JPS6119619A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition excellent in handling and flow during molding and suitable for use in the production of FRP moldings by SMC process, comprising an unsaturated polyester, a polyisocyanate as a thickener and a fatty acid. CONSTITUTION:About 20-100pts.wt. unsaturated polyester (of a hydroxyl value of about 100-5 and an acid value of about 50-5, preferably dicyclopentadiene- modified one) is mixed with about 0.1-10pts.wt. polyisocyanate compound (e.g., diphenylmethane diisocyanate), about 0.1-10pts.wt. fatty acid (e.g., caproic or stearic acid) and optionally about 0-80pts.wt. polymerizable monomer (e.g., styrene). Said unsaturated polyester may be replaced by or may be used in combination with an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid.

Description

Detailed Description of the Invention (Field of Application of the Invention) The present invention relates to a resin composition, and more particularly, a resin composition containing a polyfunctional isocyanate compound as a thickener and having excellent handling workability and fluidity during molding. relating to things.

(Background of the invention) Conventionally, sheet molding compounds (hereinafter referred to as S
FRP molded products such as bathtubs are manufactured by the MC method. In this case, metal oxides such as magnesium oxide are commonly used as thickeners, but this has the disadvantage that the water resistance and strength of the molded product are reduced.

On the other hand, a method of using a polyfunctional isocyanate compound as a thickener has also been carried out, but in this case, the water resistance and strength of the molded product are improved, but the surface tackiness of the SMC increases significantly, making it difficult to handle. In addition, the fluidity during molding was extremely low, and as a result, short shots, pregels, etc. were likely to occur in molded products.

Therefore, there are methods of using an isocyanate compound and metal oxide in combination (Japanese Patent Laid-Open No. 49-39691), and methods of limiting the composition of unsaturated polyester (Japanese Patent Laid-Open No. 57-12102).
No. 3) has been carried out, but the current situation is that it cannot be said to be fully satisfactory.

(Objective of the Invention) The object of the present invention is to eliminate the drawbacks of the prior art, and to create a resin composition that has excellent handling workability and fluidity during molding even if it contains a polyfunctional isocyanate compound as a thickener. It's about providing things.

(Summary of the Invention) In order to achieve the above object, the present inventors focused on the excellent water resistance and strength of molded products when using a polyfunctional isocyanate compound as a thickener, and investigated the surface tackiness and moldability of SMC. As a result of extensive research, we have arrived at the present invention in order to improve the fluidity of this product.

The present invention provides a resin composition containing (A) an unsaturated ester and/or an unsaturated polyester obtained by reacting an epoxy resin with an unsaturated monobasic acid, (B) a polyfunctional isocyanate compound, and (e) a fatty acid. relating to things.

The acid component of the unsaturated polyester used in the present invention includes unsaturated dibasic acids such as maleic anhydride and fumaric acid, and if necessary, isophthalic acid, terephthalic acid, orthophthalic acid, phthalic anhydride, and tetrachlorophthalic anhydride. Saturated dibasic acids such as

Examples of the alcohol component of the unsaturated polyester include ethylene glycol, propylene glycol, neopentyl glycol, dibromoneopetyl glycol,
Polyhydric alcohols such as dipropylene glycol, 2.2bis[para(hydroxy-n-propoxy)phenyl]propane, tricyclodecanediol, and trimethylolpropane are used.

The unsaturated polyester used in the present invention may be one obtained by condensing the acid component and the alconyl component, but it is also possible to use an unsaturated polyester modified with dicyclopentadiene. , S
It is particularly effective in improving the surface tackiness of MC. Methods for modifying unsaturated polyester with dicyclopentadiene include (1) a one-stage synthesis method in which an acid component, an alcohol component, and dicyclopentadiene are simultaneously charged and modified at the same time as condensation; (2) an acid component and There is a two-step synthesis method in which alcohol components are condensed and dicyclopentadiene is added during the process to denature the reaction temperature.
The amount of dicyclopentadiene added is preferably in the range of 30°C, but there is no particular restriction on the amount of dicyclopentadiene added. is 0.01~0.
A range of 0.04 mol is preferred.

The hydroxyl value of the unsaturated polyester used in the present invention is preferably in the range of 100 to 5, particularly preferably in the range of 50 to 15. In addition, the acid value of the unsaturated polyester is preferably in the range of 50 to 5, from the viewpoint of preventing carbonation reaction caused by the reaction between the isocyanate compound and the carboxyl group;
A range of 5 is particularly preferred.

