JPH0573782B2 - - Google Patents

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a preform mated metal die method for molding fiber-reinforced plastics (FRP);
The present invention relates to a conductive resin composition for molding that is extremely useful as a molding material for prepreg methods, bulk molding compound methods, sheet molding methods, etc.

(Prior art) A resin composition obtained by adding a thickener to a mixture consisting of an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a curing catalyst, a mold release agent, a filler, a coloring agent, etc. A molding resin composition obtained by coating and impregnating a reinforcing material such as glass fiber, or kneading it with a reinforcing material using a kneader, etc., and then increasing the viscosity is a so-called bulk molding compound or sheet molding compound. It is a material known as However, since the above-mentioned molding resin composition shrinks significantly during curing, the resulting molded product is likely to have distortions and cracks, and the reinforcing material may bulge out on the surface of the molded product, resulting in loss of surface smoothness. It has the disadvantage of being damaged.
Furthermore, since it has high electrical insulation properties, it also has the disadvantage of being highly susceptible to contamination due to static electricity.

Conventionally, in order to eliminate such drawbacks, thermoplastic resins such as polymethyl methacrylate, polystyrene, propylene glycol, and saturated polyesters made of adipic acid or sebacic acid are mixed and cured in the above-mentioned molding resin composition. A method of significantly reducing shrinkage during curing is known. Also, methods of mixing various surfactants, carbon black, etc. are known to prevent static electricity.

However, in these conventional methods, the unsaturated polyester resin and the thermoplastic resin phase separate and stickiness remains even after curing.Even after molding, the thermoplastic resin bulges out onto the surface of the molded product, resulting in a mottled pattern. Uniformity cannot be obtained. Paintability of molded products is poor. The antistatic effect of molded products changes over time.
In addition, there was a drawback that the antistatic effect was reduced due to washing (a problem to be solved by the invention).An object of the present invention is to provide a conductive resin composition for molding that has improved the above-mentioned drawbacks. .

(Means for Solving the Problems) The present invention comprises an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a thermoplastic resin compatible with the monomer, a conductive alkali metal titanate, an inorganic The present invention relates to a conductive resin composition for molding containing a filler.

The unsaturated polyester used in the present invention is 50 to 100 mol % of α,β-unsaturated dibasic acid and 50 to 0 mol % of aliphatic saturated dibasic acid, aromatic saturated dibasic acid, or alicyclic dibasic acid. % and a polyhydric alcohol or alkylene oxide through a polycondensation reaction. At this time, in order to exhibit sufficient low shrinkage during molding, α,
It is preferable to use 60 mol% or more of the β-unsaturated dibasic acid.

α, β used in the production of unsaturated polyester
- Examples of unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and the like. Further, examples of the aliphatic saturated dibasic acid used in combination with the α,β-unsaturated dibasic acid include adipic acid, sebacic acid, etc.
Examples of aromatic saturated dibasic acids include phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid, and further examples of alicyclic dibasic acids include tetrahydrophthalic anhydride and endomethylenetetrahydrophthalic acid.

In addition, polyhydric alcohols that are one of the components used in the production of unsaturated polyesters include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3
-butanediol, 1,4-butanediol,
Examples include glycols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, and triols such as glycerin and trimethylolpropane. Furthermore, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Furthermore, dicyclopentadiene and cyclopentadiene-maleic acid adducts are used as substitutes for the above raw materials.

The vinyl ester resin used in the present invention has a carboxyl group in an unsaturated monobasic acid per equivalent of epoxy group contained in the epoxy compound.
It is obtained by adding a polymerizable monomer to an ester obtained by heating in the presence of an esterification catalyst and reacting until the acid value becomes 20 to 0 within the range of 0.5 to 1.5 equivalents. Examples of epoxy compounds used in the production of vinyl ester resins include 2,
Diglycidyl ether obtained by the reaction of 2'-bis(4-hydroxyphenyl)propane with epichlorohydrin or methylepichlorohydrin; diglycidyl ether obtained by the reaction of glycols with epichlorohydrin or methylepichlorohydrin; phenol and Examples include polyglycidyl ethers obtained by reacting novolac obtained by reaction with formaldehyde and epichlorohydrin or methylepichlorohydrin, and polyepoxy compounds obtained from polybutadiene. Can be used together.

