JPS63205312A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which gives a cured product having a high heat distortion temperature and excellent impact resistance, by mixing an unsaturated polyester with a specified dihydroxy compound, a polyisocyanate compound and a polymerizable vinyl monomer at a specified ratio. CONSTITUTION:An unsaturated polyester (A) obtained from a dicarboxylic acid component containing 65-100mol% unsaturated carboxylic acid (anhydride) and a polyhydric alcohol containing prim. hydroxyl groups, a dihydroxy com pound (B) of the formula (wherein X is CH2, O, CO or the like, (m) and (n) are each 1-7, and m+n=2-8), a polyisocyanate compound (C) and a polymerizable vinyl monomer (D) are mixed together so that the total of the hydroxy residues of component A and the component B may be 1.5-4.5 times by mole that of the dicarboxyl residues of component A, that the unsaturated dicarboxylic acid residues of component A may be 0.5-3.5mmol/g per total of components A and B, and that the total of the hydroxyl groups of components A and B may be 0.8-1.2 times by mole that of the isocyanate groups of component C to obtain the title resin composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a novel unsaturated polyester resin composition for obtaining a cured product that has high mechanical strength and has both excellent impact resistance and heat resistance. It is related to.

More specifically, unsaturated polyester (A), general formula [I
] to obtain a cured product with extremely excellent impact resistance having a specific composition composed of a dihydroxy compound (B), a polyisocyanate compound (C), and a polymerizable vinyl monomer (D). This invention relates to a saturated polyester resin composition.

, [Prior art] Unsaturated polyester resin is usually produced by polymerizing unsaturated polyester obtained by dehydration condensation reaction of a mixture of an unsaturated dicarboxylic acid or its acid anhydride and a saturated dicarboxylic acid or its acid anhydride with a polyhydric alcohol. It is obtained by mutually dissolving a vinyl monomer and a polymerization inhibitor.

Cured products of such unsaturated polyester resins have excellent mechanical strength, chemical resistance, heat resistance, etc. Taking advantage of these properties, unsaturated polyester resins can be used for casting, painting, and decorative laminates. It is widely and effectively used as a material for glass fiber-reinforced unsaturated polyester resins and resin concrete in various applications such as ships, bathtubs, water tanks, septic tanks, and chemical storage tanks.

However, it is difficult to obtain a cured product having both impact resistance and heat resistance from such conventional unsaturated polyester resins. That is, as a method for improving the heat resistance of unsaturated polyester resin, unsaturated polyester is produced by a dehydration condensation reaction of a mixture of an unsaturated dicarboxylic acid or its acid anhydride, a saturated dicarboxylic acid or its acid anhydride, and a polyhydric alcohol. In doing so, there is a method of increasing the amount of unsaturated dicarboxylic acid or its acid anhydride in the dicarboxylic acid component. However, the cured product of unsaturated polyester resin obtained by dissolving the unsaturated polyester produced in this way in a polymerizable vinyl monomer has the disadvantage that although it improves heat resistance, impact resistance decreases. .

On the other hand, many attempts have been made to improve impact resistance.
For example, a method using aliphatic dicarboxylic acids such as adipic acid or cepatic acid as a saturated dicarboxylic acid, which is a component of unsaturated polyester, and a method using polyether glycols such as polyethylene glycol or polypropylene glycol as a polyhydric alcohol component. It has been known. Furthermore, many attempts have been made to improve impact resistance by introducing urethane bonds into unsaturated polyester resins. For example, Unexamined Japanese Patent Publication No. 51. -143096, unsaturated polyester and saturated oligomers such as polyethylene glycol and polypropylene glycol are bonded together in a block form via a polyisocyanate compound in the presence of a polymerizable vinyl monomer to create an unsaturated polyester with excellent impact resistance. A resin composition is obtained. Special Public Service 1977-
No. 1969.6 discloses that the molecular weight obtained by reacting a polyester polyol and a polyisocyanate is 30,000 to 2.
We are proposing a method of dispersing 00,000 polyurethane resin into unsaturated polyester resin. However, although all of these methods improve impact resistance, the drawback of reduced heat resistance remains unsolved.

These drawbacks of conventional unsaturated polyester resin compositions are hindering the expansion of demand for unsaturated polyester resins.

[Problem that the invention seeks to solve]

The present inventors have arrived at the present invention as a result of extensive studies aimed at solving these problems and obtaining an unsaturated polyester resin composition that has both impact resistance and heat resistance.

