JPH107777A - Unsaturated polyester and unsaturated polyester resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an unsatd. polyester which has a high clarity, is excellent in resistances to water, hydrolysis, heat, and weather, and gives a compsn. highly compatible with styrene by selecting a specific unsatd. polyester. SOLUTION: This polyester is obtd. by the condensation of a polyhydric alcohol or polyhydric alcohol mixture contg. 10-100mol% at least one diol compd. selected from among diol compds. represented by formula I (wherein R<1> to R<4> are each H or methyl) and formula II (wherein R<5> to R<10> are each H oar methyl) and a polycarboxylic acid or polycarboxylic acid mixture contg. 5-100mol% aliph. unsatd. dicarboxylic acid. A so-called unsated. polyester resin compsn. is obtd. by dissolving and diluting this polyester with a free-radical- polymerizable monomer and is used for curing reaction. The amt. of the polymerizable monomer mixed is 80-5wt.% of the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester and an unsaturated polyester resin composition using the same, and more particularly, to a specific amount of a specific diol compound and a specific aliphatic unsaturated dicarboxylic acid. Unsaturated polyester, and an unsaturated polyester using this unsaturated polyester, which has high transparency, and is excellent in water resistance, hydrolysis resistance, heat resistance, and weather resistance, and has good compatibility with styrene. The present invention provides a resin composition.

[0002]

2. Description of the Related Art Unsaturated polyester resins used in applications such as gel coats, paints, decorative plates, artificial marbles, and FRPs have high transparency and excellent physical properties such as water resistance, heat resistance, and weather resistance. Required. Conventionally, aliphatic polyesters such as propylene glycol and neopentyl glycol have been mainly used as polyhydric alcohol components in unsaturated polyester resins used for such purposes.

[0003]

However, when propylene glycol is used, the concentration of ester groups in the produced unsaturated polyester increases, and the water resistance and weather resistance deteriorate. In addition, since it has a secondary alcohol, the reaction during the synthesis of the unsaturated polyester is relatively slow,
There is a disadvantage that it is difficult to control the composition ratio of polyhydric alcohol / polycarboxylic acid due to high volatility.

When neopentyl glycol is used,
The crystallinity of the polyester chain is high, and particularly those having a highly symmetrical component such as terephthalic acid as a polycarboxylic acid in the molecule have high crystallinity, and therefore are likely to be molded products having poor transparency. In addition, since the temperature difference between the melting point and the boiling point is relatively close, and the raw material neopentyl glycol tends to volatilize during the synthesis, there is a disadvantage that the adjustment of the composition ratio is troublesome as in the case of propylene glycol.

In order to solve these drawbacks, polyhydric alcohol raw materials such as 1,4-cyclohexanedimethanol (JP-A-50-28595) and bisphenol A
Alkylene oxide adduct, hydrogenated bisphenol A,
Tricyclodecane dimethanol and the like (UK Patent No. 766,
666, British Patent 1,319,432) may be added. However, unsaturated polyesters made from these polyhydric alcohols are less transparent due to crystallinity,
There are disadvantages such as poor weather resistance, poor reactivity during synthesis, and brittle molded products due to rigid functional groups entering the main chain.

[0006]

In view of these circumstances, the present inventors have conducted intensive studies, and as a result, have found that a cyclohexane ring having a 2-methyl group in the side chain or 3-methylbicyclo [2,2,1] heptane. Unsaturated polyester using a propanediol compound having a ring as a polyhydric alcohol raw material has few disadvantages shown above, and a molded product of an unsaturated polyester resin composition using this unsaturated polyester has transparency, weather resistance, Both water resistance and heat resistance are increased, and by using the diol compound as a polyhydric alcohol raw material, there is also an effect that the compatibility between the generated unsaturated polyester and styrene is enhanced. It has only a highly reactive primary alcohol group and has a high boiling point, so that the reaction during the synthesis of unsaturated polyester is fast and polyvalent. Deviation of the composition of a polyhydric alcohol / polybasic carboxylic acids coming from the loss due to volatilization of the alcohol component found that there is little, was led to form a present invention. These advantages obtained by the present invention are considered to be derived from the fact that the diol compound has a structure having both a somewhat large hydrophobic saturated hydrocarbon group and a methyl group that suppresses crystallinity, but is limited to this reason. Not something.