Examples of unsaturated monobasic acids include acrylic acid,
Examples include methacrylic acid and crotonic acid.
These unsaturated monobasic acids may be used in combination with saturated monobasic acids or polybasic acids, if desired.

Examples of esterification catalysts include secondary amines such as dimethylamine and diethylamine, N,
Examples include tertiary amines such as N'-dimethylaniline, pyridine, and triethylamine, quaternary ammonium salts such as tetramethylammonium chloride, and sulfonates such as paratoluenesulfonate.

The polymerizable monomer to be mixed with the unsaturated polyester or vinyl ester resin is not particularly limited as long as it polymerizes with the unsaturated polyester or vinyl ester resin, and specifically, styrene, α-methylstyrene, chlorostyrene, Vinyl toluene, diallyl phthalate, diallyl isophthalate, lower esters of acrylic acid or methacrylic acid,
Examples include vinyl acetate and triallyl isocyanurate, and the amount of the polymerizable monomer used is preferably 20 to 120 parts by weight per 100 parts by weight of the unsaturated polyester or vinyl ester resin.

The thermoplastic resin used in the present invention is not particularly limited as long as it is compatible with the polymerizable monomer, and specifically, styrene, ethylene, propylene, vinyl chloride, vinyl acetate, methyl methacrylate, Methyl acrylate, ethyl methacrylate, ethyl acrylate, acrylic acid,
Homopolymers and copolymers of polymerizable monomers such as methacrylic acid, maleic acid monoester, acrylamide, etc., styrene-acrylonitrile copolymers, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, saturated polyesters etc. There is no particular limit to the molecular weight of thermoplastic resin, but generally speaking it is 2000~
A range of 1,000,000 is preferable, and the amount used is:
1 to 100 parts by weight of the total amount of unsaturated polyester and/or vinyl ester resin and polymerizable monomer
40 parts by weight is preferred.

Preferred conductive alkali metal titanates used in the present invention are (1) general formula M ₂ O・aTiOx・bH ₂ O (where M is Li,
Alkali metals such as Na and K, 0<a≦8,0
≦b≦4, 0<x<2, a, b, x are real numbers), and is generally referred to as reduced alkali metal titanate or bronze alkali metal titanate (), (2) General formula M ₂ O・aTiOy・bH ₂ O (in the formula M, a,
b is the same as above, an alkali metal titanate represented by 0<y≦2), and one or more types of conductive metals and/or conductive metal compounds such as metal oxides and halides exhibiting conductivity. conductive alkali metal titanate () coated with (3) general formula M ₂ O・aTiOy・bH ₂ O (in the formula
b, y are the same as above) When producing the alkali metal titanate group represented by (b, y are the same as above), conductive metals and/or conductive metal compounds such as metal oxides and halides of these metals are eutectic with alkali metal titanates, or Conditions that cause crystallization or precipitation on the surface of alkali metal titanate, i.e. raw materials for alkali metal titanate, metals that exhibit conductivity, or oxides, hydroxides, halides, carbonates, nitrates, and sulfates of these metals. When producing alkali metal titanates under conditions in which one or a mixture of two or more metal compounds such as metal compounds coexist, after production in a reducing atmosphere or in an oxidizing atmosphere, reduction treatment or doping treatment is performed as necessary. These various conductive alkali metal titanates can be used alone or in combination of two or more.

The conductive alkali metal titanate of the present invention is
It is distinguished from alkali metal titanate () represented by the general formula M ₂ O.aTiO _{2.bH 2} O (a and b are the same as above).

In general, alkali metal titanate () is obtained as a fibrous single crystal and is excellent as a heat-resistant and reinforcing filler, but it is an electrical insulator, and alkali metal titanate () alone cannot be used as a filler. A composition exhibiting electrical conductivity cannot be obtained. Therefore, in order to obtain a conductive composition that takes advantage of the reinforcing properties and heat resistance of alkali metal titanate (), in addition to alkali metal titanate (), the conductive alkali metal titanate of the present invention and other commonly used alkali metal titanates must be used. Conductive fillers, conductive resins, etc. are used in combination, and conductivity can only be achieved by utilizing the conductive properties of materials other than alkali metal titanates.