Examples of the epoxy resin used in the present invention include bisphenol epoxy resin, novolac epoxy resin, and alicyclic epoxy resin.

Commercially available bisphenol epoxy resins include Epikote 828 and Epiiod 1001 manufactured by Shell Chemical Co., Ltd.
, Epicor) 1004, Asahi Kasei Corporation AER-664
8, AER-331, AER-337, manufactured by Dow Chemical Company, E, R330°D, E, R66G, D, 'E, R
664 (both are product names), etc. Also, a type of resin in which some of the hydrogen atoms are replaced with halogen (e.g. bromine), such as Epo (manufactured by Tobu Kasei Co., Ltd.) YDB-340, Y
Commercial products of this novolac epoxy resin using DB-400 (all trade names) are, for example, E, N431, D, E, -N43 manufactured by Dow Chemical Company.
8. Epikote 152, Epicoat 15 manufactured by Shell-i Co., Ltd.
'4. Examples include EPN1138 manufactured by fba.
' As the alicyclic epoxy resin, for example, vinyl cyclohexene dioxide (manufactured by Chisso Corporation, trade name Chissonox 2)
06)1. Dicyclopentadiene dioxide (Chissonox 207X), 3,4-epoxy-6-methylcyclohexylmethyl, 3゜4-epoxy-6-methylcyclo↑xanka, luponate (Chissonox 201)
etc.

These epoxy resins can be used alone or in combination of two or more.

Examples of unsaturated acids to be reacted with epoxy resin include acrylic acid, methacrylic acid, crotonic acid,
Partially esterified carboxylic acids containing cinnamic acid, tricyclo(5,2,1,O'')-4-decene-8 or 9 residues and unsaturated dibasic acid residues as constituent elements, etc. can be used. It is also possible to partially replace the unsaturated monobasic acid with a polybasic acid such as maleic acid, fumaric acid, phthalic acid, or isophthalic acid.

Epoxy resin and unsaturated monobasic acid at 60 to 150°C,
Preferably, an unsaturated ester is obtained by heating the reaction at 70 to 130°C. Approximately 1 equivalent of the unsaturated monobasic acid is used per 1 equivalent of the epoxy resin.

The acid value of the unsaturated ester produced is preferably 50 or less,
Particularly preferably, it is 20 or less. In order to prevent gelation due to polymerization during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, ditertiary butylcatechol, or hydroquinone monomethyl ether.

In addition, in the esterification reaction between this epoxy resin and an unsaturated monobasic acid, for example, ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, etc. The reaction time can also be shortened by using an esterification catalyst such as , lithium chloride, or stannic chloride.

In the present invention, the above-mentioned unsaturated ester, unsaturated polyester, or both are used.

Used as a thickener in the resin composition of the present invention (
B) Examples of polyfunctional isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, and isocyanate-terminated prepolymers derived from these isocyanates. An isocyanate compound having a higher value than the above value is used. Among these compounds, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate □1 are particularly preferred in terms of handling and workability and thickening properties.

Examples of fatty acids (C) used in the present invention include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, liluic acid, etc. saturated or unsaturated fatty acids. These fatty acids may also contain functional groups such as hydroxyl groups.

These compounds may be used alone or in combination of two or more.

Furthermore, the resin composition of the present invention may contain a polymerizable monomer if desired. Examples of polymerizable monomers include styrene, divinylbenzene, vinyltoluene, vinyl acetate,
Examples include methyl methacrylate and ethyl acrylate.

In the resin composition of the present invention, there are no particular restrictions on the proportions of unsaturated polyester and/or unsaturated ester, polyfunctional isocyanate compound, fatty acid, and polymerizable monomer, but unsaturated polyester and/or unsaturated ester The amount used is preferably in the range of 20 to 100 parts by weight.

The amount of the polyfunctional isocyanate compound to be used is preferably 0.1 to 10 parts by weight from the viewpoint of thickening effect and prevention of foaming due to reaction between water content 9 and isocyanate.

In addition, as a thickener, a metal oxide such as magnesium oxide or a metal hydroxide such as magnesium hydroxide can also be used in combination. The amount of fatty acid used is preferably in the range of 0.1 to 10 parts by weight from the viewpoint of improving the surface tackiness and fluidity of SMC and improving the strength. In addition, the amount of polymerizable monomer used is 0 to 8
A range of 0 parts by weight is preferred.

