JPH0453869A - Molding resin composition and production of molding - Google Patents

Abstract

PURPOSE:To provide a molding resin composition which can give an FRP molding excellent in gloss, glass fiber whitening resistance, water whitening resistance, etc., by mixing an unsaturated polyester of a specified composition with an unsaturated monomer having a polymerizable double bond and two specified low-melting waxes. CONSTITUTION:An acid component 30-40mol% of which is maleic or fumaric anhydride is reacted with an alcohol component 30-60mol% of which is diethylene glycol to produce an unsaturated polyester. This unsaturated polyester is mixed with an unsaturated monomer having at least one polymerizable double bond in the molecule (e.g. styrene), a microcrystalline wax having a 22-59C distribution and a melting point of 166 deg.F or below, a paraffin wax and optionally a filler, a cure accelerator, etc., to produce a molding resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition for molding, particularly by oven molding methods such as dry-up and spray-up. Fiber-reinforced glass molded products (hereinafter referred to as F) have excellent surface gloss, glass fiber whitening resistance, and surface water whitening resistance.
The present invention relates to a molding resin composition capable of obtaining RP (abbreviated as RP) and a method for manufacturing molded articles using the same.

(Prior art) Conventionally, in molding FRP using an oven mold method, an unsaturated polyester obtained by reacting an acid component containing an α,β-unsaturated dibasic acid with a polyhydric alcohol,
Unsaturated polyester resin consisting of an unsaturated monomer that has a polymerizable double bond in its molecule, wax to prevent contact with air and to sufficiently proceed with curing, and to prevent sagging during F'FLP molding. A resin composition containing a thixotropic agent is known. Recently, calcium carbonate has been added to the above resin composition for the purpose of increasing the rigidity of FRP molded products or reducing the cost.

When FRP is molded by oven molding using a conventional resin composition to which calcium carbonate is added, the gloss of the FRP molding surface is reduced. After coming into contact with moisture such as rain or night dew, the F'RP molding surface turns white (hereinafter abbreviated as "mizuguchi").

Glass fibers appear white inside the FRP and on the mold surface. (
Phenomena such as glass fiber whitening (hereinafter abbreviated as glass fiber whitening) are observed.
There is a drawback that the commercial value of FRP is greatly impaired.
A solution to these shortcomings has been strongly desired.

(Problems to be Solved by the Invention) The purpose of the present invention is to create an FRP molded product that has excellent surface gloss, water whitening resistance, and glass fiber whitening resistance even when calcium carbonate is added using the oven mold method. The object of the present invention is to provide a molding resin composition that can be obtained and a method for producing molded articles using the same.

(Means for Solving the Problems) The present invention provides an acid component in which 30 to 40 mol% of the acid component is maleic anhydride or fumaric acid and 30 to 6 mol% of the alcohol component.
Unsaturated polyester obtained by reacting an alcohol component with 0 mol% diethylene glycol, unsaturated monomer having at least one polymerizable double bond per molecule, distribution of carbon numbers 22 to 59 The present invention relates to a molding resin composition containing microcrystalline wax and paraffin wax having a melting point of 166°F or less, and a method for producing molded articles using the same.

In the acid component of the unsaturated polyester used in the resin composition of the present invention, 30 to 40 mol% of the acid component is maleic anhydride or fumaric acid. If the proportion of maleic anhydride or fumaric acid exceeds 40 mol%, glass fiber whitening will occur inside the FRP molded product, and if it is less than 30 mol%, the physical properties and curability of the resulting cured product will deteriorate, resulting in F'R , Glass fiber whitening occurs on the mold surface of P molded products. Furthermore, when other unsaturated acids 9 such as itaconic acid and citraconic acid are used in place of maleic anhydride or fumaric acid, the physical properties and curability of the cured product deteriorate.

As an alcohol component, 30 to 60 mol% of the component
is considered diethylene glycol, and its proportion is 30 mol%
If it is less than 60 mol %, the gloss will decrease and water droplets will occur, and if it exceeds 60 mol %, glass fiber whitening will occur inside the FRP molded product.

As the acid component other than maleic anhydride or fumaric acid, a saturated dibasic acid is used as necessary.9 For example, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride. , adipic acid.

Cepatine, tetrabromophthalic anhydride, het acid, etc. are used.

