbonate, potassium carbonate, etc. In the presence of a deoxidizing agent such as a weak acid salt of an alkali metal, at room temperature or under heating, the hydroxyl group of the reaction product (3) obtained in the first step is converted into an ester of acrylic acid and/or methacrylic acid. Process. However, the present invention is not dependent on such a method for producing (meth)acrylate (C). Among (meth)acrylates (C), alkylene oxide is added per equivalent of divalent phenol compound (1).
When (meth)acrylate of reaction product (3) obtained by addition reaction of 1.5 to 2.5 equivalents of (2) is used, it is particularly preferable because its action and effect are large. The amount of (meth)acrylate (C) used is 15 to 100 parts by weight per 100 parts by weight of unsaturated polyester (A), and if it is outside this range, the unsaturated polyester resin of the present invention with excellent physical properties No composition is obtained. The unsaturated polyester resin (A), the polymerizable unsaturated monomer (B), and the (meth)acrylate (C) may be mixed in any order, and may be mixed using commonly used equipment. can. The unsaturated polyester resin composition of the present invention thus obtained can be used in the same manner as conventionally known unsaturated polyester resins, and is a cured product that has excellent heat resistance, corrosion resistance, and mechanical properties. It provides: Therefore, the disadvantages of the present invention are particularly useful in fields where contradictory performances such as high corrosion resistance, high heat resistance, and high mechanical properties are simultaneously required, such as corrosion-resistant tanks, corrosion-resistant pipes, corrosion-resistant linings, bathtubs, and gel coats. The saturated polyester resin composition exhibits its performance to the fullest. Hereinafter, the present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples. In addition, "parts" in the examples represent "parts by weight" unless otherwise specified. Example 1 Unipol BP-2P (N) (Sanyo Chemical Co., Ltd.) was added to the flask.
Co., Ltd.), addition reaction product of bisphenol A and propylene oxide, hydroxyl value 315, alkylene oxide addition rate per equivalent of phenolic hydroxyl group (hereinafter referred to as AO/BP) = 1.1) 370 parts and 116 parts of fumaric acid, and the acid value was adjusted according to the usual method.
32 unsaturated polyester (A-1) was obtained. Separately, put Uniol DB-400 (manufactured by Nippon Oil & Fats Co., Ltd., addition reaction product of bisphenol A and propylene oxide, hydroxyl value 275, AO/BP=
1.6) 204 parts, toluene 500 parts, methacrylic acid 130 parts
1 part, 0.1 part of hydroquinone, and 4 parts of para-toluenesulfonic acid were charged, and esterified at 105 to 110°C while removing the toluene-water azeotrope in a fractionating tube, and then washed with water to remove volatile components to obtain UNIONOL. D.B.
-400 methacrylic acid ester (hereinafter referred to as (meth)acrylate (C-1)) was obtained. (meta)
Acrylate (C-1) had a hydroxyl value of 13.4 and an ester value of 184, and 93.2% of the hydroxyl groups in Uniol DB-400 were esterified. 100 parts of unsaturated polyester (A-1), 80 parts of styrene and 50 parts of (meth)acrylate (C-1)
Cobalt octenoate (metal content 8%, hereinafter referred to as OcCo (8%) was added to 100 parts of resin (1) obtained by dissolving two parts
%). ) and 1.5 parts of methyl ethyl ketone peroxide (peroxide content, 55%, hereinafter referred to as MEKPO (55%)) was poured between two glass plates and cured. The physical properties are shown in Table 1. Comparative Example 1 A resin obtained by mutually dissolving 100 parts of unsaturated polyester (A-1) and 80 parts of styrene (relative to
Regarding 1), cure it in the same manner as in Example 1,
A resin plate was obtained. Its physical properties are shown in Table 1. Comparative Example 2 Epicote 828 (manufactured by Ciel, bisphenol A)
An epoxy polymethacrylate was obtained according to a conventional method using a type epoxy resin (epoxy equivalent: 187 parts), 88 parts of methacrylic acid, 0.05 part of hydroquinone, and 1.0 part of triethylamine. Next, 100 parts of unsaturated polyester (A-1), 80 parts of styrene, and 50 parts of the epoxy polymethacrylate were mutually dissolved to obtain a resin (ratio-2).
Table 1 shows the physical properties of a resin plate obtained by curing the resin (ratio -2) in the same manner as in Example 1.

