JP3144436B2 - Unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition, and more particularly to one having excellent injection characteristics during molding.

[0002]

2. Description of the Related Art Conventionally, in an RTM molding without a filler, if the resin viscosity is 3 poise or less at a molding temperature, the unsaturated polyester resin composition concentrates on a portion having low flow resistance at the time of resin injection. There is an inconvenience of flowing. In particular, it is remarkable in the case of a large molded product having an area of 1 m ² or more. Therefore, the resin needs to have a resin viscosity of 3 poise or more at the molding temperature. In addition, resin 1
In the case where the filler is compounded in an amount of 30 parts by weight or more with respect to 00 parts by weight, if the resin viscosity is 2 poise or more at the molding temperature, the injection time becomes extremely long or the resistance becomes too large, so that injection becomes impossible. . Further, when a filler is blended, there is a problem that the filler sediments when left for several hours.

[0003]

SUMMARY OF THE INVENTION The present invention can be carried out by adding a thixotropic agent to an unsaturated polyester resin and injecting it with or without a filler. Particularly, up to about 100 parts by weight per 100 parts by weight of the resin. Even if the filler filling amount is increased, the injection time hardly increases. In the case of a high filler content, the injection time is shorter than the conventional one, and the unsaturated polyester resin composition which does not settle for more than one month after compounding the filler is used. To provide.

[0004]

SUMMARY OF THE INVENTION The present invention relates to an unsaturated polyester having a weight average molecular weight (Mw) of 4500 to 5500 and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.0 or more. (A) an unsaturated polyester resin composition comprising a polymerizable unsaturated monomer (B) and a thixotropic agent, in particular, finely divided silica (C);
The present invention also relates to a resin composition obtained by adding a filler, particularly calcium carbonate, to the composition.

[0005]

[Constitution] As the α, β-unsaturated dibasic acid of the unsaturated polyester (A) or its acid anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid,
There are chlormaleic acid and esters thereof, and the aromatic saturated dibasic acid or anhydride thereof includes phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, and endmethylenetetrahydroanhydride. There are phthalic acid, halogenated phthalic anhydride and esters thereof, etc., as aliphatic or alicyclic saturated dibasic acids, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, There are hexahydrophthalic anhydride and esters thereof, which are used alone or in combination.
As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Tetraethylene glycol, 1,5-pentanediol, 1,
6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,
Examples thereof include 2-di (4-hydroxypropoxydiphenyl) propane and the like, which are used alone or in combination. In addition, oxides such as ethylene oxide and propylene oxide can also be used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and the acid component.

The weight average molecular weight of the unsaturated polyester is
According to GPC measurement, it is 4500 to 550 in terms of polystyrene.
0. As the unsaturated polyester, those having a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.0 or more, preferably 2 to 4 are used. The number average molecular weight of the unsaturated polyester is measured in the same manner as the weight average molecular weight. Here, the GPC measurement was performed by Nippon Kagaku Kogyo LC-08.
Type and column are SHOdex A-804 + 803 + 8
02 + 801, eluent THF, flow rate is 1 cc / mi
n, detector RI.

The polymerizable unsaturated monomer (B) of the present invention is an α, β-ethylenically unsaturated monomer, such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, Vinyl compounds such as vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, triallyl cyanurate, etc. Examples thereof include an unsaturated monomer crosslinkable with an unsaturated polyester or an oligomer thereof, and these are used alone or in combination, but styrene is preferably used.

[0008] The mixing ratio of the unsaturated polyester and the polymerizable unsaturated monomer is not particularly limited as long as the effects of the present invention are achieved.
90% by weight and 10 to 55% by weight of the polymerizable unsaturated monomer (B).

