JPH07309935A - High-molecular-weight unsaturated polyester resin composition and its cured item - Google Patents

Abstract

PURPOSE:To obtain a high-molecular-weight unsaturated polyester resin compsn. excellent in bending strength, bending modulus, and insulation resistance after boiling treatment. CONSTITUTION:This compsn. contains a high-mol.wt. unsatd. polyester which is obtd. by reacting a polyhydric component s contg. 1,4-cyclohaxamethanol with an acid component comprising 10mol% of higher alpha,beta-unsatd. polybasic acid (anhydrid) and 90mol% or lower satd. on usatd. polybasic acid (anhydride) and has number-average mol.wt. of 5,000 or higher an ally ester copolymerizable with the polyester and/or an allyl ester resin, and a silica powder and/or glass fibers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an unsaturated polyester resin composition, and more specifically toughness,
A high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more, which is excellent in flexibility, flexural strength, impact resistance, dimensional stability, adhesiveness, heat resistance, etc., an allyl ester copolymerizable with the unsaturated polyester, and TECHNICAL FIELD The present invention relates to an unsaturated polyester resin composition containing an allyl ester resin and / or silica powder and / or glass fiber, which has little shrinkage during curing and is excellent in mechanical strength and electrical properties, and a cured product thereof.

[0002]

2. Description of the Related Art Heretofore, a molded article molded from a thermosetting resin composition containing a filler in an unsaturated polyester resin has been known, and is used in a bathtub, a wash counter, a kitchen counter or a table. Has been done. Further, in recent years, by using glass powder as the above-mentioned filler, a molded product excellent in depth feeling (transparency) has been produced.
However, the number average molecular weight of the conventional unsaturated polyester resin is at most about 3,000, and the thermosetting resin composition using the same has toughness, flexibility, bending strength, bending elastic modulus, water resistance, Physical properties such as insulation resistance (boiling 2 hr) were not always satisfactory.

[0003]

The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a molded article excellent in bending strength, bending elastic modulus, heat resistance, water resistance and insulation resistance (boiling 2 hr). An object is to provide an unsaturated polyester resin composition and a cured product thereof that can be obtained.

[0004]

As a result of intensive studies conducted by the present inventors to improve these drawbacks, the present inventors have found that a number average molecular weight of 5,0 is used in place of a usual low molecular weight unsaturated polyester resin.
It was found that an unsaturated polyester resin composition excellent in flexural strength, flexural modulus, heat resistance, water resistance, and insulation resistance (boiling 2 hr) can be obtained by using a high molecular weight unsaturated polyester of 00 or more, and the present invention Has been completed.

That is, the present invention relates to [I] (a) a polyhydric alcohol component in which at least one type of polyhydric alcohol is 1,4-cyclohexanedimethanol, and (b) α, β
-The proportion of unsaturated polybasic acid (or its anhydride) used is 1
The number average molecular weight obtained by reacting with an acid component is 0 mol% or more and (c) the proportion of the saturated or unsaturated polybasic acid (or its anhydride) used is 90 mol% or less, and the number average molecular weight is 5,0.
00 or more high molecular weight unsaturated polyester, [II] allyl ester and / or allyl ester resin copolymerizable with the unsaturated polyester, and [III] silica powder and / or
Alternatively, the present invention relates to a high molecular weight unsaturated polyester resin composition containing glass fiber and a cured product thereof.

The present invention will be described in more detail below.

At least one of the polyhydric alcohol components of the high molecular weight unsaturated polyester used in the present invention is 1,
It needs to be 4-cyclohexanedimethanol. In other words, in the present invention, as the polyhydric alcohol component, 1,4-cyclohexanedimethanol may be used alone, or 1,4-cyclohexanedimethanol may be used in combination with another polyhydric alcohol. . 1,4-
When cyclohexanedimethanol and other polyhydric alcohol are used in combination, the properties of the 1,4-cyclohexanedimethanol used alone, that is, the physical properties of the cured resin, particularly that the toughness is improved, esterification and deglycolization are performed. It is necessary to blend other polyhydric alcohols within the range that does not impair the features such as no gelation risk in the process of polymerization, good compatibility of the produced unsaturated polyester with solvent and monomer, etc. For that purpose, it is preferable to use 1,4-cyclohexanedimethanol in at least 50 mol% of the whole polyhydric alcohol component.

Examples of other polyhydric alcohols used in combination include:
For example ethylene glycol, propylene glycol, 2
-Methylpropanediol-1,3, diethylene glycol, dipropylene glycol, 2,2-diethylpropanediol-1,3, butanediol-1,4, butanediol-1,3, neopentyl glycol, hydrogenated bisphenol, bisphenol A propylene oxide adduct and the like can be mentioned.

