JPH1088004A - Molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding material excellent in halogen-free flame retardancy, moldability, uniform colorability, and the appearance of a molded article made therefrom by producing a sheet molding compound containing an aluminum hydroxide composition having a specified particle diameter. SOLUTION: This material comprises an unsaturated resin composition containing aluminum hydroxide which consists of 10-90wt.% particles with a mean diameter of 10-100μm and 90-10wt.% particles with a mean diameter of 5μm or smaller and which is in an amount of at least 250 pts.wt. based on 100 pts.wt. unsaturated resin. The unsaturated resin composition preferably comprises an unsaturated resin (A) and an unsaturated polymerizable monomer (B). The resin A used preferably comprises an unsaturated polyester or an epoxy acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material which is excellent in halogen-free flame retardancy, moldability, uniform coloring, and appearance of a molded article.

[0002]

2. Description of the Related Art Sheet molding compound (hereinafter, abbreviated as polyester) having an unsaturated polyester resin as a matrix is excellent in productivity, and is used for housing members such as bathtubs, water tanks, septic tanks, and automobile members such as automobile outer panels. Used in large quantities. The reason is that the molding is easy, and the molded product has excellent water resistance, strength and appearance of the molded product. However, the flame-retardant polyester SMC currently on the market does not have sufficient flame-retardant performance, and the use of a flame-retardant containing a halogen such as chlorine or bromine in the matrix resin generates harmful gases during combustion. have.

[0003] Recently, an SMC (hereinafter abbreviated as phenol SMC) using a phenol resin having excellent flame retardancy as a matrix has been developed. This achieves the flame-retardant performance that was difficult with the conventional flame-retardant polyester SMC, and has been put to practical use for interior parts of railway vehicles and the like. No harmful gases are generated during combustion. However, phenol SMC has problems such as the necessity of a degassing step due to generation of water vapor at the time of molding, and the necessity of further painting due to the poor appearance of the molded article.

[0004] Therefore, the flame retardancy is equivalent to phenol SMC,
There is a demand for molding materials whose moldability, uniform colorability, and appearance of molded products are equivalent to those of conventional polyester SMC, for example, indoor and outdoor building materials, railway vehicle materials, electric parts and the like.

[0005]

An object of the present invention is to provide a molding material which is excellent in halogen-free flame retardancy, moldability, uniform colorability and appearance of a molded article.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on these problems and as a result have completed the present invention.

That is, the present invention relates to a molding material comprising an unsaturated resin composition containing aluminum hydroxide, wherein the aluminum hydroxide has (a) an average particle size of 10 to 100 μm,
10 to 90% by weight, (b) average particle size 5 μm or less, 90
A molding material characterized by containing at least 250 parts by weight based on 100 parts by weight of the unsaturated resin, preferably an unsaturated resin composition, containing the unsaturated resin (A) and the unsaturated resin (A). The present invention provides a molding material comprising the polymerizable monomer (B), preferably wherein the unsaturated resin (A) is an unsaturated polyester.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The molding material of the present invention refers to a fiber reinforced material impregnated with an unsaturated resin composition comprising an unsaturated resin, an unsaturated polymerizable monomer, a curing agent and, if necessary, a curing accelerator, or It is a so-called sheet molding compound or bulk molding compound manufactured by mixing.

The unsaturated resin used in the present invention is preferably an unsaturated polyester (I) or an epoxy acrylate (II).

The unsaturated polyester (I) is defined as α, β-
An ester reaction product of a dibasic acid containing an unsaturated dibasic acid and a polyhydric alcohol, or a product obtained by a condensation reaction of these with a dicyclopentadiene-based compound. Preferably, it has a molecular weight in the range of 500 to 5,000.

Examples of the α, β-unsaturated dibasic acid used in preparing the unsaturated polyester include maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. As the saturated dibasic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, Hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-
Dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,
7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride,
4,4′-biphenyldicarboxylic acid and dialkyl esters thereof can be mentioned.

The polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, -Methyl-1,3-propanediol, 1,3
-Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexaneglycol, 1,3
-Cyclohexaneglycol, 1,4-cyclohexaneglycol, 1,4-cyclohexanedimethanol, paraxyleneglycol, bicyclohexyl-4,4'-
And diol, 2,6-decaling glycol, and 2,7-decaling glycol.

The dicyclopentadiene compound includes, for example, dicyclopentadiene and derivatives thereof. Dicyclo unsaturated polyester is obtained by reacting dicyclopentadiene and maleic anhydride dropwise with water to obtain a reaction product, and further reacting the reaction product with a polyhydric alcohol, or an unsaturated dibasic acid and a polyhydric alcohol. It is produced by a method of reacting dicyclopentadineene with the reaction product of the above.

The epoxy (meth) acrylate (II) of the present invention may be, for example, a bisphenol type epoxy resin alone or a combination of a bisphenol type epoxy resin and a novolak type epoxy resin. Di (meth) of 6-naphthalene type epoxy resin
An acrylate or the like is referred to, and an epoxy resin having an average epoxy equivalent preferably in the range of 150 to 450 and an unsaturated monobasic acid are reacted in the presence of an esterification catalyst. It is obtained.

As the above-mentioned bisphenol-type epoxy resins, only typical ones are mentioned. Di (meth) acrylate of bisphenol A type epoxy resin and di (meth) acrylate of hydrogenated bisphenol A type epoxy resin are mentioned. Di (meth) acrylate of bisphenol A ethylene oxide addition type epoxy resin, di (meth) acrylate of bisphenol A propylene oxide addition type epoxy resin, di (meth) acrylate of bisphenol F type epoxy resin, 1,6-naphthalene type epoxy resin Di (meth) acrylate and the like.

As the above-mentioned novolak type epoxy resin, if only typical ones are mentioned, epoxy resins obtained by reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin, etc. It is.

Further, if only the above-mentioned unsaturated monobasic acids are particularly representative, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid,
Examples include monomethyl malate, monopropyl malate, monobutyl malate, or mono (2-ethylhexyl) malate.

These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the above-mentioned epoxy resin and unsaturated monobasic acid is preferably 60 to 14
The reaction is carried out at 0 ° C, particularly preferably at a temperature in the range of 80 to 120 ° C, using an esterification catalyst.

As the esterification catalyst, known and commonly used compounds can be used as they are, but among them, triethylamine,
Various tertiary amines such as N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; and diethylamine hydrochloride.

The epoxy (meth) acrylate preferably has a number average molecular weight of 450 to 2,500.
0, particularly preferably in the range of 500 to 2,200 is appropriate. If the molecular weight is less than 450, the resulting cured product will be tacky or the strength properties will be reduced, while if it is greater than 2,500, the curing time will be longer. , Your productivity will start to deteriorate.

The polymerizable unsaturated monomer (B) used in the present invention includes, for example, styrene and α-methyl which are usually used in unsaturated polyester resin compositions as long as the effects of the present invention are not impaired. Styrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinylacetate, diarylphthalate, triarylcyanurate, acrylate, methacrylate, etc .; (meth) acrylic Methyl acid,
Ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth)
Acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate , Diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, neopentyl glycol di (meth) acrylate, PTMG dimethacrylate, 1,3-butylene Rikoruji (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
2-hydroxy-1,3 dimethacryloxypropane, 2,
2-bis [4- (methacryloxyethoxy) phenyl]
Propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n = 2) Diacrylate, isocyanuric acid EO-modified (n = 3) diacrylate, pentaerythritol diacrylate monostearate, and the like can be used in combination, and examples thereof include an unsaturated monomer or unsaturated oligomer crosslinkable with a resin. Further, when it is necessary to improve the abrasion resistance, scratch resistance, agitation resistance, chemical resistance, etc. of the cured product surface, a polyfunctional unsaturated monomer, preferably a trifunctional or higher (meth) acrylic Acid ester monomers are preferably used in combination. Specifically, trimethylolpropane tri (meth) acrylate, tetramethylol metal triacrylate, tetramethylol methanetetraacrylate, pentaerythritol triacrylate, trimethylolpropane PO-modified (n = 1) triacrylate,
Isocyanuric acid EO-modified (n = 3) triacrylate, isocyanuric acid EO (n = 3) -ε-caprolactone-modified triacrylate, dipentaerythritol penter and hexa-acrylate, pentaerythritol
Polymerizable monomers such as -tetra (meth) acrylate may be used in combination.