The thixotropic agent (C) used in the present invention is a finely divided silica-based or castor oil derivative (THIXCIN).
E; NL CHEMICALS). Preferable examples thereof include fine powder silica, for example, AEROSIL manufactured by Nippon Aerosil Co., Ltd., Silodex manufactured by Fuji Depison Chemical Co., Ltd.
b-O-Sil and the like. Further, the amount of the thixotropic agent to be added is 100% of an unsaturated polyester and a polymerizable unsaturated monomer (hereinafter referred to as an unsaturated polyester resin).
The amount is preferably from 0.1 to 10 parts by weight, more preferably from 0.2 to 3 parts by weight, based on parts by weight.

When molding using the composition of the present invention, a curing catalyst is usually used. Such catalysts include:
For example, azo compounds such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoate, benzoyl peroxide, acetylacetone peroxide, methyl ethyl ketone peroxide, organic peroxides such as dicumyl peroxide, and the like. It can be used in the range of usually 0.3 to 3 parts by weight based on 100 parts by weight of the unsaturated polyester resin.

Further, a curing accelerator can be used in combination with the curing catalyst. Such curing accelerators include metal salts of organic acids, especially cobalt salts, for example, cobalt naphthenate,
Cobalt octylate, cobalt acetylacetone and the like are used. The amount used may be about the same as the curing catalyst.

The composition of the present invention may further contain a filler. Such fillers include, for example, whiskers, aluminum powder, copper powder, silica, diatomaceous earth, alumina, calcium carbonate, stone mackerel, mica, clay, talc, asbestos, graphite, carbon fiber, glass fiber, glass powder, cement , Linter, linen, wood powder, synthetic resin powder, tire powder, pigment and the like, alone or in combination. In particular, calcium carbonate, preferably fine powder calcium carbonate having an average particle size of 2 μm or less is used. It is preferable to use such calcium carbonate because the injection time can be shortened. Examples of the calcium carbonate include NS-200 or NS-1000 manufactured by Nitto Powder Chemical Co., Ltd. An appropriate amount of the filler is 1 to 120 parts by weight based on 100 parts by weight of the unsaturated polyester resin. (Average particle diameter is the average particle diameter of the powder measured by a water surface specific surface measuring instrument manufactured by Shimadzu Corporation. Average particle diameter = 6 / (specific gravity x specific surface area))

The composition of the present invention may contain a curing property modifier in addition to the compounds and additives. Also,
Reinforcing agents such as glass fiber and organic fiber, other fillers,
Pigments, weathering agents, flame retardants, waxes, internal mold release agents, coloring inhibitors and the like can also be added.

The composition of the present invention can be formed by various moldings, and in particular, RTM (ResinTransfer).
Molding) It is suitable for molding, and is used after being molded into various molded articles, particularly, septic tanks and the like.

[0015]

The resin composition of the present invention has a high injection rate at the time of molding, and particularly contains a filler such as calcium carbonate.
Even if it is added over a wide range of up to about 120 parts by weight, the injection rate is high and the injection time is not extended, and the filler does not settle during storage for more than one month. In addition, high filling of the filler is possible, and it is possible to significantly reduce the cost.

[0016]

EXAMPLES The present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 These were charged in a ratio of 50 mol% of maleic anhydride, 50 mol% of phthalic anhydride and 105 mol% of propylene glycol into a four-necked flask equipped with a stirrer, a condenser, a thermometer and an inert gas inlet. 21 under the introduction of inert gas
The reaction was carried out at 5 ° C. under normal pressure to obtain an unsaturated polyester having a weight average molecular weight of 5,100, a number average molecular weight of 2,040 and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.5 in terms of GPC polystyrene. . 44% by weight of a styrene monomer and 200 ppm of methylhydroquinone were added to 56% by weight of the unsaturated polyester to obtain an unsaturated polyester resin (Resin 1). To 100 parts by weight of the unsaturated polyester resin (resin 1), 2 parts by weight of fine powder silica (AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd.) was added.
A thixotropic unsaturated polyester resin composition (composition 1) dispersed in a homomixer M type manufactured by Tokushu Kikai Kogyo Co., Ltd. for 20 minutes was obtained.