The invention of claim 1 of the present invention provides at least one of the diol compounds represented by the following formula (1) or (2):
A polyhydric alcohol or polyhydric alcohol mixture containing 10 to 100 mol% of seeds;

[0008]

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Wherein R ^{1 to} R ⁴ each represent hydrogen or a methyl group. ]

[0010]

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Wherein R ^{5 to} R ¹⁰ each represent hydrogen or a methyl group. An unsaturated polyester obtained by condensation with a polycarboxylic acid or a mixture of polycarboxylic acids containing 5 to 100 mol% of an aliphatic unsaturated dicarboxylic acid.

According to a second aspect of the present invention, there is provided an unsaturated polyester comprising a mixture of 20 to 95% by weight of the unsaturated polyester according to the first aspect and 80 to 5% by weight of a radical polymerizable monomer. It is a resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The diol compounds represented by the above formulas (1) and (2) used as a raw material of the unsaturated polyester of the present invention are synthesized by a known method.
That is, these glycol compounds can be easily obtained by reacting a Diels-Alder adduct of a diene compound such as butadiene, isoprene, piperylene, or cyclopentadiene with crotonaldehyde with formalin and an alkali, and hydrogenating the generated unsaturated diol. .

Specific examples of the diol compounds represented by the above formulas (1) and (2) include, for example, 2-methylcyclohexane-1,1-dimethanol and 2,3-dimethylcyclo-oxane-1,1-dimethol. Methanol, 2,4-dimethylcyclohexane-1,1-dimethanol, 2,5-dimethylcyclohexane-1,1-dimethanol, 2,6-
Dimethylcyclohexane-1,1-dimethanol, 3-
Methyl-bicyclo [2,2,1] heptane-2,2-dimethanol, 3,4-dimethyl-bicyclo [2,2,
1] Heptane-2,2-dimethanol, 3,5-dimethyl-bicyclo [2,2,1] heptane-2,2-dimethanol, 3,6-dimethyl-bicyclo [2,2,1] heptane- 2,2-dimethanol, 3,7-dimethyl-bicyclo [2,2,1] heptane-2,2-dimethanol, 1,3-dimethyl-bicyclo [2,2,1] heptane-2,2- Examples include, but are not limited to, dimethanol.

In the present invention, in addition to using the diol compounds represented by the above formulas (1) and (2) alone, a mixture of these diol compounds and a polyhydric alcohol generally used generally for unsaturated polyesters is used. It is possible to In this case, one or more polyhydric alcohols may be mixed. However, in the present invention, the polyhydric alcohol mixture used contains at least one diol compound represented by the following formula (1) or (2) in an amount of 10 to 100 mol%, preferably 30 to 100 mol%.
It is important that the content be in the range of 100 to 100 mol%. 10 mol%
If it is less than 1, any of the properties of transparency, heat resistance, weather resistance and water resistance of the molded product of the unsaturated polyester or unsaturated polyester resin composition is greatly reduced, and is represented by the following formula (1) or (2). The effect of using the diol compound is hardly observed.

Specific examples of these polyhydric alcohols include saturated aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene and the like. Diols having an ether bond such as glycol, 1,4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A, xylylene glycol, diols having an aromatic ring such as bisphenol A alkylene glycol adduct,
Examples include, but are not limited to, diols having an ester group such as hydroxypivalyl hydroxypivalate, and diols having a halogen group such as dibromoneopentyl glycol. Further, a trifunctional or higher functional polyol compound can be used in combination, and specifically, glycerin, trimethylolpropane, pentaerythritol and the like can be used.

As the aliphatic unsaturated dicarboxylic acid used for preparing the unsaturated polyester of the present invention, any aliphatic unsaturated dicarboxylic acid having a radical polymerizable double bond in the molecule can be used. . Specific examples include maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. In addition to using these aliphatic unsaturated dicarboxylic acids alone as raw materials for the unsaturated polyester of the present invention, they do not participate in polymerization with aliphatic unsaturated dicarboxylic acids, that is, have a radical polymerizable double bond in the molecule. Mixtures with no polyvalent carboxylic acids can be used.

As the polyvalent carboxylic acid that can be used by mixing, any one can be used as long as it is generally used for unsaturated polyester resins. These may be used alone or in combination of two or more. However, in the present invention, the polyvalent carboxylic acid mixture used is a mixture of the above-mentioned aliphatic unsaturated dicarboxylic acid in 5 to 5.
It is important to contain 100 mol%, preferably 20 to 100 mol%. If it is less than 5 mol%, it becomes difficult to obtain a molded product having sufficient physical properties by curing.

