JPH04309557A - Molding resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which is excellent in storage stability, cures in a short time, and is suitable, e.g. for a sheet molding compound. CONSTITUTION:The title compsn. comprises an unsatd. polyester modified with dicyclopentadiene in the presence of an org. phosphonic ester, a polymerizable monomer, aluminum salt of N--nitrosophenylhydroxylamine, and if necessary, a thickener.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding resin composition which has excellent storage stability and a short molding time.

0002

[Prior Art] Unsaturated polyesters modified with dicyclopentadiene have been known for a long time. By modifying unsaturated polyesters with dicyclopentadiene, material costs can be significantly reduced, shrinkage rate can be reduced, and the appearance of molded products can be improved. It is also known to have the following effects.

However, unsaturated polyester modified with dicyclopentadiene has poor storage stability as a resin alone;
Further, when used in a molding method such as a sheet molding compound method, there is a drawback that the storage stability of the resin composition mixed with a curing agent is poor.

Various inhibitors have been investigated to improve this drawback, but when toluhydroquinone or parabenzoquinone is used, the storage stability of the resin composition mixed with a curing agent is poor, and hydroquinone ,2,5-
When di-tert-butyl-4-methylphenol is used, it is extremely difficult to balance the storage stability of the resin itself, as the storage stability of the resin alone is poor. Although it is possible to balance the two by increasing the amount of the inhibitor, there is a drawback that the gelation time becomes longer, resulting in a significantly longer molding time.

[0005]

[Problems to be Solved by the Invention] The present invention provides an industrially useful molding resin composition suitable for molding methods such as sheet molding compound methods, excellent storage stability, and short molding time. It is.

[0006]

[Means for Solving the Problems] The present invention provides (a) an unsaturated polyester modified with dicyclopentadiene in the presence of an organic phosphite, (b) a polymerizable monomer, (
c) A molding resin composition comprising an N-nitrosophenylhydroxylamine aluminum salt and optionally (d) a thickener.

The present invention will be explained below. The unsaturated polyester material modified with dicyclopentadiene has
Dicyclopentadiene is used in addition to the acids and alcohols used in conventional unsaturated polyesters.

As the acid, unsaturated dibasic acids such as maleic anhydride and fumaric acid, and, if necessary, saturated dibasic acids such as isophthalic acid, terephthalic acid, orthophthalic acid, and tetrachlorophthalic anhydride are used.

[0009] Alcohols include ethylene glycol,
Propylene glycol, neopentyl glycol, dibromoneopentyl glycol, dipropylene glycol, 2,2bis[para(hydroxy-n-propoxy)phenyl]propane, tricyclodecanediol, trimethylolpropane, etc. are used.

Methods for modifying unsaturated polyester with dicyclopentadiene include (1) a one-step synthesis method in which acid, alcohol, and dicyclopentadiene are simultaneously charged and condensed, and modified at the same time; and (2) a method in which acid and alcohol are condensed, There is a two-step synthesis method in which dicyclopentadiene is added and modified during the process, and either method is possible.

The unsaturated polyester modified with dicyclopentadiene in the present invention is not limited to those in which dicyclopentadiene is contained in the unsaturated polyester skeleton, but also those in which cyclopentadiene is contained in the unsaturated polyester skeleton. good.

[0012] In the present invention,

It is also possible to use a material using dicyclopentadiene such as [Image Omitted] as part of the acid or alcohol component.

In the present invention, the presence of an organic phosphite is required during the synthesis of the unsaturated polyester modified with dicyclopentadiene. Specific examples of organic phosphites include triphenyl phosphite, tris-tridecyl phosphite, dibutylhydrodiene phosphite, tris (nonylphenyl) phosphite, trilauryl tri-thiophosphite, tris-chloroethyl phosphite, etc. There is. Commercially available products include TP-1, PS-365, manufactured by Daihachi Chemical Industry Co., Ltd.
Examples include CLP-1, TTDP-1, DBP-1, and JP351, JP310, and JP360 manufactured by Joko Chemical Industry Co., Ltd.

[0014] The amount of organic phosphite used is not particularly limited, but is 0.01 to 3.0 with respect to the total amount charged during synthesis.
A weight percent range is preferred. Particularly in the case of triphenyl phosphite, even a small amount of 0.3% by weight or less is preferable since it provides excellent storage stability effects. Furthermore, the organic phosphite may be added before or during the synthesis, but it is preferable to add it before the synthesis starts in order to improve storage stability. Further, even if an organic phosphite is present, the method for synthesizing the unsaturated polyester does not require any particular changes. The reaction temperature is preferably in the range of 150 to 230°C,
The amount of dicyclopentadiene added is not particularly limited, but
0.0 mol of dicyclopentadiene per 1.0 mol of acid component.
It is preferable to use it in a range of 0.01 to 0.40 mol. If the amount of dicyclopentadiene added is less than 0.01 mol, the effects of the present invention on gloss, water resistance, strength, and SMC workability will be slightly inferior, and if it exceeds 0.40 mol, the strength will be slightly reduced, making it difficult to mold. This is because there is a tendency for the removability of the mold to deteriorate. The amount of dicyclopentadiene added is 0.01 to 0.
．． Neopentyl glycol in the range of 40 moles and 0.
When using an unsaturated polyester modified with dicyclopentadiene obtained using 0.01 to 0.40 mol, the molded article of the present invention with excellent balance of gloss, water resistance, and strength can be obtained.