Example 2 The unsaturated polyester resin composition of Example 1 (Composition 1)
60 parts by weight of calcium carbonate (NS-200 (average particle size: 1.85 μm) manufactured by Nitto Kaka Kogyo Co., Ltd.) was blended with 100 parts by weight to obtain an unsaturated polyester resin composition (composition 2).

Example-3 Calcium carbonate (NS-200, manufactured by Nitto Kagaku Kogyo Co., Ltd. (average particle size: 1.85 μm)) based on 100 parts by weight of the unsaturated polyester resin composition (composition 1) of Example 1. 1
The unsaturated polyester resin composition (composition 3) was obtained by mixing 00 parts by weight.

Example-4 Calcium carbonate (NS-1000, manufactured by Nitto Kagaku Kogyo Co., Ltd. (average particle diameter: 1.17 μm)) based on 100 parts by weight of the unsaturated polyester resin composition (composition 1) of Example-1 Was added to obtain an unsaturated polyester resin composition (composition 4).

Example-5 Calcium carbonate (NS-1000, manufactured by Nitto Kaka Kogyo Co., Ltd. (average particle size: 1.17 μm)) based on 100 parts by weight of the unsaturated polyester resin composition (composition 1) of Example-1 Was added to obtain an unsaturated polyester resin composition (composition 5).

Comparative Example 1 In Example 1, an unsaturated polyester resin composition to which fine powdered silica was not added (composition 1) was used.

Comparative Example 2 Unsaturated polyester resin (resin 1) 100 of Example 1
Calcium carbonate (NS by Nitto Toka Kogyo Co., Ltd.)
-200) was mixed with 100 parts by weight to obtain an unsaturated polyester resin composition (composition 6).

Comparative Example 3 These were charged in a ratio of 50 mol% of maleic anhydride, 50 mol% of phthalic anhydride and 105 mol% of propylene glycol into a stirrer, a condenser, a thermometer and a four-necked flask equipped with an inert gas inlet. 21 under the introduction of inert gas
The reaction was carried out at 5 ° C. under normal pressure to obtain an unsaturated polyester having a weight average molecular weight of 6,500, a number average molecular weight of 2,320, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.8 in terms of GPC polystyrene. . To 60% by weight of the unsaturated polyester, 40% by weight of a styrene monomer and 200 ppm of methylhydroquinone were added to obtain an unsaturated polyester resin (Resin 2). 60 parts by weight of calcium carbonate (NS-200 manufactured by Nitto Kagaku Kogyo KK) was added to 100 parts by weight of the unsaturated polyester resin (resin 2) to obtain an unsaturated polyester resin composition (composition 7).

Comparative Example 4 Unsaturated polyester resin (Resin 2) 100 of Comparative Example-3
Calcium carbonate (NS by Nitto Toka Kogyo Co., Ltd.)
-200) was added in an amount of 100 parts by weight to obtain an unsaturated polyester resin composition (composition 8).

Comparative Example-5 The unsaturated polyester resin (Resin 2) 100 of Comparative Example-3
To the parts by weight of fine powder silica (AERO
(ROSIL200) was added and dispersed with a homomixer M type manufactured by Tokushu Kikai Kogyo Co., Ltd. for 20 minutes to obtain a thixotropic unsaturated polyester resin composition (composition 9).

Comparative Example -6 Calcium carbonate (NS-200, manufactured by Nitto Kagaku Kogyo Co., Ltd. (average particle size: 1.85 μm)) based on 100 parts by weight of the unsaturated polyester resin composition (composition 9) of Comparative Example-5 6
0 parts by weight were blended to obtain an unsaturated polyester resin composition (composition 10).

Comparative Example-7 100 parts by weight of the unsaturated polyester resin composition (composition 9) of Comparative Example-5 was calcium carbonate (NS-200, manufactured by Nitto Kaka Kogyo Co., Ltd. (average particle size: 1.85 μm)). 1
The unsaturated polyester resin composition (composition 11) was obtained by mixing 00 parts by weight.