Also, if desired, trimellitic acid, pyromellitic anhydride,
Polybasic acids such as pyromellitic acid may also be used.

1 for polyhydric alcohols other than diethylene glycol
For example, ethylene glycol, propylene glycol, triethylene glycol, dipropylene glycol, 1.
3-butylene glycol, 2゜3-phthylene gelicol, neopentyl glycol, 1,6-hexanediol, hydrogenated bisphenol A, isopentyl glycol,
Glycerin.

Trimethylolpropane, pentaerythritol, etc. are used.

Examples of unsaturated monomers having at least one polymerizable double bond in one molecule include 2, such as styrene.

Chlorstyrene, vinyltoluene, vinyl acetate.

Acrylic acid ester, methacrylic acid ester.

Diallyl phthalate, triarylisocyanurate trimethylolpropane acrylate, trimethylolpropane methacrylate, glycidyl methacrylate, allyl glycidyl ether, etc. are used. From the viewpoint of hardness of the cured product, t of the unsaturated monomer having at least one polymerizable double bond in one molecule is 100% of the unsaturated polyester.
A range of 80 to 120 parts by weight is preferred.

The microcrystalline wax has a carbon number distribution of 22 to 59 and a melting point of 166°F (75°C) or lower, such as Hi-Mic-2065, Hi-Mi, manufactured by Nippon Seiro Co., Ltd.
-2070 etc. are used. If the carbon number distribution is smaller than 22, the formation of a good wax layer will be impaired due to changes in F'RPti, outside temperature during molding, curing furnace, etc., and the FR
The surface gloss and water whitening resistance of the P molded product decrease. If the carbon number distribution is larger than 59, the melting point is 166.
If it exceeds °F.

Wax precipitation is insufficient and the F'RP molded product remains sticky, resulting in a decrease in surface water whitening resistance.

The paraffin wax used in combination preferably has a melting point in the range of 115°F to 155°F, such as paraffin wax 115°F or 120°F manufactured by Nippon Seiro.

125°F, 130°F, 135@F', 140°F,
145'F, 150°F', 155°F, etc. are used. Compared to Microcrystalline Wanox, a combination system of microcrystalline wax and paraffin wax,
It is possible to maintain excellent surface gloss and surface water whitening resistance even under conditions of temperature changes such as outside temperature and curing furnace during FRP molding.

Furthermore, regarding the blending ratio of the above wax.

In order to improve the surface gloss and water whitening resistance of FR, P molded products, add 100 parts by weight of unsaturated polyester and unsaturated monomers having at least one polymerizable double bond per molecule. 0.02 to 0.1 parts by weight of microcrystalline wax and 0 parts of paraffin wax
．． It is preferable to use it in a range of 0.01 to 0.06 parts by weight.

In the molding resin composition of the present invention, an unsaturated polyester is prepared by reacting the acid component and the alcohol component in a conventional manner. An unsaturated polyester resin is prepared by dissolving it in an unsaturated monomer having a double bond, and the two types of waxes described above are mixed together with the unsaturated polyester resin, and the mixture is heated and stirred to a temperature above the melting point.

The resin composition of the present invention may contain clay talc,
Fillers such as silica powder, alumina, aluminum hydroxide, and mica powder may be added and contained.

Furthermore, the resin composition of the present invention may optionally contain a metal salt of naphthenate such as cobalt naphthenate or cobalt octenoate, a metal salt of octenoate, or a curing accelerator such as amines, such as hydroquinone.

Polymerization inhibitors such as rosebenzoquinone, 2,5-diphenylbarabenzoquinone, tolbenzoquinone, mono-t-butylno-itoquinone, and phenolic resins.

1IJI1. fi fee, each Wi wax (ceresin wax).

Polyethylene wax, etc.) may also be added.

Examples of the curing agent for the resin composition of the present invention include evamethyl ethyl ketone peroxide, benzoyl peroxide, t
Organic peroxides such as -butyl-perbenzoate, acetylacetone peroxide, inbutyl ketone peroxide, dicumyl peroxide, and cumene hydroperoxide are used.

Lay up the molding resin composition of the present invention.

Laminated on top of the mold along with fiber reinforcement using oven molding methods such as spray-up.

A molded product is produced by hardening and demolding.