When manufacturing a molded article using the resin composition of the present invention, for example, a curing organic peroxide, a polymerization inhibitor, a filler, a reinforcing material, a mold release agent, a coloring agent, etc. are added and mixed as necessary. be able to.

Examples of the organic peroxide used for curing include t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, and methyl ethyl ketone peroxide.

As the polymerization inhibitor, for example, hydroquinone, parabenzoquinone, catechol, 2,5-diphenylparabenzoquinone, etc. are used.

As the filler, for example, calcium carbonate, clay, barium sulfate, aluminum hydroxide, etc. are used.

Examples of reinforcing materials used include roving-like fibers made of fibers such as glass fiber, vinylon fiber, carbon fiber 6, and polyamide fiber, and materials processed into short fibers, woven fabrics, knitted fabrics, threads, braided fabrics, etc. Ru.

As the mold release agent, for example, zinc stearate, calcium stearate, etc. are used.

As the colorant, inorganic or organic colorants commonly used for coloring unsaturated polyester resins are used.

The resin composition of the present invention may also contain thermoplastic polymers such as polystyrene, polyvinyl acetate, and polymethyl methacrylate, and thermosetting polymers such as phenol resins, epoxy resins, and melamine resins. It may also contain flame retardants such as antimony dioxide, hexabromobenzene, and chlorinated paraffin.

The resin composition of the present invention is particularly useful in the SMC method. Unlike conventional thickening methods using metal salts such as magnesium oxide, the resin composition of the present invention can be heated at room temperature (20 to 25
℃), it can be molded in about 4 hours after SMC production, and there is no need for a maturing chamber or the like to keep it warm. The resin composition of the present invention can also be applied to bulk molding compound (BMC) methods, such as preform matted metal die molding method, hand lay-up molding method, spray-up molding method,
It can also be widely applied to injection molding methods, etc.

(Effects of the Invention) According to the present invention, a polyfunctional isocyanate compound can be used as a thickener without reducing the mechanical strength and water resistance of a molded product, unlike the conventional method of using a metal oxide as a thickener. Even if the resin composition contains , it is possible to obtain a resin composition with extremely excellent handling workability and fluidity during molding.

(Examples of the Invention) The present invention will be explained below with reference to Examples. Parts in the examples below mean parts by weight.

Example 1 7.0 mol of maleic anhydride, 3.0 mol of phthalic anhydride, 7.0 mol of propylene glycol, 4.5 mol of dipropylene glycol, and 0.2 g of hydroquinone were mixed at room temperature under a nitrogen stream, After raising the temperature to 150°C, it took 5 hours to raise the temperature from 150°C to 210°C, followed by dehydration condensation for another 5 hours, resulting in an acid value of 1511. An unsaturated polyester with a hydroxyl number of 25 was obtained. 65 g of this unsaturated polyester was dissolved in 35 g of styrene containing 0.01 g of hydroquinone to obtain unsaturated polyester resin UP-1. , this resin, UP-1, was used, and the blending ratio shown in Table 1 was used.
0 (manufactured by NOF Corporation) and others? using a compound,
An SMC containing 24% (by weight) of glass fiber (1-inch chopped strand of glass roving, F, ER-0730 manufactured by Fuji Fiberglass Co., Ltd.) was produced. This S
MC cormorant rapidly thickens at room temperature (20-25℃),
The film peelability after 4 hours was good, and no stickiness was observed on the SMC surface, indicating good handling workability.

This SMC was molded using a box shape using a compression molding machine (molding temperature 140℃, pressure 100kg/cd, time 3 minutes, thickness 3m)
), a molded product with an excellent appearance was obtained. Furthermore, when the pressure at which SMC starts to flow during molding was measured, it flowed at a pressure of 3 Q kg/cw, which was about the same as SMC thickened with magnesium oxide, and had excellent fluidity.

Furthermore, when the mechanical strength of the molded product was measured, it showed a high value and was particularly excellent in impact resistance. In addition, when the water resistance of the molded product was examined, it showed a low boiling water absorption rate and a high mechanical strength after deterioration. These results are shown in Table 1.

Comparative Example 1 Resin UP-1 obtained in Example 1 was used, Isolo 143L and other compounds were used in the proportions shown in Table 1, no fatty acid was added, and the rest was the same as in Example 1. SMC was produced by processing.

Although this SMC rapidly thickened at room temperature (20 to 25° C.), its film releasability was extremely poor, and the SMC surface showed tackiness, resulting in poor handling workability.

