JPS6037794B2 - Packaging materials for unsaturated polyester resin molding materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to packaging materials for unsaturated polyester resin molding materials.

An object of the present invention is to provide a storage-stabilized unsaturated polyester resin molding material.

The unsaturated polyester resin molding materials in the present invention include BRIMIX, BMC, SMC, prepreg, etc.
Its shape is sheet-like, lump-like, rod-like, granular, pellet-like,
They are in the form of flakes, straws, etc., and are processed into mature shapes by compression molding, transfer molding, injection molding, rotary molding, extrusion molding, etc., and are used for bathtubs, bathroom vanities, waterproof barns, electrical/electronic parts, automobile parts, laminates, etc. It is used for a wide range of purposes. Conventionally, unsaturated polyester resin molding materials have had serious problems with deterioration of moldability due to volatilization of the styrene copolymerizable monomer contained therein, that is, storage stability, and major improvements have been made to this problem. , which was strongly requested by the industry.

In particular, when styrene, which has a low boiling point, is used as the styrenic copolymerizable monomer and polyethylene film or polypropylene film is used as the packaging material, the deterioration of moldability over time due to styrene volatilization is very large. One way to prevent the volatilization of styrenic monomers is to use thin aluminum films or polyvinylidene chloride films as packaging materials, but both are expensive and cannot be used in materials such as unsaturated polyester resin molding compounds. This leads to a significant increase in costs, so its use is inappropriate. From the viewpoint of preventing the volatilization of styrene, it is possible to use packaging materials with so-called gas barrier properties.

Such packaging materials include polyester, polyamide, polyvinyl alcohol, polyvinyl acetate, ethylene and
It is well known that there are films made of vinyl acetate copolymers, vinyl chloride/vinyl acetate copolymers, and the like. The present inventors have conducted various studies on improving the storage stability of unsaturated polyester resin molding materials containing styrenic copolymerizable monomers using the various films with good gas barrier properties described above. Surprisingly, if a film with good gas barrier properties is used as a packaging material,
We discovered that, among films with good gas barrier properties, only polyethylene terephthalate, polybutylene terephthalate, and polyxylylene adipamide films improved storage stability, rather than directly improving storage stability. It was.

Furthermore, when polyethylene terephthalate, polybutylene terephthalate or polyxylylene adipamide films are used alone, if the thickness is too thin, the film strength will not be sufficient as a packaging material, while if the thickness is too thick, the film will It was found to be hard and unsuitable for use as packaging material.

To solve this problem, we have found that it is best to use a laminate film in which a polyolefin film or a polyvinyl film is laminated onto a thin film of polyethylene terephthalate, polybutylene terephthalate, or polymethaxylylene adipamide. This laminate film has sufficient strength for practical use.
It is flexible, easy to handle, and can be heat-sealed, making it highly practical. That is, the present invention uses pseudopolyethylene terephthalate. This packaging material for unsaturated polyester resin molding materials is made of a laminate film of a polybutylene terephthalate film or a polyxylylene adipamide film and a {B} polyolefin film or polyvinyl film.

By using the packaging material of the present invention, the storage stability of unsaturated polyester resin molding compositions is significantly improved compared to the polyethylene films used hitherto.

In the present invention, the unsaturated POIJ ester resin has Q, B-unsaturated dibasic acid as an essential component as a carboxylic acid component, and if necessary, a saturated dibasic acid or other polybasic acid as a concomitant component, and as an alcohol component. It is made by blending an unsaturated polyester mainly consisting of dihydric alcohol with a copolymerizable monomer. Examples of Q,B-unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid,
Examples of saturated dibasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydro-phthalic anhydride, hexahydrophthalic anhydride, hetaconic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and adipine. acids, such as sepathic acid.

Examples of dihydric alcohols include ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, dipropylene glycol, and 1,3-propylene glycol.
- and 1,4-butanediol, 1,6-hexanediol, neobentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, dichloro and dipromone-neobentyl glycol, cyclohexanedimethanol, 2 , 2-bis[4-(2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-pis[
2,6-dipromo 4-(2-hydroxypropoxy)
phenyl]propane, 2,2-bis[2,6-dibromo(2-hydroxyethoxy)phenyl]propane, and the like.

As the alcohol component, in addition to dihydric alcohol, a small amount of trivalent or higher polyol such as glycerin, trimethylolethane, or trimethylolpropane may be used in combination. There are no particular limitations on the method for producing unsaturated polyester, and it is produced according to a general method.

As the styrenic copolymerizable monomer, styrene, rt
-butylstyrene, vinyltoluene, chlorostyrene,
Examples include Q-methylstyrene and divinylbenzene. Styrene copolymerizable with acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, and glycidyl methacrylate, AJ-based single star monomers such as diallyl phthalate and triallyl cyanurate, and pinyl acetate and dibutyl fumarate. It may also be used in combination with monomers. The blending ratio of the unsaturated polyester and these copolymerizable monomers is not particularly limited, but is preferably 90:10 to 20:80 (weight ratio). In the present invention, the unsaturated polyester resin molding material includes calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, alumina, hydrated alumina, silica, and clay. , fillers such as talc, reinforcing materials such as glass fiber, asbestos, carbon fiber, vinylon fiber, pulp, polymerization inhibitors, grading agents, pigments, thickeners,
It refers to a product that contains a polymerization initiator, template agent, etc.