Regarding the conductive alkali metal titanate of the present invention,
The present inventor has already discovered a method for producing conductive alkali metal titanate () from alkali metal titanate ();
Regarding the production method of conductive alkali metal titanate () from conductive alkali metal titanate (), and furthermore, various methods for producing conductive alkali metal titanate (), including the production method of alkali metal titanate (). Furthermore, as a method to impart conductivity to the electrically insulating alkali metal titanate (2), we have developed a method of chemically coating or eutectic with a conductive metal and/or metal compound, and further coating the surface of the alkali metal titanate (2) with a conductive metal and/or metal compound. We have completed the invention to obtain conductive alkali metal titanate by precipitation or crystallization.If we place emphasis on economic efficiency, we can apply chemical vapor deposition (CVD) or physical vapor deposition ( PVD)
It has been technically clarified that it is possible to coat conductive materials by chemical or physical treatments such as, etc., and the present inventors have discovered that it is possible to coat conductive materials with chemical or physical treatments. We have developed various methods for manufacturing effectively used conductive alkali metal titanates, and applications are already pending.

The conductive alkali metal titanate used in the present invention is a conductive material with excellent reinforcing properties and deterioration resistance, and the main methods for producing it will be exemplified below.

(i) The conductive alkali metal titanate () is prepared by converting the alkali metal titanate () into a reducing atmosphere, for example a reducing gas atmosphere such as H ₂ or CO, or a non-oxidizing atmosphere in the presence of a reducing agent such as a carbon substance. at 300℃
Above, a method of heat treatment preferably at 500°C or higher,
Or, during the production of alkali metal titanate (),
It can also be directly produced by maintaining a reducing atmosphere or a non-oxidizing atmosphere in the presence of a reducing agent. In addition, the general formula M ₂ O・aTiOx・bH ₂ O (M, a,
In the alkali metal titanates represented by (b, x are the same as above), M is potassium, that is, reduced potassium titanate changes in color as x changes, such as whitish-purple, purple, black, black-purple, gold, Examples of materials that change to silvery white and can be applied as the conductive alkali metal titanate () of the present invention include:
From the viewpoint of electrical conductivity, it is preferable to use a substance that is reduced to a degree of x≦1.99, preferably x<1.95, and exhibits a light purple to black color.

(ii) Conductive alkali metal titanate () is a conductive alkali metal titanate () and/or alkali metal titanate () coated with a conductive compound, and the method for coating the conductive compound is as follows: Electroless plating, wet neutralization method, CVD,
Although currently commonly used surface conductivity methods such as PVD can be applied, the present inventors deposited conductive compounds such as tin, indium, antimony, copper, and nickel on the surface of alkali metal titanate (2008) by wet reaction. We have completed the technology to produce conductive alkali metal titanate (), and we have also completed the technology to produce conductive alkali metal titanate (), and we have also developed a technology with the general formula K ₂ O・aTiOy・bH ₂ O (a, b,
A conductive alkali titanate having a metal coating consisting of at least one metal selected from the group consisting of Ni, Cu, Pt, Ag, Au, Cr and Pd in the potassium titanate group represented by (y is the same as above) We have perfected the manufacturing technology for metals (), and in particular, we have developed metals () with the general formula M ₂ O, aTiOx, bH ₂ O.
The reduced titanate compound represented by (M, a, b, x are the same as above) exhibits conductivity itself, and electroless plating can be easily applied as a method for coating with a conductive metal compound. By discovering what can be done, it is possible to further improve conductivity.

Conductive alkali metal titanate () of the present invention
In particular, the conductive alkali metal titanate () has improved conductivity, and the surface of the insulating alkali metal titanate () can be coated with transparent conductive metal compounds such as tin oxide, antimony oxide, indium and It is practically advantageous as a white conductive alkali metal titanate by coating with copper iodide or the like.