Unsaturated polyesters modified with dicyclopentadiene synthesized using acid, alcohol and dicyclopentadiene in the presence of an organic phosphite include styrene, divinylbenzene, vinyltoluene, vinyl acetate, methyl methacrylate, It is used after being dissolved in a polymerizable monomer (b) such as ethyl acrylate. total amount to 100
The preferred range is 15 to 55 parts by weight of the polymerizable monomer to 85 to 45 parts by weight of the unsaturated polyester.

The present invention requires the use of N-nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor. By using this N-nitrosophenylhydroxylamine aluminum salt, a molding resin composition with excellent storage stability and a short molding time can be obtained. There is no particular limit to the amount of N-nitrosophenylhydroxylamine aluminum salt used, but from the viewpoint of storage stability and gel time of the resin composition, the amount of the unsaturated polyester modified with dicyclopentadiene and the amount of polymerizable monomer
The range is preferably from 0.001 to 0.1 parts by weight per 00 parts by weight.

[0017] Further, in the present invention, hydroquinone, tert-butylhydroquinone, toluhydroquinone, 2,5-diterbutyl-4-methylphenol, α-naphthoquinone, P-t-
Butylcatechol, 2,5-diphenyl-p-benzoquinone, parabenzoquinone, etc. may be used in combination, and storage stability can be further improved by using these in combination. Preferably, toluhydroquinone is used.

[0018] An organic thickener and/or an inorganic thickener may be used if necessary. Isocyanate compounds are examples of organic thickeners. As the isocyanate compound, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, or isocyanate-terminated prepolymers derived from these isocyanates are used. Among these, diphenylmethane diisocyanate and hexamethylene diisocyanate are excellent in handling and workability and thickening properties. From the viewpoint of thickening effect and foaming, the amount of the isocyanate compound used is preferably in the range of 0.1 to 7.0 parts by weight based on 100 parts by weight of the unsaturated polyester modified with dicyclopentadiene and the polymerizable monomer. Inorganic thickeners include magnesium oxide,
There are metal oxides or metal hydroxides such as magnesium hydroxide, calcium oxide, and calcium hydroxide. From the viewpoint of thickening effect and water resistance, the amount of metal oxide or metal hydroxide used is 0.00 parts by weight per 100 parts by weight of the unsaturated polyester modified with dicyclopentadiene and the polymerizable monomer.
A range of 1 to 3.0 parts by weight is preferred.

To thicken the composition with an isocyanate compound, for example, these may be mixed at room temperature and left to stand. When thickening with a metal oxide or metal hydroxide, it is also possible to shorten the thickening time by heating to 30 to 45°C.

[0020] When producing a molded article, a curing organic peroxide (cured product), a filler, a reinforcing material, a mold release agent, a coloring agent, etc. can be added as necessary.

Examples of the organic peroxide for curing include t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide,
Cyclohexanone peroxide, methyl ethyl ketone peroxide, etc. are used.

[0022] Examples of fillers include calcium carbonate, clay, barium sulfate, and aluminum hydroxide. The reinforcing material may be a roving made of fibers such as glass fibers, vinylon fibers, carbon fibers, etc., processed into short fibers, woven fabrics, knitted fabrics, threads, braided fabrics, etc.

[0023] Examples of mold release agents include zinc stearate and calcium stearate. Inorganic colorants, which are currently used for coloring unsaturated polyester resins, are used as colorants.
All organic colorants can be used.

If necessary, thermoplastic polymers such as polystyrene, polyvinyl acetate, and polymethyl methacrylate, and thermosetting polymers such as phenol resins, epoxy resins, and melamine resins may also be used in combination. Flame retardants such as antimony trioxide, hexabromobenzene, and chlorinated paraffins may also be used.

The molding resin composition of the present invention can be applied not only to sheet molding compound methods, but also to bulk molding compound methods, preform matched metal die molding methods, hand lay-up molding methods, resin injection molding methods, etc. It is.