(Example) The present invention will be explained below with reference to an example. 1% by weight means % by weight.

Example 1 3 moles of maleic anhydride, 7 moles of phthalic anhydride.

3 moles of diethylene glycol and 8 moles of hyfropylene glycol were charged into a four-bottle flask equipped with a stirrer, a condenser, a thermometer and an inert gas inlet, and the mixture was reacted in a conventional manner at 210° C. while introducing nitrogen gas. 47 parts of styrene monomer and 300 pI)m of hydroquinone were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin circle.

To 100 parts of this unsaturated polyester resin (A), a thixotropic agent (product name Aeroseal $200. Nippon Aeroseal Co., Ltd. gLL5m, microcrystalline wax (product name H)
i-Mic-2065. Heiradaku carbon number 36.7. melting point 16
6°F1 (manufactured by Nichiki Seirosha) 0.07 part.

Paraffin wax (melting point 130°F0, manufactured by Nichiki Seirosha)
o, o3m, + cobalt phthenate (cobalt content 6%
) and 0.5 parts of dimethylaniline. By adding IN and stirring and dispersing while heating the wax to a temperature above the melting point of the wax, a viscosity of 5.0. Rocking degree 4.5
A resin composition (I) with a gelation time of 25 minutes was obtained. Viscosity is JIS K 6901 Section 4, 4.1, thixotropy Fi
Section 4.5 of JIs K 6901.

The gelation time was measured according to section 4.8 of JIS K 6901. In addition, when measuring the curing time, 55% concentration of methyl ethyl chloride peroxide 1 was used as the curing agent.
．． 0% was used (the same applies in the following examples).

A resin composition was prepared by adding 100 parts of the obtained resin composition (I), 50 parts of calcium carbonate (trade name: R heavy carbon, manufactured by Maruo Riki Rusoum Co., Ltd.) and 1 part of methyl ethyl ketone peroxide at a concentration of 55%. use.

Chopped strand cloak (F
'EM-450, Fuji Fiber Glass Company! ! The three layers were laminated by hand lay-up so that the glass content was 24%, and left to harden at 25°C for 4 hours to obtain an FRP molded product.

Example 2 3 moles of maleic anhydride, 7 moles of phthalic anhydride.

6 moles of diethylene glycol and 5 moles of propylene glycol were charged into a four-bottle flask equipped with a stirrer, a condenser, a thermometer, and an inert gas inlet, and reacted in a conventional manner at 210° C. while introducing nitrogen gas. 47 parts of styrene monomer and aooppm of hydroquinone were added to 53 parts of the obtained nine-unsaturated polyester to obtain an unsaturated polyester resin LB).

Using this unsaturated polyester resin (Bl 100 Ni), a resin composition (I [
I got it.

Using 1100 parts of the obtained resin composition (I), an F'RP molded article was obtained in the same manner as in Example 1.

Example 3 774,724 moles of anhydride, 6 moles of phthalic anhydride.

3 moles of diethylene glycol, 8 moles of propylene glycol
A four-piece flask with a seven-hole stirrer, condenser, hot water and inert gas inlet is installed.

The reaction was carried out in a conventional manner at 210° C. while introducing nitrogen gas.

47 parts of styrene monomer and 300 ppm of hydroquinone were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin fC)e4.

Using 100 parts of this unsaturated polyester resin ((:'), a resin composition CI with a viscosity of 5.1°, a thixotropy of 4.6, and a gelation time of 22 minutes was prepared at 25°C in the same manner as in Example 1.
II) was obtained.

Using 100 parts of the obtained resin composition (III), an FRP molded article was obtained in the same manner as in Example 1.

Example 4 4 moles of maleic anhydride, 6 moles of phthalic anhydride.

6 moles of diethylene glycol and 57 liters of propylene glycol were charged into a four-bottle flask equipped with a stirrer, a condenser, a thermometer and an inert gas inlet, and the mixture was reacted in a conventional manner at 210° C. while introducing nitrogen gas. 47 parts of styrene monomer and 7300 ppm of hydroquino were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (Dl).

Using 100 parts of this unsaturated polyester resin, the following procedure was carried out in the same manner as in Example 1, with a viscosity of 5.2° and a thixotropy of 4 at 25°C.
6 and a resin composition (goods) having a gelation time of 23 minutes was obtained.