(iii) Conductive alkali metal titanate () is used when producing the general formula M ₂ O・aTiOy・bH ₂ O (M, a, b, y are the same as above), such as tin, copper, silver, etc. oxides, halides, carbonates, sulfates, nitrates, etc. as titanium sources, titanium oxide, titanium hydroxide, and alkali carbonates and halides as an alkali source, and heated at 500 to 1200℃ or microwave etc. As a typical example, a white conductive potassium titanate in which tin oxide is precipitated on the surface of a potassium titanate whisker is obtained by a melting reaction of titanium oxide, potassium carbonate, and tin chloride.

Although typical conductive alkali metal titanates of the present invention have been described, the conductive alkali metal titanates of the present invention include one or more of these conductive alkali metal titanates () to (). This includes all mixtures and reinforcing or non-reinforcing conductive alkali metal titanates, but from a practical point of view, those in the form of fine fibers are preferred, and usually the fiber diameter is
A thickness of 0.1 to 100 μm and an aspect ratio of about 1 to 1000 is preferable from the viewpoint of imparting a reinforcing effect and surface smoothness. In particular, as a raw material for the conductive alkali metal titanate of the present invention, fibrous potassium titanate with a fiber diameter of 0.2 to 0.5 μm and an aspect ratio of about 20 to 60 is optimal, and therefore, fibrous potassium titanate that has been imparted with conductivity is suitable. is the most suitable as the conductive alkali metal titanate of the present invention.

The amount of conductive alkali metal titanate added is 100% by weight of the resin composition including unsaturated polyester and/or vinyl ester resin, polymerizable monomer, thermoplastic resin, filler, curing catalyst, coloring agent, mold release agent, etc. Generally 5 to 60 parts by weight, preferably 15 to 60 parts by weight
Use 50 parts by weight. When the amount added is within this range, excellent conductivity and reinforcing effects can be obtained, and the moldability is also excellent without causing problems such as thickening.

Curing catalysts used in the present invention include benzoyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, cumene hydroperoxide, dicumyl peroxide, and fillers include calcium carbonate, clay, and barium sulfate. , aluminum hydroxide, chopped strands of glass fiber, sheet materials, and release agents include stearic acid metal salts, phosphoric acid esters, and the like. Other additives to unsaturated polyester and/or vinyl ester resins can also be used.

The conductive resin composition for molding of the present invention includes, for example, an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a curing catalyst, a mold release agent, a filler, a conductive alkali metal titanate, etc. It is obtained by adding a thickener to the composition, if necessary, and stirring and mixing. The above-mentioned composition of the present invention can be used by impregnating a reinforcing material such as glass fiber, or by kneading the resin composition and the reinforcing material, before the composition thickens. This conductive resin composition for molding can be molded using compression molding, injection molding, or transfer molding.
Preferably, the molding is carried out at a temperature of 160-170°C.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. It should be noted that all "parts" shown in the examples mean "parts by weight" unless otherwise specified.

Example 1 444 g of phthalic anhydride, 686 g of maleic anhydride, and 837 g of propylene glycol were heated at 200°C under a nitrogen stream.
The mixture was reacted in a conventional manner for about 9 hours to obtain an unsaturated polyester having an acid value of 25. 0.02 part of hydroquinone was added to 65 parts of this polyester and then dissolved in 35 parts of styrene monomer to obtain a liquid unsaturated polyester resin. 80 parts of the unsaturated polyester thus obtained, 8 parts of polystyrene [manufactured by Asahi Kasei Industries, Ltd.], 80 parts of calcium carbonate, conductive potassium titanate [Teismo BK-200, Otsuka Chemical Co., Ltd.]
After stirring and mixing 20 parts of zinc stearate and 4 parts of zinc stearate, 420 g of the resulting resin composition was kneaded with 180 g of glass chopped strands, and the mixture had a thickness of about 6 mm.
A sheet with a width of 2.0 cm and a length of 10.0 cm was molded.
The obtained sheet was cured and molded under conditions of 50 kg/cm ² and 140° C. for 5 minutes to obtain a molded product. After crimping silver foil to the cross section of both ends of this sample, adhere silver electrodes to the surface of the silver foil, and set the distance between the two electrodes to 10.0 cm using a digital multimeter TR-6841 (manufactured by Takeda Riken Co., Ltd.). The electrical resistance between the electrodes was measured, and the volume resistivity was calculated using the following formula.