[0026]

[Examples] Examples of the present invention will be described below. Parts are parts by weight, and % are weight %. Example 1 Maleic anhydride 686 g (0.7 mol), isophthalic acid 498 g (0.3 mol), propylene glycol 571
g (0.75 mol), neopentyl glycol 312 g
(0.3 mol), dicyclopentadiene 132 g (0.3 mol), dicyclopentadiene 132 g (0.3 mol),
1 mol) and triphenylphosphite, an organic phosphorous acid ester (Johoku Kagaku Kogyo Co., Ltd. trade name: JP360)
) 1.1g (0.05% by weight based on the total weight of the preparation) were mixed at room temperature under a nitrogen stream, and after raising the temperature to 150°C, the temperature was raised from 150°C to 210°C over 6 hours, and further 8 Dehydration condensation was carried out for a period of time to obtain unsaturated polyester A modified with dicyclopentadiene having an acid value of 30. This unsaturated polyester A
, 65 g was dissolved in 35 g of styrene containing 0.01 g of N-nitrosophenylhydroxyamine aluminum salt to obtain unsaturated polyester resin UP-1. The viscosity of UP-1 was 15 poise (25°C, Gardner method). Using UP-1, a curing agent (t-
The storage stability of a resin composition containing a mixture of butylperoxyisopropyl carbonate (butylperoxyisopropyl carbonate) and a thickener was excellent.

Comparative Example 1 Maleic anhydride 686g (0.7 mol), isophthalic acid 498g (0.3 mol), propylene glycol 571
g (0.75 mol), neopentyl glycol 312 g
(0.3 mol), dicyclopentadiene 132 g (0.3 mol), dicyclopentadiene 132 g (0.3 mol),
1 mol) was mixed at room temperature under a nitrogen stream, heated to 150°C, then heated from 150°C to 210°C over 6 hours, and then heated to 210°C for 8 hours.
Dehydration condensation was carried out for a period of time to obtain unsaturated polyester B modified with dicyclopentadiene having an acid value of 30. 65 g of this unsaturated polyester B was dissolved in 35 g of styrene containing 0.01 g of hydroquinone, and the unsaturated polyester resin UP
-2 was obtained. The viscosity of UP-2 was 16 poise (25°C, Gardner method). As shown in Table 1, the storage stability of UP-2 and the resin composition in which a curing agent was mixed were both poor.

Comparative Example 2 65 g of unsaturated polyester A obtained in Example 1 was dissolved in 35 g of styrene containing 0.01 g of hydroquinone to obtain unsaturated polyester resin UP-3. As shown in Table 1, the storage stability of UP-3 and the resin composition in which a curing agent was mixed therewith was both improved but inferior to UP-2 of Comparative Example 1.

Comparative Example 3 65 g of unsaturated polyester A obtained in Example 1 was dissolved in 35 g of styrene containing 0.009 g of toluhydroquinone and parabenzoquinone to obtain unsaturated polyester resin UP-4. As shown in Table 1, the storage stability of UP-4 and the resin composition in which a curing agent was mixed was inferior to that of the resin composition in which a curing agent was mixed.

Example 2 65 g of unsaturated polyester A obtained in Example 1 was treated with N-
Nitrosophenylhydroxyamine aluminum salt 0.
Unsaturated polyester resin U
P-5 was obtained. As shown in Table 1, the storage stability of UP-5 and the resin composition in which a curing agent is mixed therein is excellent, and the storage stability of the resin alone is particularly improved compared to UP-1 of Example 1. was.

Example 3 65 g of unsaturated polyester A obtained in Example 1 was treated with N-
Nitrosophenylhydroxylamine aluminum salt 0
．． 007 g, toluhydroquinone 0.002 g and parabenzoquinone 0.001 g were dissolved in 35 g of styrene to obtain unsaturated polyester resin UP-6. U.P.
As shown in Table 1, the storage stability of -6 and the resin composition in which a curing agent was mixed therein was very good, and
It is even better than P-1.

[0032]

[Table 1]

[0033]

Effects of the Invention: The molding resin composition of the present invention has excellent storage stability, so its properties do not change even when stored for a long period of time, preventing molding defects such as poor thickening, short shots, and poor appearance. can be significantly reduced. In addition, since storage stability is excellent even if the gelation time is short, molding time can be shortened and productivity can be improved.

Claims (3)

[Claims] Claim 1: (a) an unsaturated polyester modified with dicyclopentadiene in the presence of an organic phosphite, (b) a polymerizable monomer, (c) an N-nitrosophenylhydroxylamine aluminum salt, and optionally (d) A molding resin composition containing a thickener. 2. The molding resin composition according to claim 1, wherein the organic phosphite is triphenyl phosphite. 3. Unsaturated polyester modified with dicyclopentadiene uses 0.01 to 0.40 mol of dicyclopentadiene and 0.01 to 0.40 mol of neopentyl glycol per 1.0 mol of the acid component. The molding resin composition according to claim 1 or 2, which is an unsaturated polyester obtained by.