[Means for solving problems]

That is, as a main component, unsaturated polyester (A),
Dihydroxy compound CB) represented by the following general formula CI) (where x is CHz, C(CH3)2, O, Go,
At least one type selected from the group consisting of S, SO2, m, n=l~7, m+r+=2~8),
It is composed of a polyisocyanate compound (C,) and a polymerizable vinyl monomer (D), and (A) is a dicarboxylic acid or its acid anhydride containing 65 to 100 mol χ of an unsaturated dicarboxylic acid or its acid anhydride. It is an unsaturated polyester obtained from and a polyhydric alcohol having a primary hydroxyl group, and the sum of the hydroxyl residues of (A) and (,B) is (
It is in the range of 1.5 to 4.5 times the mole of the dicarboxylic acid residue of A), and ■ The unsaturated dicarboxylic acid residue of (A) is
B) is 0.50 to 3.50 mmol/g, and ■ the total of hydroxyl groups in (A) and (B)
) is 0.8 to 1.2 times the isocyanate group by mole.

The unsaturated polyester (A) used in the composition of the present invention is a mixture of 65 to 100 mol χ of an unsaturated dicarboxylic acid or its acid anhydride and 35 mol % or less of a saturated dicarboxylic acid or its acid anhydride as an acid component. It is a polycondensate obtained by subjecting these to a dehydration condensation reaction using a method known per se, using a polyhydric alcohol having a primary hydroxyl group as the alcohol component.

The unsaturated polyester used in the composition of the present invention has a molecular weight (
(based on the terminal group method) is preferably 350 to 1,500, and this unsaturated polyester has a hydroxyl group or carboxyl group at the molecular end, but when considering reactivity with the polyisocyanate compound, Those having a hydroxyl group are preferred.

In the present invention, if an unsaturated polyester containing 65 mol% or less of an unsaturated dicarboxylic acid or its acid anhydride (based on the total dicarboxylic acid components) is used, the heat resistance will decrease and the purpose of the present invention cannot be achieved. .

Here, examples of the unsaturated dicarboxylic acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic anhydride, and saturated dicarboxylic acid or its acid anhydride. Examples thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, het's acid, tetrahydrophthalic anhydride, adipic acid, and cehatic acid.

In addition, examples of polyhydric alcohols having a -grade hydroxyl group include ethylene glycol, diethylene glycol, 1.4
-butanediol, neopentyl glycol, and a dihydroxylated metal compound represented by the following formula (where X is CH2, C(CH3)2, O, Co, S
, SO2, n=1 to 7, m+n=2 to 8). Secondary hydroxyl such as propylene glycol, dipropylene glycol, bisphenol A-propylene oxide adduct.

Polyhydric alcohols containing sil groups can also be used, but the amount is preferably 15 mol% or less. 15 mol% of polyhydric alcohols containing secondary hydroxyl groups
When using the unsaturated polyester manufactured using the above,
The purpose of the present invention cannot be achieved.

Examples of the polymerizable vinyl monomer to be mixed with the unsaturated polyester include styrene, chlorostyrene, vinyltoluene, (meth)acrylic acid, and derivatives thereof.

In preparing the unsaturated polyester resin by the method of the present invention, the unsaturated polyester can be used in an amount of 80 to 30 parts by weight, and the polymerizable vinyl monomer can be used in an amount of 20 to 70 parts by weight.

In the composition of the present invention, the dihydroxy compound (B)
It is an essential condition to use at least one type selected from the group consisting of general formula (1) shown below.
1-7, m + n = 2-8).

In the present invention, the total of the hydroxy residues of the unsaturated polyester (A) and the dihydroxy compound (B) is (A)
The amount is in the range of 1.5 to 4.5 times the mole of the dicarboxylic acid residue.

Moreover, the dicarboxylic acid residue of (A) is (A) and (B)
It is essential that the amount is 0.50 to 3.50 mmol/g. If an unsaturated polyester with a dicarboxylic acid residue of 0.5 mmol/g or less is used, the heat resistance will not be sufficient, and if an unsaturated polyester with a dicarboxylic acid residue of 3.5 mmol/g or more is used, the impact resistance will be insufficient. However, neither of these methods can fully satisfy the purpose of the present invention. The dihydroxy compounds (B) of the invention can be used in several different ways. For example, an unsaturated polyester (A) obtained by a dehydration condensation reaction of a mixture of an unsaturated dicarboxylic acid or its acid anhydride, a saturated dicarboxylic acid or its acid anhydride, and a polyhydric alcohol.
is dissolved in the polymerizable vinyl monomer (D) to produce an unsaturated polyester resin, and then the unsaturated polyester resin and the dihydroxy compound (B) are mutually dissolved. Alternatively, unsaturated polyester (A) is produced by a dehydration condensation reaction between an unsaturated dicarboxylic acid or its acid anhydride, a mixture of a saturated dicarboxylic acid or its acid anhydride, and a polyhydric alcohol, and the unsaturated polyester (A) and dihydroxy After mixing with compound (B) while hot, it is dissolved in polymerizable vinyl monomer (D). Furthermore, in producing the unsaturated polyester (A) by a dehydration condensation reaction of a mixture of an unsaturated dicarboxylic acid or its acid anhydride and a saturated dicarboxylic acid or its acid anhydride and a polyhydric alcohol,
It is also possible to add the dihydroxy compound (B) in advance.