The aluminum hydroxide of the present invention comprises (a)
Average particle size 10-100 μm, 10-90% by weight,
(B) Average particle size: 5 μm or less, composed of 90 to 10% by weight, preferably (a) :( b) = 30 to 70% by weight: 70 to 30% by weight. Exceeding these ranges is not preferable because the viscosity of the resin composition becomes large and handling becomes difficult. These aluminum hydroxide compositions are used in an amount of 25 parts per 100 parts by weight of the unsaturated resin.
0 parts by weight or more, preferably 300 to 500 parts by weight. However, when using as a BMC molding material, it is preferable to use 300 parts by weight or more. If the amount is less than 250 parts by weight, sufficient flame retardancy cannot be obtained, which is not preferable. In addition, other fillers may be added.

Other fillers include, for example, hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, silica stone powder, talc, barium sulfate, silica powder,
Examples include glass powder, glass beads, mica, and cellulose yarn.

The resin composition preferably uses a polymerization inhibitor, for example, trihydrobenzene, toluhydroquinone, 1,4-naphthoquinone, parabenzoquinone,
Toluhydroquinone, hydroquinone, benzoquinone,
Hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-
Methyl phenol and the like can be added. Preferably, 10 to 1000 ppm can be added to the resin composition.

The resin composition of the present invention preferably contains a curing agent to accelerate the curing, and examples thereof include an organic peroxide. Specifically, known materials such as diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxyketal, alkylperester, and percarbonate are used. .

The amount of the curing agent to be added is 0.01 to 5 parts by weight based on 100 parts by weight of the total of the polymerizable resin and the polymerizable monomer. The above curing agents may be used in combination of two or more.

The resin composition of the present invention preferably contains a curing accelerator, for example, metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate. And examples of metal chelate compounds include vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetyl acetonate. The amines include N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol Examples include amine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline and the like.

The amount of the curing accelerator to be added depends on the amount of the unsaturated resin (A)
It is preferably used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total of the monomer and the monomer (B). In the present invention, an amine accelerator is preferred. The curing accelerator may be added to the resin (A) in advance, or may be added at the time of use.

In the present invention, a fiber reinforced material is used. For example, glass fibers, organic fibers such as amide, aramid, vinylon, polyester, and phenol, carbon fibers, metal fibers, ceramic fibers, or a combination thereof are used. From the viewpoint of economy, glass fibers are particularly preferable. In addition, the form of the fiber includes plain weave, satin weave, non-woven fabric, and mat shape. The glass roving is preferably cut into 5 to 100 mm and used in a chopped strand.

In the present invention, various additives such as a filler, an ultraviolet absorber, a pigment, a thickener, a thickener, a low shrinkage agent,
Anti-aging agent, plasticizer, aggregate, flame retardant, stabilizer, reinforcing material,
A light curing agent or the like may be used.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, "parts" in the text indicates parts by weight.

Example 1 Comparative Examples 1 to 4 Example 1 (SMC1) and Comparative Examples 1 to 4 according to the formulation examples shown in Tables 1 and 2.
(SMC2-5) were prepared. Of these SMCs, SM
C2 and 3 had high resin compound viscosity, so that the impregnating property of the glass fiber was poor, and many non-wet glass fibers were observed. SMC1, 4, 5 were good. These SM
When C was press-molded, swelling frequently occurred on the surface of SMCs 2 and 3, and a molded product could not be obtained.