When this SMC was processed and molded in the same manner as in Example 1, the pressure at which the SMC began to flow was 8Q kg/
cm, and the fluidity was poor: These results were
Shown in the table.

Comparative Example 2 Maleic anhydride 7.0 mol, phthalic anhydride 3.0 mol,
7.0 mol of propylene glycol, 3.7 mol of dipropylene glycol, and 0.2 g of hydroquinone were mixed under a nitrogen stream, and after heating to 150°C, it took 5 hours to
The temperature was raised from 0°C to 210°C, and dehydration condensation was further carried out for 5 hours.
An unsaturated polyester having an acid value of 30 and a hydroxyl value of 15 was obtained. 65 g of this unsaturated polyester was dissolved in 35 g of styrene containing 0.01 g of hydroquinone to obtain unsaturated polyester resin UP-2. Using this resin UP-2 and magnesium and other compounds in the proportions shown in Table 1, an SMC with a glass fiber content of 24% (by weight) was produced. This SMC required aging at 40°C for 48 hours.

When this SMC was treated and molded in the same manner as in Example 1, the pressure at which the SMC began to flow was 30 kg/-. The mechanical strength and water resistance of the molded article were also tested in the same manner as in Example 1, but both were inferior to those in Example 1. These results are shown in Table 1.

Notes in the following margin ■ Rheometer method: Compressive load 320 g/ad (2
(Peeling force of 0φ disk) (2) A pressure transducer was used to detect the pressure when the press was pressurized, and the pressure when the SMC started flowing was measured.

■ Measured according to JISK6911.

■ Bending strength retention Example 2 Methacrylic acid 172.6 g (2.0 mol), Epicote 828 (Shell Chemical Co., Ltd. bisphenol epoxy resin, epoxy equivalent 189) 151.2 g (0.4
0 mol), Epicote 1.001 (bisphenol epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent: 475) 570
．． 0 g (0,60 mol), Epicote 1001 (
Bisphenol epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent 475) 570.0 g (0.60 mol), hydroquinone 0.40 g and trinotylbenzylammonium chloride 0.50 gt - 11 Heated at 20°C for 7 hours to remove the unsaturated ester. Obtained.

Then, 70 parts of the obtained unsaturated ester having an acid value of 9 and 30 parts of styrene were mixed to obtain an unsaturated ester resin VE-1. Using this resin, VB-1, isone) 143L and lauric acid NAA-12 with the blending ratio shown in Table 2.
2 (manufactured by NOF Corporation) and other compounds,
An SMC containing glass fiber (manufactured by Fuji Fiber Glass Co., Ltd., glass roving, 1-inch chopped strand of FER-0730) and having an amount of 601i was produced. This S
MC rapidly thickened at room temperature (20 to 25°C), had good film removability after 24 hours, and no stickiness was observed on the SMC surface, indicating good handling workability.

When this SMC was molded using a box-shaped compression molding machine (molding temperature: 140° C., pressure: 100 kg/cd, time: 3 minutes, thickness: 3 mm), a molded product with an excellent appearance was obtained. We also measured the pressure at which SMC starts to flow during molding, and found that 4. Qkg/c+J, and had excellent fluidity. Furthermore, when the mechanical strength of the molded product was measured, it showed a high value. These results are shown in Table 2.

Comparative Example 3 Resin VE-1 obtained in Example 2 was used, Isonate 143L and other compounds were used in the proportions shown in Table 2, no fatty acid was added, and the rest was treated in the same manner as in Example 2. SMC was prepared by doing this.

This SMC rapidly thickened at room temperature (20 to 25°C), but had poor film releasability, and adhesiveness was observed on the SMC surface, resulting in poor handling and workability.

When this SMC was treated and molded in the same manner as in Example 2, the pressure at which the SMC began to flow was as high as 85 kg/cd, and the fluidity was poor. These results are shown in Table 2.

atomic margin stem Table 2 Note: Measurement methods for ■ to ■ are the same as in Table 1.

As is clear from the results in Tables 1 and 2, the resin composition of the present invention has excellent handling workability and fluidity during molding, as well as mechanical properties, compared to Comparative Example 2. It also has excellent strength and water resistance.

Claims (1)

[Claims] 1, (A) an unsaturated ester and/or an unsaturated polyester obtained by reacting an epoxy resin with an unsaturated monobasic acid, (B) a polyfunctional isocyanate compound, and (C
) A resin composition containing a fatty acid.