The acid component used in the present invention is α,
β-unsaturated polybasic acid (or its anhydride) is 10 mol%
Above, the saturated or unsaturated polybasic acid (or its anhydride) is 90 mol% or less.

In the present invention, the use of α, β-unsaturated polybasic acid (or its anhydride) is essential, and specific examples thereof include maleic anhydride, fumaric acid, itaconic acid and the like.

The use of a saturated or unsaturated polybasic acid (or its anhydride) is not essential to the invention,
For example, phthalic anhydride, isophthalic acid, terephthalic acid (and dimethyl ester), tetrahydrophthalic anhydride,
Examples include endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, succinic acid, adipic acid, sebacic acid, dodecanoic acid and hettic acid.

The ratio of the α, β-unsaturated polybasic acid (or its anhydride) to be used can be changed according to the purpose in the range of 10 mol% to 100 mol%. Use ratio of α, β-unsaturated polybasic acid (or its anhydride) is 10 mol%
If it is less than the above range, the physical properties, particularly the mechanical properties of the cured product, are rapidly deteriorated, the curability is also deteriorated, and there is a marked tendency that complete curing becomes difficult.

In order to synthesize the unsaturated polyester having a number average molecular weight of 5,000 or more according to the present invention, an organic compound such as antimony, titanium, zirconium, zinc, lead, manganese or a transesterification catalyst such as antimony trioxide is used in combination. Is necessary, especially an organic compound of titanium,
For example, alkoxy titanium compounds, chelate compounds such as titanium oxyacetylacetonate, and antimony trioxide are preferably used. The amount of the transesterification catalyst used is 0.0001 to 0.5 phr, and the optimum range is 0.01 to 0.1 phr.

The unsaturated polyester is synthesized by first performing an esterification reaction and then performing a deglycolization reaction in the presence of a transesterification catalyst to obtain a high molecular weight. At this time, under a high vacuum of 1 Torr or less as much as possible. It is necessary to carry out. The unsaturated polyester thus obtained has a number average molecular weight of 5,000 or more, and the terminal groups are substantially hydroxyl groups.

In the present invention, even if the high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more is used as it is as a component for preparing a high molecular weight unsaturated polyester resin composition, the effect of the present invention is obtained. By expressing the above-mentioned high molecular weight unsaturated polyester with a polybasic acid anhydride having or not having a free carboxyl group, 10 mol% or more of the terminal hydroxyl groups of the high molecular weight unsaturated polyester are carboxylated. It is preferable to use the modified high molecular weight unsaturated polyester. In the present invention, both polyesters are referred to as a high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more.

The polybasic acid anhydride used for modification includes
Polybasic acid anhydrides with or without free carboxyl groups are used. Examples of the anhydride having no free carboxyl group include maleic anhydride, succinic anhydride, adipic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, and pyropyrolic anhydride. Examples include meritic acid. Phthalic anhydride is also available, but is sublimable and difficult to carboxylate in calculated amounts. As the polybasic acid anhydride having a free carboxyl group, trimellitic acid anhydride is preferred. Since tetrafunctional polybasic acid anhydrides such as pyromellitic dianhydride are in danger of gelation when used in an equimolar amount, it is convenient to use one acid anhydride group by monoesterification.

As a matter of course, since the number of end groups per unit weight varies depending on the molecular weight, the number average molecular weight referred to in the present invention is GPC (column Showdex, No. KF-
805 type, exclusion limit molecular weight polystyrene 4 × 10
⁶ ) Based on measurement. The amount of polybasic anhydride with or without free carboxyl groups needed to modify the high molecular weight unsaturated polyester was calculated assuming that both ends of the high molecular weight unsaturated polyester are hydroxyl groups. A polybasic acid anhydride having or not having a free carboxyl group will be added at a required amount at the reaction temperature at the end of the deglycolization reaction, and if necessary, treated at a reduced pressure of 5 Torr or less. This makes it possible to modify part or all of the terminal hydroxyl groups without reducing the number average molecular weight.

When the number average molecular weight of the high molecular weight unsaturated polyester and the modified high molecular weight unsaturated polyester is less than 5,000, heat resistance, mechanical properties and chemical resistance are inferior.

When the terminal group of the conventional low molecular weight unsaturated polyester is acid-modified, the ratio of the terminal group becomes too high,
As a result, water resistance and alkali resistance of the resulting unsaturated polyester resin are impaired, miscibility with the filler is deteriorated, and the kneaded product solidifies and becomes unmoldable. However, in the high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more according to the present invention, such a defect is alleviated because the ratio of the terminal groups is lowered. As a result, it is possible to obtain a high molecular weight unsaturated polyester resin composition having a high molecular weight, good miscibility with a filler, and excellent mechanical properties and chemical resistance.