In SMC 1, 4, and 5, good appearance quality was obtained. When the oxygen index was measured for SMCs 1, 4, and 5 (see Tables 6 and 7), the SMC 1 was 70.2 or more (the measurement upper limit of the instrument was 70.2), and both SMCs 4 and 5 were 32.3. It was confirmed that the product of the present invention was excellent in flame retardancy.

[Comparative Examples 5 to 7] Comparative Examples 5 to 7 of the formulation examples in Tables 3 to 5 were prepared, and molded plates of SMCs 6 to 8 were obtained. Comparative Example 5 (SMC6) is based on a general residential SMC, Comparative Example 6 (SMC7) is based on a halogen-containing SMC, and Comparative Example 7 (SMC8) is a phenol resin SMC. SM
With respect to C1, 6, 7, and 8, the oxygen index, the combustion gas analysis, and the higher calorific value were measured.

As a result, Example 1 (SMC1) obtained as shown in Tables 6 to 8 had an oxygen index and combustion gas analysis showed Comparative Example 7.
(Phenolic resin SMC8), the highest calorific value is the lowest, and it can be said that it is excellent in flame retardancy. Comparative example 5 (SMC6) of the conventional product is inferior in flame retardancy, and comparative example 6 (SMC6)
7) has excellent flame retardancy, but harmful hydrogen chloride gas is detected.

Comparative Example 7 (SMC8) has a fatal defect that the flame retardancy is excellent, but it is necessary to drain water during molding, and it is difficult to color, so that the molded product needs to be painted. ing. On the other hand, SMC1 of the present invention is superior to other SMCs because it has excellent flame retardancy, does not generate harmful gas, and is easy to mold and color.

[Test method]-Oxygen index: JIS K-7201-Combustion gas analysis: JIS K-7217-Higher heating value: JIS M-8814-Building material flame retardancy test: JIS A-1321-Vehicle material combustion Test: Ministry of Transport

Note) Polylite: Dainippon Ink and Chemicals
Products "Unsaturated polyester resin" 0P White PS-5820: Dainippon Ink and Chemicals
Products FLOWSEN UF-80: Sumitomo Seika Co., Ltd. Products Kayabutyl B: Kayaku Akzo Co., Ltd. products

[0039]

[Table 1] Table-1

[0040]

[Table 2] Table 1 continued

[0041]

[Table 3] Table 1 continued

[0042]

[Table 4] Table 1 continued

[0043]

[Table 5] Table-1 continued

[0044]

[Table 6]

[0045]

[Table 7]

[0046]

[Table 8]

[0047]

[Table 9]

[0048]

[Table 10] Physical properties

[0049]

According to the present invention, an SMC molding material containing an aluminum hydroxide composition having a specific particle size is obtained, which is excellent in halogen-free flame retardancy, moldability, uniform coloring property, and appearance of a molded article. A molded article can be obtained.

Therefore, taking advantage of this flame retardancy, it has the same moldability as the conventional unsaturated polyester-based SMC, and uses the flame-retardant phenol SMC for vehicle interior materials, vehicle materials, indoor / outdoor civil engineering building materials, and other electrical materials. It can be widely used for electronic parts materials, medical equipment materials, housing equipment (bathtubs, counters, etc.) materials.

Claims (3)

[Claims] 1. A molding material comprising an unsaturated resin composition containing aluminum hydroxide, the aluminum hydroxide comprising: (a) an average particle size of 10 to 100 μm, 10 to 90% by weight, (b) an average particle size of 5 μm or less, 90 to 10% by weight, based on 100 parts by weight of the unsaturated resin, 25 parts by weight.
A molding material containing at least 0 parts by weight. 2. An unsaturated resin composition comprising the unsaturated resin (A)
The molding material according to claim 1, comprising: and an unsaturated polymerizable monomer (B). 3. The molding material according to claim 1, wherein the unsaturated resin (A) is an unsaturated polyester.