The polyisocyanate compound (C) used in the composition of the present invention includes 4,4'-diphenylmethane diisocyanate, 2.4-)lylene diisocyanate, 2.
．． In addition to polymethylene polyphenylisocyanate (e.g. PAPI20, PAP1135, PAI
) I580), liquid diphenylmethane diisocyanates (e.g. l5ON
Compound commercially available under the trade name ATE143L)
, 4,4'-diphenylmethane diisocyanate polyether prepolymer (e.g. l5ONATE18
Chemical compound sold under the trade name 1), 4.4°
- Known and commonly used ones such as diphenylmethane diisocyanate polyester elastomer (a compound commercially available under the trade name rsONATE240), etc., and polymethylene polyphenylisocyanate, liquid diphenylmethane diisocyanate, etc.
Preference is given to using polyisocyanate compounds having more than one isocyanate group.

The amount of these polyisocyanate compounds (C) used is limited to a range in which the total of the hydroxyl groups of the unsaturated polyester (A) and the hydroxyl groups of the dihydroxy compound CB) is 0.8 to 1.2 times the isocyanate group by mole. be done.

The thus obtained unsaturated polyester resin composition of the present invention contains not only conventional polymerization inhibitors such as hydroquinone, parahenzoquinone, and methylhydroquinone, but also
Conventional curing catalysts such as benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl perbenzoate, conventional curing accelerators such as dimethylaniline, cobalt naphthenate, etc., cobalt octoate, dibutyltin dilaurate, etc. Commonly used urethanization catalysts such as calcium carbonate,
conventional fillers such as clay, aluminum hydroxide, etc.
A conventional mold release agent such as zinc stearate, other organic or inorganic pigments, and a low shrinkage agent such as a thermoplastic resin can be added.

The unsaturated polyester resin composition obtained by the present invention can be used in contact pressure molding, pultrusion molding, resin transfer, press molding, etc., which are commonly used in the industry in which the composition is used.

EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

11DT of unsaturated polyester resin cured on each side
(Heat distortion temperature) is JIS K6919, 120 (]
Impact strength was evaluated according to the method of JIS K6911. However, from a casting board with a thickness of 3 mm, the length is 127 cm and the width is 1.
A specimen machined to 2.7 mm was machined to a length of 6 for HDT.
Specimens machined to 3.5 mm and width 12.7 mm were used for Izod impact strength, and the load was applied perpendicular to the width direction. In addition, the hydroxyl value of unsaturated polyester is determined by the acetylation method, and the acid value is determined by JIS K6901.
Measured according to

〔Example〕

Synthesis Examples (1) to (■), Comparative Synthesis Examples (1) to (2) [Synthesis of unsaturated polyester (A)] Synthesis Example (I) Stirrer, thermometer, nitrogen gas introduction tube, and temperature control at the top of the column In a reactor equipped with a metered partial reflux, isophthalic acid 5
53g, neopetyl glycol 680g.

406 g of ethylene glycol was charged, heated while flowing nitrogen gas, and the temperature was raised to 205°C to carry out a dehydration condensation reaction according to a conventional method. lOO for partial reflux
OC steam was flowed to reflux the glycols, and water of condensation was distilled out of the reaction system. The acid value of the reaction mixture is 5.
Heating was stopped when the temperature reached 0°C, and after cooling to 150°C, 654g of maleic anhydride was charged.
The temperature was again started to rise, and the dehydration condensation reaction was continued until the temperature reached 230°C, whereupon the reaction was terminated to obtain 2053 g of unsaturated polyester having an acid value of 2.3 and a hydroxyl value of 99.0. This unsaturated polyester was cooled to 170°C and 0.4
After adding 7 g of hydroquinone, 0.103 g of parahenzoquinone was added in advance and dissolved in 1206 g of styrene kept at 25 °C to obtain an unsaturated polyester resin (rA-I J
) 3259g was obtained.