Volume resistivity = sheet thickness × electrode length × electrical resistance / spacing between electrodes Under the above measurement conditions, the thickness of the electrodes and the spacing between the electrodes are 2.0 cm and 10.0 cm, respectively.

Also, from the resin compound of this example, one side is 10 cm.
Make a square sheet-like molded body, sample chamber model TR-42, and digital multimeter.
Measure the resistance between the electrodes using TR-6841,
The surface resistivity was calculated based on the following formula in accordance with JISK-6911.

Surface resistivity = π(D+d)/D-d×electrical resistance Under the above measurement conditions, D (outer diameter of the metal ring in the middle),
d (outer diameter of the inner metal ring) is 7.0 cm and 5 cm, respectively.
cm.

The volume resistivity calculated from the above measurements is 1.07×
10 ⁵ Ω·cm, and the surface resistivity was 2.23×10 ⁷ Ω.
Furthermore, the molding shrinkage rate was 0.1% or less, the surface of the obtained molded product was extremely smooth, and its paintability was also extremely good.

Example 2 Epicote 828 (epoxy equivalent: 187, manufactured by Ciel)
561 g of methacrylic acid, 258 g of methacrylic acid, 0.25 g of hydroquinone as a polymerization inhibitor, 2.2 g of triethylamine as an esterification catalyst, and 384 g of styrene monomer as a polymerizable monomer were reacted at 120°C for 5 hours using a conventional method to obtain a vinyl ester with an acid value of 10. Resin was obtained. 80 parts of the vinyl ester resin thus obtained,
A resin composition was obtained by mixing 8 parts of polystyrene, 30 parts of calcium carbonate, 30 parts of conductive potassium titanate (Teismo BK-100, manufactured by Otsuka Chemical Co., Ltd.), 1 part of magnesium oxide, and 4 parts of zinc stearate. Add 420g of this resin composition to 180 glass chopped strands.
After kneading g, the thickness is approximately 6 mm, width 2.0 cm, and length 10.0 cm.
A sheet with a ^shape of cm, surface resistivity 3.53
It was ×10 ⁹ Ω. In addition, the molding shrinkage rate is 0.2%,
This is an extremely low shrinkage rate. Furthermore, the surface of the molded product obtained was smooth and its paintability was also extremely good.

Example 3 1161g of fumaric acid and 837g of propylene glycol
were reacted in a conventional manner at 200° C. for about 9 hours under a nitrogen stream to obtain an unsaturated polyester having an acid value of 30. After adding 0.02 parts of hydroquinone to 70 parts of this unsaturated polyester, it was dissolved in 40 parts of styrene monomer to obtain a liquid unsaturated polyester resin. Further, 1,660 g of isophthalic acid and 837 g of propylene glycol were reacted in a conventional manner at 200° C. under a nitrogen stream for about 18 hours to obtain a saturated polyester having an acid value of 36. After adding 0.02 parts of hydroquinone to 70 parts of this polyester, the mixture was dissolved in 30 parts of styrene monomer to obtain a liquid saturated polyester resin.