The allyl ester and allyl ester resin which are copolymerized with the high molecular weight unsaturated polyester used in the present invention are used for improving the processability when preparing the composition and the miscibility and adhesiveness with the filler. Is a diallyl ester of orthophthalic acid, isophthalic acid, and terephthalic acid, a partially polymerized product of the diallyl ester, and is a relatively linear oligomer containing a double bond in the molecule and the diallyl ester and glycol. Examples of the reaction product include a reaction product obtained by reacting the compounds with an excess of diallyl ester, and a mixture thereof. When the allyl ester and the allyl ester resin are used in combination, the usage ratio is arbitrary.

The silica powder used in the present invention has a particle size of 2 to 50 .mu. The silica powder may be used after being treated with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or a surface treatment agent according to other purposes in order to have an affinity with the base resin of the present invention. it can.

The glass fiber used in the present invention is a glass fiber having a predetermined diameter, which is obtained by rapidly cooling molten glass while drawing it by various methods. , Roving obtained by uniformly aligning strands into a bundle, crushed glass fiber, and the like, and any of them can be used in the present invention. The glass fiber can be used after being treated with a silane coupling agent such as aminosilane or epoxysilane, a chromic chloride, or a surface treatment agent depending on the purpose in order to have an affinity with the base resin of the present invention.

The length of the glass fiber in the present invention has a great influence on the physical properties of the obtained molded product and the workability at the time of manufacturing the molded product. Generally, as the glass fiber length increases, the physical properties of the molded product improve, but conversely, the workability during the manufacturing of the molded product deteriorates. For this reason, in the present invention, glass fibers having a length of 0.1 to 6 mm, preferably 0.1 to 4 mm are suitable in terms of balance of physical properties and workability of the molded product.

The amount of the allyl ester and / or allyl ester resin used for preparing the high molecular weight unsaturated polyester resin composition of the present invention is 10 to 10 parts by weight based on 100 parts by weight of the high molecular weight unsaturated polyester resin.
It is 0 part by weight, preferably 30 to 100 parts by weight. When the amount of the allyl ester and / or the allyl ester resin used is less than 10 parts by weight, the processability when adjusting the composition and the miscibility / adhesiveness with the filler are poor, and the high molecular weight unsaturated polyester composition has sufficient performance. It is difficult to get things. If it is more than 100 parts by weight, the processability in preparing the composition and the miscibility and adhesiveness with the filler are sufficient, but the crosslink density becomes high, and as a result,
The toughness of the cured product decreases, and it becomes difficult to obtain a molded product having sufficient performance.

The amount of silica powder and / or glass fiber used is as follows: Base resin 1 consisting of high molecular weight polyester and allyl ester and / or allyl ester resin
10 to 400 parts by weight, preferably 5 to 100 parts by weight
0 to 350 parts by weight. If it is less than 10 parts by weight, the reinforcing effect peculiar to the silica powder and / or glass fiber, which is the feature of the present invention, cannot be obtained. On the other hand, if it is used in an amount of more than 400 parts by weight, the fluidity of the composition at the time of molding becomes poor, and it becomes difficult to obtain a satisfactory molded product.

In the high molecular weight unsaturated polyester resin composition of the present invention, in addition to the above high molecular weight unsaturated polyester, allyl ester and / or allyl ester resin, silica powder and / or glass fiber,
A radical generating catalyst, an internal mold release agent, a stabilizer and the like are appropriately blended if necessary.

The radical generating catalyst is not particularly limited, but when the molding temperature is 100 ° C. or higher,
A so-called high temperature decomposition type, for example, dicumyl peroxide type is used. The amount used is 0.5 to 3 phr, preferably 1 to 3 phr.

Examples of the internal release agent include stearic acid, oleic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, stearic acid amide, oleic acid amide, carnauba wax, silicone oil, synthetic wax and the like. And these can be used in an appropriate ratio.

Examples of the stabilizers include publicly known stabilizers such as hydroquinone, benzoquinone, copper salts, tetramethylthiuram compounds and nitrophenylhydroxy compounds.

There is no particular limitation on the method for preparing the high molecular weight unsaturated polyester resin composition of the present invention. The high molecular weight unsaturated polyester resin composition of the present invention, a pigment, a dye is blended by a conventional method, compression molding, transfer molding,
It can be molded into a desired shape by any method of injection molding, and after curing, a cured product having sufficient heat resistance, water resistance, mechanical strength, electrical properties and chemical stability can be obtained.