Using 100 parts of the obtained resin composition (1), an F'RP shaped article was obtained in the same manner as in the example below.

Example 5 3.5 mol of maleic anhydride, 6.5 mol of phthalic anhydride,
5 moles of diethylene glycol and 6 moles of propylene glycol were placed in a four-bottle flask equipped with stirring, a condenser thermometer, and an inert gas inlet, and reacted in a conventional manner at 210'C while introducing nitrogen gas. 47 parts of styrene monomer was added to 53 parts of the obtained unsaturated polyester.
% and Hydro*/7300 pI)m to obtain an unsaturated polyester resin LE).

Using 100 parts of this unsaturated polyester resin (E), a resin composition (■) with a viscosity of 4.8 degrees, a thixotropy of 4.3, and a gelation time of 22 minutes was prepared at 25°C in the same manner as in Example 1. Obtained.

Using two parts of the obtained resin composition (v), the following procedure was carried out in the same manner as in Example 1 to obtain FR, P molded products.

Example 6 3.5 mol of maleic anhydride, 6.5 mol of phthalic anhydride,
5 moles of diethylene glycol and 6 moles of hyfurobilenoglycol were charged into a four-bottle flask equipped with a stirrer, a condenser thermometer, and an inert gas inlet, and reacted in a conventional manner at 210° C. while introducing nitrogen gas. 50 parts of styrene monomer and 6 parts of hydrogynone isoppm were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (F).

Using 100 parts of this unsaturated polyester resin (F), a resin composition (■) with a viscosity of 4.7°, a thixotropy of 4.3 and a gelation time of 15 minutes was prepared at 15°C in the same manner as in Example 1. Obtained.

Using a resin composition prepared by adding 50 parts of calcium carbonate (trade name: R heavy carbon, manufactured by Maruo Calcium Co., Ltd.) and 1 part of methyl ethyl ketone peroxide at a concentration of 55% to 00 parts of the obtained resin M parabolic (■l I), Three layers of chopped strand mat (FEM-450, manufactured by Fuji Fiber Glass Co., Ltd.) were formed at a molding temperature of ℃.

They were laminated by hand lay-up so that the glass content was 24%, and left to harden at 15°C for 4 hours.

PR, P molded products were obtained.

The state of the surface gloss of the PR and P molded products obtained in Examples 1 to 6, the state of glass fiber whitening occurring on the mold side of the FRP molded product, and the surface after immersion in water maintained at 25°C for 24 hours. Table 1 shows the state of submergence.

The symbols ◯, △, and × in the table represent the degree of surface gloss, glass fiber whitening resistance, and surface water whitening resistance.

Comparative example 1 5 moles of maleic anhydride, 5 moles of phthalic anhydride.

5 moles of diethylene glycol and 6 moles of propylene glycol were placed in a four-bottle flask equipped with a stirrer, a condenser, a thermometer, and an inert gas inlet, and the mixture was reacted in a conventional manner at 210° C. while introducing nitrogen gas. To 53 parts of the obtained unsaturated polyester, 47 parts of styrene monomer and aooppm of hinohydroquinone were added to obtain an unsaturated polyester resin (0).

Using 100 parts of this unsaturated polyester resin [G], a resin composition (4) with a viscosity of 5.3°, a thixotropy of 46 and a gelation time of 20 minutes was obtained at 25°C in the same manner as in Example 1. .

Using the obtained resin composition (100 parts of VI), an FRP molded article was obtained in the same manner as in Example 1.

Comparative Example 2 3.5 mol of maleic anhydride, 6.5 mol of phthalic anhydride,
2 moles of diethylene glycol and 9 moles of hyphropyrenoglycol were charged into a four-bottle flask equipped with a stirrer, a condenser thermometer, and an inert gas inlet, and the mixture was reacted in a conventional manner at 210° C. while introducing nitrogen gas. 47 parts of styrene monomer and 7300 ppm of hydroxyl were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin circle.

Using 100 parts of this unsaturated polyester resin (H),
Thereafter, in the same manner as in Example 1, a resin composition (2) with a viscosity of 4.7 degrees, a thixotropy of 4.3, and a gelation time of 23 minutes at 25 DEG C. was obtained.