Isophthalic acid 4
15g, neopentyl glycol 677g.

404 g of ethylene glycol was charged, heated while flowing nitrogen gas, and the temperature was raised to 202'C to carry out a dehydration condensation reaction according to a conventional method. 10 for partial reflux
Steam at 0°C was flowed to reflux the glycols, and water of condensation was distilled out of the reactor system. Heating was stopped when the acid value of the reaction mixture reached 5.7, and after cooling to 150°C, 736 g of maleic anhydride was charged. Start raising the temperature again and continue the dehydration condensation reaction to 224°
The reaction was terminated when the temperature reached C, and 2007 g of unsaturated polyester with an oxidation rate of 4.0 and a hydroxyl value of 120.6 was obtained. The unsaturated polyester was cooled to 170'C, 0.46g of hydroquinone was added, and 0.46g of hydroquinone was added.
Add 10g of parahenzoquinone in advance and heat at 25°
Dissolved in 1081 g of styrene kept at 35
Unsaturated polyester resin containing χ styrene (rA
-II J) 3088 g was obtained.

Anvil flame (I [[) 332 g of isophthalic acid was placed in a reactor similar to synthesis example (1)
, 677 g of neopentyl glycol, 404 g of ethylene glycol, and 785 g of maleic anhydride were charged, and the synthesis example (
Using the same method as in 1), the acid value was 3.8 and the hydroxyl value was 12.
After synthesizing an unsaturated polyester having 4.2, it was dissolved in styrene to form an unsaturated polyester resin (rA-II [''
) 3049g was obtained.

Using the same reactor as in Synthesis Example (n), isophthalic acid 91
4 g, fumaric acid 522 g, diethylene glycol 8
Synthesis example (II) of 49g and 137g of ethylene glycol
After reacting in the same manner as above to synthesize an unsaturated polyester with an acid value of 23, it was dissolved with styrene to obtain an unsaturated polyester resin (RA-1'') with a styrene content of 40χ.

Comparative Synthesis Example (2) Using the same reactor as Synthesis Example (n), isophthalic acid 41
5g, fumaric acid 871g, propylene glycol 244
g and 729 g of neopentyl glycol were reacted in the same manner as in Synthesis Example (■) to synthesize an unsaturated polyester with an acid value of 22, and then dissolved in styrene to give a styrene content of 4.
An unsaturated polyester resin ("a-2J") of 0.chi. was obtained.

Example 1 2 mole adduct of bisphenol F (bis(4-hydroxyphenyl)methane)/ethylene oxide (hereinafter referred to as B15F) was added to 50.2 g of r A-I J obtained in Synthesis Example (I).
・After adding 21.70 g of Eo2 (manufactured by Nippon Nyukazai ■) and 2 g of Niper-FF (trade name of Henzoyl peroxide manufactured by Nippon Oil & Fats ■) and mixing thoroughly, a polyisocyanate compound (trade name 15onate, MD) was added and mixed thoroughly.
Add 27.68g of chemical preparation and 0.2g of N,N-diethylaniline, mix quickly and uniformly, pour into a glass plate cell prepared in advance, leave at 20°C for 16hrs, then at 80°C for 2hrs. , 140°
C. for 2 hours. The heat distortion temperature (HDT) and Izodi impact strength of the cured product thus prepared were
Shown in the table.

As is clear from Table 1, it is clear that the cured products obtained from the compositions of the present invention have excellent impact resistance and high heat distortion temperatures.

Examples 2 to 3 The procedure was the same as in Example 1 except that the types and amounts of (A) and (B) and the amount of (C) were changed as shown in Table 1.
15A.Eo4 indicates an adduct of 4 moles of bisphenol A and ethylene oxide). HDT of the obtained cured product,
The Izod impact strength is also shown in Table 1.

Comparative Examples 1 to 2 Polyethylene glycol other than (B) of the present invention (molecular weight 300. PEG 300) as a dihydroxy compound
, polypropylene glycol (molecular weight 70 (+, PPG
The procedure was almost the same as in Example 1 except that 700) were used in each case. Table 2 shows the HDT and Izod impact strength of the obtained cured product.

Comparative Examples 3 to 4 The types and amounts of (A) and (B) and the amount of (C) were changed as shown in Table 1, and A
The procedure was almost the same as in Example 1 except that the total amount of hydroxyl residues in ) and (B) was 1.5 or less. The HDT and Izod impact strength of the obtained cured product are also shown in Table 2.