Comparative Example-8 These were charged in a ratio of 50 mol% of maleic anhydride, 50 mol% of phthalic anhydride and 105 mol% of propylene glycol into a stirrer, a condenser, a thermometer and a four-necked flask equipped with an inert gas inlet. 21 under the introduction of inert gas
The reaction was carried out at 5 ° C. under normal pressure to obtain an unsaturated polyester having a weight average molecular weight of 4,000, a number average molecular weight of 1,740, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.3 in terms of GPC polystyrene. . To 60% by weight of this unsaturated polyester, 40% by weight of a styrene monomer and 200 ppm of methylhydroquinone were added to obtain an unsaturated polyester resin (Resin 3).

Comparative Example-9 50 mol% of maleic anhydride, 50 mol% of phthalic anhydride,
And propylene glycol at a ratio of 105 mol% into a four-necked flask equipped with a stirrer, a condenser, a thermometer and an inert gas inlet.
The reaction was carried out at 15 ° C. under normal pressure to obtain an unsaturated polyester having a weight average molecular weight of 5,100, a number average molecular weight of 3,400, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.5 in terms of GPC polystyrene. . To 56% by weight of this unsaturated polyester, 44% by weight of a styrene monomer and 200 ppm of methylhydroquinone were added to obtain an unsaturated polyester resin (Resin 4). To 100 parts by weight of the unsaturated polyester resin (Resin 4), 2 parts by weight of fine silica powder (AEROSIL200 manufactured by Nippon Aerosil Co., Ltd.) was added. To 100 parts by weight of the obtained compound, 100 parts by weight of calcium carbonate (NS-200 (average particle size: 1.85 μm) manufactured by Nitto Kagaku Kogyo Co., Ltd.) was added, and the mixture was dispersed for 20 minutes using a homomixer M type manufactured by Tokushu Kikai Kogyo. A thixotropic unsaturated polyester resin composition (composition 12) was obtained.

The GPC analysis in the above example was performed by Nippon Kagaku Kogyo LC-08 type, and the column was SHODEX A-804 +.
803 + 802 + 801, eluent THF, flow rate is 1c
c / min, with detector RI.

Each of the unsaturated polyester resins and the unsaturated polyester resin compositions of Examples 1 to 5 and Reference Examples 1 to 9 was subjected to RTM molding. That is, a chopped strand mat MC450D manufactured by Nitto Boseki Co., Ltd. was applied to a bat-shaped Ni electroforming mold (5 m ² × thickness 3 mm) at an original pressure of 3 kgf / cm ² of a standard type (pump ratio: 11: 1) RTM injector manufactured by Venus-Gasmer. 3 ply,
The injected resin or resin composition is filled (resin filling volume 1.
6L) The time and molding state were examined. The results are shown in Tables 1 and 2. In Comparative Example-8, acid was precipitated during molding, and the compatibility with styrene was poor, and injection was impossible.

[0033]

[0034]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-218773 (JP, A) JP-A 1-229067 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08L 67/06-67/07

Claims (6)

(57) [Claims] (1) a weight average molecular weight (Mw) of 4,500 to 55,
An unsaturated polyester (A) having a weight average molecular weight (Mw) / number average molecular weight (Mn) of at least 2.0, a polymerizable unsaturated monomer (B), and a thixotropic agent (C)
An unsaturated polyester resin composition comprising: 2. The unsaturated polyester resin composition according to claim 1, wherein the thixotropic agent is finely divided silica. 3. The unsaturated polyester resin composition according to claim 1, further comprising a filler. 4. The unsaturated polyester resin composition according to claim 3, wherein the filler is calcium carbonate. 5. The unsaturated polyester resin composition according to claim 4, wherein the calcium carbonate has an average particle size of 1 to 2 μm. 6. A thixotropic agent is added to 100 parts by weight of an unsaturated polyester resin comprising 45 to 90 % by weight of an unsaturated polyester (A) and 10 to 55% by weight of a polymerizable unsaturated monomer (B). The unsaturated polyester resin composition according to claim 1, which is contained in a ratio of 5 parts by weight.