[0031]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 Synthesis of Modified High Molecular Weight Unsaturated Polyester [I] In a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer and a gas introduction tube, 1,4-cyclohexanedimethanol 152.7 g. , 80.8 g of neopentyl glycol, 205.1 g of isophthalic acid and 0.41 g of tetraisopropyl titanate were added, and after esterification reaction at 205 ° C. in a nitrogen stream to an acid value of 5, fumaric acid 61.4 g and hydroquinone 0. 12 g was added, and the esterification reaction was carried out at a temperature of 185 ° C. until the acid value became 16. Next, 0.22 g of phosphorous acid and 0.22 of phenothiazine
g, tetraisopropyl titanate 0.87 g,
Finally, the deglycolization reaction was carried out at a temperature of 200 ° C. for 8 hours under a reduced pressure of 0.7 Torr. Then, 22.2 g of trimellitic anhydride was added, and terminal treatment was performed at 170 to 190 ° C. for 30 minutes. The obtained modified high molecular weight unsaturated polyester [I] was yellowish brown, transparent pine and had a number average molecular weight of 7,600.

Example 1 50 g of the modified high molecular weight unsaturated polyester [I] synthesized in Synthesis Example 1, allyl resin AA101 (Showa Denko KK)
50 g, silane coupling agent 2 g, silica powder (Fuselex RD-8; manufactured by Tatsumori Co., Ltd.) 300 g,
4 g of zinc stearate and 2 g of dicumyl peroxide were weighed and mixed with stirring until uniform. The obtained mixture was kneaded with a hot roll heated to 90 ° C. for 15 minutes to obtain a sheet-like uniform composition. This sheet-shaped composition was cooled, pulverized, and compression-molded under the following molding conditions to measure bending strength, bending elastic modulus, and insulation resistance.

Molding conditions: Press temperature 180 ° C., press pressure 50 kg / cm ² Press time 30 minutes Post-curing 150 ° C., 3 hours

Bending strength: 16.0 kgf / mm ² ; Flexural modulus: 3070 kgf / mm ² ; Insulation resistance (normal state): 5.8 × 10 ¹⁴ Ω; Insulation resistance (D-2 / 100; boiling for 2 hours) : 5.7 x 1
0 ¹⁴ Ω; Heat distortion temperature: 200 ℃ or more

Example 2 In Example 1, the silica powder (Hugh Rex RD
-8) A molding material was prepared and compression molded in the same manner as in Example 1 except that 400 g was used instead of 300 g.

Bending strength: 17.6 kgf / mm ² ; Bending elastic modulus: 3640 kgf / mm ² ; Insulation resistance (normal state): 6.1 × 10 ¹⁴ Ω; Insulation resistance (D-2 / 100; boiling for 2 hours) : 6.1 x 1
0 ¹⁴ Ω; Heat distortion temperature: 200 ℃ or more

Example 3 In Example 1, silica powder (Hugh Rex RD
-8) Milled fiber (glass powder, EPG 140M-80A; Nippon Electric Glass Co., Ltd.) instead of 300 g
A molding material was prepared and compression molding was performed by the same operation as in Example 1 except that 300 g of the product) was used.

Bending strength: 18.1 kgf / mm ² ; Bending elastic modulus: 3590 kgf / mm ² ; Insulation resistance (normal state): 5.4 × 10 ¹⁴ Ω; Insulation resistance (D-2 / 100; boiling for 2 hours) : 5.1 x 1
0 ¹⁴ Ω; Heat distortion temperature: 200 ℃ or more

Comparative Examples 1 to 3 In Example 1, instead of the modified high molecular weight polyester [I], commercially available number average molecular weights were 2,900 (Comparative Example 1), 2,100 (Comparative Example 2) and 1, A molding material was prepared under the same conditions as in Example 1 except that the unsaturated polyester of 700 was used, compression molding was performed, and the properties thereof were examined. The results are shown in Table 1.

[0041]

[Table 1]

[0042]

The number average molecular weight according to the present invention is 5,000.
The above-mentioned unsaturated polyester resin composition containing a high molecular weight unsaturated polyester, an allyl ester and / or an allyl ester resin which is copolymerizable with the unsaturated polyester, and silica powder and / or glass fiber can be obtained by conventional techniques. It has excellent flexural strength, flexural modulus, and insulation resistance after boiling for 2 hours, which makes it widely used as an unsaturated polyester resin composition useful in the electrical, electronic, automobile, and other industries. It is possible to use.

Claims (2)

[Claims] 1. A polyhydric alcohol component in which at least one kind of [I] (a) polyhydric alcohol is 1,4-cyclohexanedimethanol, and (b) an α, β-unsaturated polybasic acid (or its anhydride). (C) a saturated or unsaturated polybasic acid (or its anhydride) is used in an amount of 90 mol% or less. A high molecular weight unsaturated polyester having an average molecular weight of 5,000 or more, [II] an allyl ester and / or an allyl ester resin copolymerizable with the unsaturated polyester, and [III] silica powder and / or glass fiber And a high molecular weight unsaturated polyester resin composition. 2. A cured product of the high molecular weight unsaturated polyester resin composition according to claim 1.