Using 100 parts of the obtained resin composition (1), Example 1 was carried out below.
An F'RP molded product was obtained in the same manner as above.

Comparative Example 3 Maleic anhydride 3.5 mol, phthalic anhydride 6.5 mol,
5 moles of diethylene glycol and 67 l of propylene glycol were charged into a four-bottle flask equipped with a stirrer, a condenser thermometer and an inert gas inlet, and the mixture was reacted in a conventional manner at 210° C. while introducing nitrogen gas. 47 parts of styrene monomer and 3 oppm of hydroquinone were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (I).

To 100 parts of this unsaturated polyester resin (I), 2.5 parts of a modifier (trade name: Aeroseal $200, manufactured by Nihon Aeroseal Co., Ltd.), microcrystalline wax (trade name: Hi-Mic1080, average carbon number: 40, melting point: 183)゜F
1 Nippon Seiro Co., Ltd.) 0.07 part, paraffin wax (melting point 130°F 1 Nippon Seiro Co., Ltd.) 0.03 part, cobalt naphthenate (cobalt containing 116X) 0.5 part, and dimethylanili 70.1 part By adding and stirring and dispersing while heating above the melting points of the two types of waxes, the viscosity at 25°C was reduced to 5. A resin composition (2) having an O9 thixotropy of 4.5 and a gelation time of 25 minutes was obtained.

Using 100 parts of the obtained resin composition IX), an FRP molded article was obtained in the same manner as in Example 1.

Comparative Example 4 Maleic anhydride #3.5 mol, phthalic anhydride 6.5 mol,
5 moles of diethylene glycol and 6 moles of diethylene glycol were placed in a four-lobe flask equipped with a stirrer, two condenser thermometers, and an inert gas inlet.
The reaction was carried out in a conventional manner at 210° C. while introducing nitrogen gas.

50 parts of styrene monomer and 50 ppm of Hydro*//l were added to 53 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (J).

To 100 parts of this unsaturated polyester resin (J), 2.5 parts of a modifier (@product name Aeroseal #200, manufactured by Nihon Aeroseal Co., Ltd.), and microcrystalline wax (product name Yama-Mic-2065, manufactured by Nippon Seiro Co., Ltd.) were added. ), 0.5 parts of cobalt naphthenate (cobalt content 6%), and 0.1 part of dimethylaniline, and the mixture was stirred and dispersed while heating above the melting point of the microcrystalline wax to reduce the viscosity at 15°C. 4.8. A resin composition (2) with a thixotropy of 4.3 O and a gelation time of 13 minutes was obtained.

To 100 parts of the obtained resin composition (X), 50 parts of carbonic acid runium (trade name R multilayer, Maruo Calcium Exhibition) and 5
Using a resin composition containing 1 part of methyl ethyl ketone peroxide at a concentration of 5%, three layers of chopped strand mat (F'EM-4SO, manufactured by Fuji Fiber Glass Co., Ltd.) were molded into glass at a molding temperature of 15°C. They were laminated using a no-dore amplifier so that the content was 24%, and left to harden at 15°C for 4 hours to obtain an FRP molded product.

The state of the surface gloss of the F'RP molded products obtained in Comparative Examples 1 to 4, the state of glass fiber whitening occurring on the mold surface side of the F'RP molded products, and the state after immersion in water maintained at 25°C for 24 hours. Table 1 (Effects of the Invention) As shown in Table 1, if the molding resin composition of the present invention is used, it will be excellent even in the oven molding method in which calcium carbonate is added. surface gloss.

An FRP molded product having glass fiber whitening resistance and water whitening resistance can be obtained.

Claims (1)

[Claims] 1. Unsaturated product obtained by reacting an acid component in which 30 to 40 mol% of the acid component is maleic anhydride or fumaric acid and an alcohol component in which 30 to 60 mol% of the alcohol component is diethylene glycol. A molded product containing polyester, an unsaturated monomer having at least one polymerizable double bond in one molecule, a microcrystalline wax with a carbon number distribution of 22 to 59 and a melting point of 166°F or less, and paraffin wax. Resin composition for use. 2. A method for producing a molded article, comprising laminating the molding resin composition according to claim 1 on a mold together with a fiber reinforcing material, and removing the mold after curing.