Specific examples of polycarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, hexahydrophthalic acid, adipic acid,
Sebacic acid, tetrabromophthalic acid, trimellitic acid,
Examples include, but are not limited to, pyromellitic acid.

In producing the unsaturated polyester, the aliphatic unsaturated dicarboxylic acid used as a raw material and the polyvalent carboxylic acid which can be used by mixing with the aliphatic unsaturated dicarboxylic acid are not limited to those used in the form of a free carboxylic acid. It is also possible to use the unsaturated polyester raw material in the form of an anhydride or an ester with a lower alcohol.

The unsaturated polyester in the present invention is synthesized in the same manner as a general unsaturated polyester.
This is achieved by an esterification or transesterification reaction between a polyhydric alcohol and a polycarboxylic acid. Usually, the synthesis is carried out by mixing a polyhydric carboxylic acid and a polyhydric alcohol and heating. In the synthesis of the unsaturated polyester in the present invention, a catalyst may be used depending on the degree of the reaction.

The unsaturated polyester obtained by the polycondensation reaction can be used as an unsaturated alkyd resin as it is. Usually, the unsaturated polyester is dissolved and diluted with a radical polymerizable monomer to obtain a so-called unsaturated alkyd resin. An unsaturated polyester resin composition is prepared and used for a curing reaction.

As the polymerizable monomer capable of being combined with the unsaturated polyester of the present invention, any polymerizable monomer can be used as long as it can be cured by radical copolymerization with the unsaturated polyester of the present invention. Specific examples include monofunctional monomers such as styrenes such as styrene, α-methylstyrene, and chlorostyrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, and hydroxyethyl ( (Meth) acrylate esters such as (meth) acrylate and glycidyl (meth) acrylate, (meth) acrylonitrile, vinyl acetate, maleic anhydride, itaconic anhydride, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, acrylamide, N- Methylmaleimide, N-phenylmaleimide, N-vinylpyrrolidone and the like can be mentioned.

In addition to the above monofunctional monomers, polyfunctional monomers can be used. Specific examples of the polyfunctional monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6
Polyfunctional acrylate esters such as hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diallyl phthalate, diallyl isophthalate, and diallyl terephthalate , Diallyl carbonate, ethylene glycol diallyl carbonate, polyallyl compounds such as triallyl isocyanurate, divinylbenzene, phenylene bismaleimide and the like, but the present invention is not limited thereto.

These polymerizable monomers may be used alone or in combination of two or more. The amount of the polymerizable monomer is
80 to 5 of the entire unsaturated polyester resin composition of the present invention
%, Preferably 10 to 50% by weight with the unsaturated polyester. 8 polymerizable monomers
If it exceeds 0% by weight, the advantages of the unsaturated polyester of the present invention cannot be utilized in the cured product. On the other hand, when the content is less than 5% by weight, the viscosity of the composition is substantially too high, so that not only the molding operation is difficult but also a good molded product is difficult to obtain.

For the purpose of adjusting the stability and curability of the unsaturated polyester resin composition of the present invention, quinones, phenols, copper salts, hydrazine salts, amidine salts, ammonium salts, amines, nitro compounds And other known inhibitors.

In order to obtain a molded article by curing the unsaturated polyester resin composition of the present invention, as in the case of a general unsaturated polyester, it is mixed with a radical initiator and other compounding agents, and heat and / or light, radiation, etc. Curing is carried out using.

The radical initiator used for the curing reaction is not particularly limited, and a known initiator such as a peroxide, an azo compound, or a combination thereof with an accelerator can be used. These are appropriately selected depending on the desired reaction mode and reaction temperature.

[0029]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. The diol compounds used in this example were synthesized by known methods.

Example 1 (Synthesis of Unsaturated Polyester and Unsaturated Polyester Resin Composition 1) 2-Methylcyclohexane was placed in a 100 ml four-necked flask equipped with a thermometer, a nitrogen gas inlet tube, an induction stirrer, and a condenser. 1,1-dimethanol 31.65
g (0.20 mol), 9.8 g of maleic anhydride (0.
10 mol), 14.8 g of phthalic anhydride (0.10 mol)
1) was added, and the contents were replaced with nitrogen. Then, the contents were immersed in an oil bath, and the temperature was gradually increased to 180 ° C. over 3 hours with stirring. At this temperature, the reaction was continued for another 2 hours until almost no water was distilled off. Thereafter, the temperature is further increased to 190
C., and the pressure was gradually reduced by an aspirator to evacuate water at about 50 mmHg. In this state, the reaction was carried out for 2 hours, the pressure was returned to normal pressure by introducing nitrogen gas, and a small amount of the content (unsaturated polyester) was collected.