【table】

[Table] As is clear from Table 1, although the resin (ratio -1) has excellent heat resistance and corrosion resistance, it has a low tensile elongation rate and is brittle. Also, mechanical strength is low. The resin (ratio -2) has a large tensile elongation rate, high mechanical strength, strong mechanical properties, and excellent heat resistance, but is inferior in corrosion resistance. On the other hand, resin (1) has the same or better performance as resin (ratio -2) in terms of heat resistance and mechanical properties, and has excellent corrosion resistance equivalent to resin (ratio -1). Resin (ratio -1), resin (ratio -2)
It can be seen that it has excellent performance, combining heat resistance, corrosion resistance, and mechanical properties that could not be achieved with other materials. Example 2 100 parts of unsaturated polyester (A-1), 120 parts of styrene, and methacrylate of the reaction product of bisphenol A and propylene oxide (AO/BP = 2.4, hydroxyl value 222) (hydroxyl value 13.3) , ester value 155, hereinafter referred to as (meth)acrylate (C-
2). ) Resin obtained by mutually dissolving 40 parts (2)
The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 3 Using 120 parts of hydrogenated bisphenol A, 57 parts of neopentyl glycol, 33 parts of isophthalic acid and 78 parts of maleic anhydride, the acid value was determined according to a conventional method.
21 unsaturated polyester (A-2) was obtained. Example 1 Regarding the resin (3) obtained by mutually dissolving 100 parts of unsaturated polyester (A-2), 100 parts of styrene, and 80 parts of methacrylate (C-1).
The physical properties of the cured product were evaluated in the same manner as above. The results are shown in Table 2. Comparative Example 3 100 parts of unsaturated polyester (A-2), 100 parts of styrene and (meth)acrylate (C-1)
Regarding the resin obtained by mutually dissolving 8 parts (ratio-3), the physical properties of the cured product were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 4 3(4),8(9)-bis-hydroxymethyl-tricyclo[5.2.1.0 ^2.6 ] Conventional method using 39 parts of decane, 65 parts of propylene glycol, 25 parts of isophthalic acid and 83 parts of maleic anhydride. An unsaturated polyester (A-4) having an acid value of 23 was obtained in accordance with the following. 100 parts of unsaturated polyester (A-4), 80 parts of styrene and 60 parts of (meth)acrylate (C-2)
Regarding the resin (4) obtained by mutually dissolving the parts, the physical properties of the cured product were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 5 100 parts of unsaturated polyester (A-1), 70 parts of styrene, and a reaction product of 2,2-bis(4-hydroxyphenyl)butane and ethylene oxide (AO/BP=1.3, hydroxyl value 315) acrylate (hydroxyl value 13.7, ester value 214, hereinafter referred to as (meth)
It is called acrylate (C-3). ), and the physical properties of the cured product were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 6 A reaction product (AO/BP=
3.2, ethylene oxide to propylene oxide addition ratio (EO/PO) = 0.7, hydroxyl value 199) acrylate (hydroxyl value 16.2, ester value 146) 80
Example 1 Regarding the resin (6) obtained by mutually dissolving the
The physical properties of the cured product were evaluated in the same manner as above. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. At least a glycol with a molecular weight of 150 or more
An unsaturated polyester obtained by esterifying an alcohol component (a) containing 10 mol% and an acid component (b) containing at least 60 mol% of an α,β-unsaturated dicarboxylic acid and/or its acid anhydride. A) 100 parts by weight of an unsaturated polyester (A) having a heat distortion temperature of 100°C or more of a cured resin liquid consisting of 60 parts by weight and 40 parts by weight of styrene, 25 to 25 parts by weight of a polymerizable unsaturated monomer (B)
200 parts by weight and general formula (However, R is an alkylene group having 1 to 5 carbon atoms.) A reaction product obtained by addition reaction of 1 to 5 equivalents of alkylene oxide (2) per 1 equivalent of divalent phenol compound (1) represented by An unsaturated polyester resin composition comprising 15 to 100 parts by weight of (meth)acrylate (C) in which at least 70% of the alcoholic hydroxyl groups of (3) are esters of acrylic acid and/or methacrylic acid. 2 (Meth)acrylate (C) contains alkylene oxide (2) per equivalent of divalent phenol compound (1).
Reaction product obtained by 1.5-2.5 equivalent addition reaction (3)
The unsaturated polyester resin composition according to claim 1, which is a (meth)acrylate of.