80 parts of the former unsaturated polyester resin, 20 parts of the latter saturated polyester resin, 35 parts of calcium carbonate,
35 parts of aluminum hydroxide, 30 parts of conductive potassium titanate [Teismo BK-300, manufactured by Otsuka Chemical Co., Ltd.],
2 parts magnesium hydroxide, 4 parts zinc stearate
Part, PCN・5C・51 Blue [Polyester Toner,
(manufactured by Tokyo Ink Co., Ltd.) were thoroughly stirred and mixed to obtain a resin composition. A sheet-like product was formed from the obtained resin composition in the same manner as in Example 1, and after further curing, the electrical conductivity was measured, and the volume resistivity was 1.30.
×10 ⁸ Ω·cm, and the surface resistivity was 7.8 × 10 ⁹ Ω.
In addition, the molding shrinkage rate of the resin composition in this example is
0.1%, the surface was extremely smooth. The paintability was evaluated by the following tests and was found to be good. That is,
After polishing the molded body and degreasing it with acetone, we spray-painted it with baking-type melamine alkyd paint.
After baking and hardening at 140°C for 30 minutes, the surface was cut in a cross pattern with a small knife, and the presence or absence of paint lifting was observed with the naked eye.The test was conducted and it was judged to be good.

Example 4 80 parts of unsaturated polyester resin and 20 parts of saturated polyester resin each synthesized in Example 3, 50 parts of calcium carbonate, 50 parts of conductive potassium titanate [Teismo BK-400, manufactured by Otsuka Chemical Co., Ltd.], oxidation 2 parts of magnesium and 4 parts of zinc stearate were stirred and mixed to obtain a resin composition. The following operations were carried out in the same manner as in Example 1, and the volume resistivity was 3.80×10 ² Ω·cm and the surface resistivity was 1.80×10 ⁴ Ω. In addition, the molding shrinkage rate is
It was as small as 0.2%, and the surface of the molded product was extremely smooth, with no protruding glass fibers. Also the first
No phase separation of the resin was observed during the next stage of sheet formation, and there was no problem with film releasability.

(Effects of the Invention) The conductive resin composition for molding of the present invention provides a uniform conductive resin composition for molding without causing phase separation between the unsaturated polyester and/or vinyl ester resin and the thermoplastic resin. The surface of a molded product created using this resin composition is not sticky.The surface of a molded product created using this resin composition is highly smooth and has good paintability and plating properties.This resin composition is sufficient for molding. It has low shrinkage and good dimensional stability.The physical properties of molded products made using this resin composition, especially the modulus properties, are extremely high.The molded products made using this resin composition are made of conductive titanium. Depending on the amount of acid-alkali metal added, it can be applied to a wide range of applications, from static electricity generation prevention to products that utilize high conductivity.

Claims (1)

[Claims] 1. Molding containing an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a thermoplastic resin compatible with the monomer, a conductive alkali metal titanate, and an inorganic filler. Conductive resin composition for use. 2 The conductive alkali metal titanate has the general formula
M ₂ O・aTiOx・bH ₂ O (in the formula, M is an alkali metal such as Li, Na, K, etc., 0<a≦8, 0≦b≦4, 0<
x < 2, a, b, x are real numbers) and is an electrically conductive alkali metal titanate, commonly referred to as reduced alkali metal titanate or bronze alkali metal titanate. thing. 3 The conductive alkali metal titanate has the general formula
An alkali metal titanate represented by M ₂ O・aTiOy・bH ₂ O (in the formula, M, a, and b are the same as above, 0<y≦2) is used as a conductive metal and/or a metal oxide exhibiting conductivity. 2. The composition according to claim 1, which is an electrically conductive alkali metal titanate coated with one or more electrically conductive metal compounds such as , halides, and the like. 4 The conductive alkali metal titanate has the general formula
When producing an alkali metal titanate group represented by M ₂ O・aTiOy・bH ₂ O (in the formula, M, a, b, and y are the same as above), conductive metals and/or their metal oxides and halides Conditions in which conductive metal compounds such as eutectic with alkali metal titanate or crystallize or precipitate on the surface of alkali metal titanate, that is, metals exhibiting conductivity with the raw material of alkali metal titanate or oxidation of these metals. When producing alkali metal titanates under conditions in which one or a mixture of two or more metal compounds such as compounds, hydroxides, halides, carbonates, nitrates, and sulfates coexist, production or The composition according to claim 1, which is a conductive alkali metal titanate that has been produced in an oxidizing atmosphere and then subjected to reduction treatment or doping treatment if necessary. 5. The composition according to claim 1, wherein the conductive alkali metal titanate is a mixture of the conductive alkali metal titanates according to claims 2, 3, and 4.