After sampling, remove the oil bath, cool, and add about 10 mg of hydroquinone at about 120 ° C.
Further, 23 ml of styrene was added, and the mixture was stirred until it became uniform. The unsaturated polyester resin composition thus obtained was pale yellow and transparent, and had a viscosity of 1.5 Pa · s.

The analysis results of the collected unsaturated polyester were as follows. Infrared absorption spectrum (chloroform solvent, liquid membrane method): 1
Strong absorption ¹ H NMR (deuterated chloroform solvent) around 728 cm ^-1 : 1.0 ppm,
1.3 to 2.0 ppm, 4.4 ppm, 6.2 ppm,
Signal at 6.7 ppm, 7.5 ppm, and 7.7 ppm, integrated intensity ratio 3: 9: 4: 2: 1 Molecular weight measurement by GPC: 2050 in terms of polystyrene Acid value: 22.0

(Example 2) (Synthesis 2 of unsaturated polyester and unsaturated polyester resin composition) 31.65 g of 2-methylcyclohexane-1,1-dimethanol was placed in the same reactor as in Example 1.
(0.20 mol), 9.8 g (0.1
0 mol), 19.4 g of dimethyl terephthalate (0.1
0 mol) and 248 mg of dibutyltin oxide. The contents were replaced with nitrogen, then immersed in an oil bath, and the temperature was slowly raised to 180 ° C. over 3 hours with stirring. The reaction was continued at this temperature for another 2 hours until almost no alcohol and water were distilled off. After that, the temperature is further increased by 2
The temperature was raised to 10 ° C., and the pressure was gradually reduced by an aspirator at about 50 mmHg to promote the distillation of alcohol and water.
In this state, the reaction was carried out for 2 hours, the pressure was returned to normal pressure by introducing nitrogen gas, and a small amount of the content (unsaturated polyester) was collected.

After sampling, remove the oil bath and cool down. At around 120 ° C., add 10 mg of hydroquinone.
Further, 23 ml of styrene was charged and stirred until the mixture became uniform. The unsaturated polyester resin composition thus obtained was pale yellow and transparent, and had a viscosity of 2.0 Pa · s. The analysis results of the unsaturated polyester sampled during the measurement were as follows. Infrared absorption spectrum (chloroform solvent, liquid membrane method): 1
Strong absorption ¹ H NMR (deuterated chloroform solvent) around 729 cm -1: 1.0 ppm,
1.3 to 2.0 ppm, 4.4 ppm, 6.2 ppm,
Signal at 6.7 ppm and 8.1 ppm, integrated intensity ratio 3: 9: 4: 0.1: 0.9: 2 Measurement of molecular weight by GPC: 2200 in terms of polystyrene Acid value: 18.0

(Example 3) (Synthesis 3 of unsaturated polyester and unsaturated polyester resin composition) In the same manner as in Example 1, 34.45 g of 2,4-dimethylcyclohexane-1,1-dimethanol
(0.2 mol), 9.8 g of maleic anhydride (0.1 m
ol) and 14.8 g (0.1 mol) of phthalic anhydride to prepare an unsaturated polyester having an acid value of 25. To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained was pale yellow and transparent, and had a viscosity of 2.7 Pa · s.

Example 4 (Synthesis 4 of Unsaturated Polyester and Unsaturated Polyester Resin Composition) 3-Methylbicyclo [2,2,1] heptane-2,2-dimethanol
45 g (0.2 mol), maleic anhydride 9.8 g
(0.1 mol), 14.8 g of phthalic anhydride (0.1 m
ol) to prepare an unsaturated polyester having an acid value of 23.
To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained is pale yellow and transparent, and has a viscosity of 2.2.
Pa · s.

Example 5 Synthesis 5 of Unsaturated Polyester and Unsaturated Polyester Resin Composition As in Example 1, 15.8 g of 2-methylcyclohexane-1,1-dimethanol (0.1 mol
l), 10.4 g of neopentyl glycol (0.1 mol
1), an unsaturated polyester having an acid value of 27 was prepared from 9.8 g (0.1 mol) of maleic anhydride and 14.8 g (0.1 mol) of phthalic anhydride. To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained was pale yellow and transparent, and had a viscosity of 1.3 Pa · s.