Comparative Examples 5 to 6 Using the unsaturated polyesters a-1 and a-2 produced in Comparative Synthesis Examples (1) and (2) alone without using the dihydroxy compound (B) and the polyisocyanate compound (C), A cured product was produced in the same manner as in Example 1, and the IIDT and Izod impact strengths of the obtained cured product were measured.

The results are also shown in Table 2.

Synthesis Examples (IV) to (Vl) [Synthesis of unsaturated polyester (A)] Synthesis Example (TV) Using the same reactor as Synthesis Example (1), fumaric acid 403
g, ethylene glycol 58g1 bisphenol A-E
1,897 g of O2 mole adduct (Nippon Nyukazai ■) was subjected to a dehydration condensation reaction according to a conventional method, and when the acid value reached 4.2, 767 g of bisphenol A-EO2 mole adduct was added and dissolved, and the acid value became 1. 6. Hydroxyl number 202
．． After synthesizing the unsaturated polyester/glycol mixture of No. 1, it was dissolved in styrene to obtain an unsaturated polyester resin ("A-■"; containing the dihydroxy compound (B) in a mixed form) with a styrene content of 23.2χ. Ta.

Synthesis Example (V) Using the same reactor as Synthesis Example (1), 333 g of fumaric acid
, 2770 g of bisphenol 8-EO 2 mole adduct,
An unsaturated polyester with an acid value of 1.3 and a hydroxyl value of 208.6 was synthesized by a humid water condensation reaction according to a conventional method, and then dissolved in styrene to obtain an unsaturated polyester resin (rA-VJ; dihydroxy) with a styrene content of 23.0χ. Compound (B) in mixed form) was obtained.

Synthesis Example (Vl) Using the same reactor as Synthesis Example (1), 390 g of fumaric acid
, 2632 g of bisphenol^・EO 2 mole adduct, and 98 g of diethylene glycol were subjected to a dehydration condensation reaction according to a conventional method to synthesize an unsaturated polyester with an acid value of 1.4 and a hydroxyl value of 210°3, and then dissolved in styrene to obtain a polyester with a styrene content of 22. .6χ unsaturated polyester resin (r
A-Vlj; containing dihydroxy compound (B) in mixed form) was obtained.

Examples 4 to 6'('A) unsaturated polyesters obtained in Synthesis Examples (■) to (VI) ('A-IV), (A-V), (A
The procedure was the same as in Example 1, except that -Vl) were used, and the type and amount of (B) and the amount of (C) were changed as shown in Table 1. The HDT and Izod impact strength of the obtained cured product are also shown in Table 1.

In Examples 4 to 6 in Table 1, unsaturated polyester (
Of the amount of A), () indicates the amount of unsaturated polyester resin excluding dihydroxy compound (B) coexisting in a mixed state, and () of the amount of dihydroxy compound (B) indicates the amount of unsaturated polyester resin (A). It shows the amount of dihydroxy compound (B) coexisting therein.

From Examples 4 to 6 in Table 1, it is clear that the cured products obtained from the compositions of the present invention have excellent impact resistance and high heat distortion temperatures.

Table 1 ■ Moles of unsaturated dicarboxylic acid residues in the sicarnene acid residues in 2 (A) χ'13 Ladle ■ - Moles of unsaturated dicarboxylic acid residues in the sicarnene acid residues in (A) χ [ Effects of the Invention] According to the present invention, the impact resistance of a cured product made from unsaturated polyester can be significantly improved without lowering the heat distortion temperature.

Claims (1)

[Claims] The main components are an unsaturated polyester (A) and a dihydroxy compound (B) represented by the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (However, X is CH_2, C(CH_3)_2, O, CO
, S, SO_2, m, n = 1 to 7, m + n = 2 to 8), a polyisocyanate compound (C), and a polymerizable vinyl monomer (D). [1] (A) is an unsaturated polyester obtained from a dicarboxylic acid or its acid anhydride containing 65 to 100 mol% of the unsaturated dicarboxylic acid or its acid anhydride and a polyhydric alcohol having a primary hydroxyl group. Yes, [2] The sum of the hydroxyl residues of (A) and (B) is (A
) is in the range of 1.5 to 4.5 times the mole of the unsaturated dicarboxylic acid residue in [3] (A), and the unsaturated dicarboxylic acid residue in (A) is 0.50 times the mole of ~3.50 mmol/g, and the total of the hydroxyl groups in [4] (A) and (B) is (
An unsaturated polyester resin composition characterized in that the amount is 0.8 to 1.2 times the isocyanate group in C) by mole.