Specifically, Primics, BMC, SMC, Fu. I.J.
There are preg etc. The harmful polyethylene terephthalate in the present invention. Film, polybutylene terephthalate
The film and the polyxylylene adipamide film are double-stretched films produced by a sequential two-rut stretching method, a simultaneous biaxial stretching method, an inflation stretching method, or the like.

The thickness of the film is 5-30 mm, preferably 10-2 mm
5 μm, and sufficient storage stability is achieved with this thickness. In the present invention, the polyolefin film refers to a thinly stretched, single-stretched, or biaxially stretched film of low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, ethylene/propylene copolymer, etc. be.

On the other hand, polyvinyl films include polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, ethylene/vinyl acetate copolymer, vinyl chloride/vinyl acetate copolymer, polymethyl methacrylate, polystyrene, acrylonitrile/styrene copolymer, and styrene. /butadiene copolymer, acrylonitrile/butadiene/styrene copolymer, ionomer, or other unstretched, uniaxially stretched or double-stretched films. The thickness of polyolefin film or polyvinyl film should be 2.
0 to 200 Buddhas, preferably 30 to 150 Buddhas.

Lamination methods include dry lamination, in which multiple single films are bonded together using an adhesive, inline lamination, in which one film is melt-extruded onto the other, and coextrusion. should be adopted. The laminate film used in the present invention may have two layers or three or more layers.

The laminate film has an outermost layer of polyethylene terephthalate film, polybutylene terephthalate film, or polyxylylene adipamide film,
Preferably, the innermost layer is a polyolefin film or a polyvinyl film.

The unsaturated polyester resin molding material containing a styrenic copolymerizable monomer that has been storage-stabilized using the packaging material of the present invention has excellent moldability over a long period of time compared to conventional storage methods. stable.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the Examples.

In the examples, parts represent parts by weight.

The acid value is determined using chloroform as a solvent and is determined according to JISK690.
Measured according to 1. The storage stability of unsaturated polyethylene resin molding materials was determined by measuring the change in disk elongation over time.

Disc elongation was measured according to the JIS K6911 disc flow test method, and the conditions were as follows: sample 3,
Mold temperature 16000, pressure 2500kg/, pressurization time 3■ Sand. Separately, moldability was also evaluated using an injection molding machine (Nestal Duromat D-120, manufactured by Sumitomo Heavy Industries, Ltd.). The molding conditions were as follows: mold temperature 160 ± 500 °C, cylinder temperature 90 °C (front part), 40 °C
00 (rear), screw rotation speed 40 RPM, injection injection pressure 1400 kg/, screw back pressure 0 (gauge),
Injection time: 12 seconds, curing time: 90 seconds. Example A conventional method using terephthalic acid and fumaric acid (terephthalic acid/fumaric acid molar ratio = 33/67) and 1,4-butanediol and propylene glycol (1,4-butanediol/propylene glycol molar ratio = 90/10) as raw materials. According to the acid number 8.7, Gardner-Holdt bubble viscosity U (
An unsaturated polyester containing 7% by weight of tetrachloroethane (2500) was obtained.

170 parts of the resulting unsaturated polyester, 7 parts of styrene, 61 parts of calcium carbonate [NS1200, Nitto Funka Kogyo ■ product], 150 parts of glass fiber [ES-06-B-32, Nippon Glass Fiber Products] , 1 part of zinc stearate, 2.0 parts of dicumyl peroxide, and 0.05 part of p-penzoquinone were thoroughly kneaded using a pressure kneader overflowing to 8,000 ℃, and then a cutter heated to 8,000 ℃. A granular unsaturated polyester resin molding material with a diameter of approximately 4 was produced using an extrusion granulator. The resulting granular molding material had no stickiness and exhibited free-flowing properties. The disc elongation was 92 Yanagi, and the moldability with an injection molding machine was good. After 20k9 of each of the granular molding materials were encapsulated in various packaging materials listed in the following table, they were left in an atmosphere of 35% relative humidity and 85% relative humidity as an accelerated storage stability test.

After being left for 3 months, the molding materials encapsulated in various packaging materials were taken out and their disk elongation was measured, and their moldability was evaluated using an injection molding machine, with the results shown in the following table.

In addition, 02 gas permeability is also listed in the table as gas barrier property data of each packaging material for reference. Storage stability test results (US) Film thickness 30〃K conversion, ASTM D143
4-58.

Unit Z/〆・hr/atm. 1) Quoted from the New Packaging Detailed Technical Report (Japan Productivity Center, published in 1971).

2) Measured value.

Claims (1)

[Claims] 1. An unsaturated polyester resin molding material and packaging material comprising a laminate film of (A) polyethylene terephthalate film, polybutylene terephthalate film, or polyxylylene adivamide film and (B) polyolefin film or polyvinyl film.