(Comparative Example 1) (Synthesis of unsaturated polyester and unsaturated polyester resin composition) As in Example 1, 15.22 g (0.2 mol) of propylene glycol and 9.8 of maleic anhydride were used.
g (0.1 mol), phthalic anhydride 14.8 g (0.1
mol)) to prepare an unsaturated polyester having an acid value of 30. To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained is pale yellow and transparent, and has a viscosity of 1.
It was 0 Pa · s.

Comparative Example 2 (Synthesis of unsaturated polyester and unsaturated polyester resin composition) In the same manner as in Example 2, 20.83 g of neopentyl glycol and 9.8 g of maleic anhydride (0.1 mol)
l), 19.4 g of dimethyl terephthalate (0.1 mol
l), acid number 32 from 248 mg of dibutyltin oxide
Was prepared. To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained was clouded at room temperature due to crystallization.

Comparative Example 3 (Synthesis of unsaturated polyester and unsaturated polyester resin composition) In the same manner as in Example 1, cyclohexane-1,
An unsaturated polyester having an acid value of 20 from 28.8 g (0.2 mol) of 1-dimethanol, 9.8 g (0.1 mol) of maleic anhydride, 19.4 g (0.1 mol) of dimethyl terephthalate, and 248 mg of dibutyltin oxide. Was prepared. To this, 10 mg of hydroquinone and 23 g of styrene were added and stirred until uniform. The unsaturated polyester resin composition thus obtained exhibited cloudiness at room temperature, which was considered to be due to crystallization.

(Curing of unsaturated polyester resin composition)
Perbutyl O (manufactured by NOF CORPORATION) at room temperature in 20 g of the unsaturated polyester resin composition obtained in Examples 1 to 5.
0.2 g was added and mixed until uniform. The mixture was poured between two glass plates spaced 3 mm apart,
Curing was performed in an oven at 80 degrees for 5 hours. Further, the glass plate was removed, and after-curing was performed in an oven at 120 ° C. for 2 hours. Transparent plates were obtained by the above curing reactions. In addition, a curing reaction was similarly performed on the unsaturated polyester resin compositions obtained in Comparative Examples 1 to 3. For the molded plates obtained by curing, respectively, Barcol hardness (JIS K-6911), light transmittance (A
STM D1003), bending strength (JIS K-720)
3) Heat distortion temperature (HDT) (JIS K-720)
7) Water absorption after boiling for 500 hours (JIS K-720)
9) was measured. Table 1 shows the results.

[0042]

[Table 1]

From Table 1, all the unsaturated polyester resin compositions obtained in Examples 1 to 5 are cured products having high light transmittance by curing, and the molded products are excellent in transparency. Recognize. Further, since the cured products obtained in Examples 1 to 5 have both high bending strength, heat deformation temperature, and low boiling water absorption, it is understood that they are also excellent in heat resistance and water resistance. On the other hand, the molded product obtained in Comparative Example 1 was inferior in heat resistance and water resistance, and the molded product obtained in Comparative Example 2 was inferior in transparency, heat resistance and water resistance, and was obtained in Comparative Example 3. The result was inferior in transparency.

[0044]

According to the unsaturated polyester of the present invention or the unsaturated polyester resin composition using the unsaturated polyester, the transparency is high and the water resistance, hydrolysis resistance, heat resistance and weather resistance are excellent. A cured product is obtained. Further, the unsaturated polyester of the present invention has good compatibility with styrene and has high reactivity at the time of polyester synthesis. Therefore, the unsaturated polyester of the present invention and the unsaturated polyester resin composition using the unsaturated polyester are useful as molding materials such as gel coats, paints, decorative plates, artificial marble, and FRP.

Claims (2)

[Claims] 1. A polyhydric alcohol or a mixture of polyhydric alcohols containing 10 to 100 mol% of at least one diol compound represented by the following formula (1) or (2): [Wherein, R ^{1 to} R ⁴ each represent hydrogen or a methyl group. ] [Wherein, R ^{5 to} R ¹⁰ each represent hydrogen or a methyl group. An unsaturated polyester obtained by condensation with a polycarboxylic acid or a mixture of polycarboxylic acids containing 5 to 100 mol% of an aliphatic unsaturated dicarboxylic acid. 2. The unsaturated polyester 20 according to claim 1,
An unsaturated polyester resin composition comprising a mixture of about 95% by weight and about 80% by weight of a radical polymerizable monomer.