JPH11148001A - Unsaturated polyester composition, sheet molding material and production of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in mold release characteristics, weather resistance and low pressure molding characteristics and the like, capable of shortening the molding cycle, by including specific unsaturated polyesters and copolymerizable monomers. SOLUTION: The subject composition is including (A) the unsaturated polyester component obtained by carrying out a reaction of an ester component containing (i) an acid component (a) including at least 20 mol.% of the α,β-unsaturated a polybasic acid (acid anhydride) based on the sum of the acid components of the components a and b and c, and as required a saturated polybasic acid (b), (ii) an ester component (c) including 80 mol.% or less of saturated polybasic ester based on the sum of the acid components of the components a and b and c, and (iii) a polyvalent alcohol in the presence of (iv) 0.01-1.0 wt.% of triphosphite or phosphoric triester based on the sum of the acid and alcoholic components in the components i and ii and (v) 0.01-0.5 wt.% of the component C of Zinc compounds, and (B) the copolymerizable monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an unsaturated polyester composition, a sheet-like molding material using the same, and a method for producing the same.

[0002] Sheet-like molding materials are usually prepared by adding a filler such as calcium carbonate, a curing agent such as an organic peroxide, a low shrinkage agent such as polystyrene, and a release agent to an unsaturated polyester and a copolymerizable monomer. , A resin composition in which a pigment, a thickener, and the like are mixed is applied on a film, and a glass fiber is applied thereon, impregnated, and aged. After thermal aging, the film is peeled off, placed in a mold, and molded at high temperature and high pressure to obtain a molded article. When removing the molded product from the mold, air or the like is used to lift the molded product from the mold, and the mold is released automatically or by hand. If the releasability of the molded product is poor, it adheres to the mold, making it difficult to release. As a result, the molding cycle is lengthened, resulting in reduced productivity. In order to solve this problem, conventionally, it has been responded by lowering the acid value at the reaction end point of the unsaturated polyester.

However, for a sheet-like molding material used for a waterproof pan, a bathtub, and the like, a shortening of a thickening period is required to improve productivity. This thickening is determined by the acid value and molecular weight of the unsaturated polyester at the reaction end point. When the reaction end point acid value is lowered, there is a problem that the thickening does not proceed or does not increase even when a thickener containing an alkaline earth metal oxide or a hydrate thereof as a main component is added. Further, conventionally, in order to improve the releasability, the shrinkage ratio has been increased by changing the mixing ratio of the unsaturated polyester and the copolymerizable monomer. In this method, the viscosity of the unsaturated polyester composition is inevitably reduced, and problems such as sagging and bleeding have occurred when forming a sheet-shaped molding material.

In the method described in JP-A-8-103030, a saturated polybasic acid such as terephthalic acid is used at the time of synthesis. When the synthesis is performed by this method, the time required for the synthesis is long, and the efficiency of the synthesis operation is extremely poor. In addition, the price of this saturated polybasic acid is high, resulting in a price unsatisfactory for the end user. Therefore, polyethylene terephthalate (hereinafter referred to as PE
A method of synthesizing an unsaturated polyester composition using a saturated polybasic acid ester such as polybutylene terephthalate (hereinafter sometimes abbreviated as PBT) or the like as a raw material has been proposed. However, when a synthetic polybasic acid polyester such as PET is synthesized as a raw material,
Invariably, a cracking agent such as t-butyl titanate must be used. However, when an unsaturated polyester composition synthesized using t-butyl titanate is used, the weather resistance of the molded product is deteriorated, and the molded product is immediately yellowed.

Further, unsaturated polyester compositions which have been used for conventional low-pressure molding materials have a temperature of 30 to 60 ° C.
Because it has a melting point of less than room temperature, it crystallizes at room temperature or less, becomes solid, increases the viscosity of the composition, and reduces the stickiness of the sheet-shaped molding material.
A method of lowering the viscosity and filling in a mold has been adopted. However, this method has a disadvantage that existing equipment cannot be used as it is, such as melting of the unsaturated polyester composition and heating during coating when producing a sheet-shaped molding material.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has good mold releasability from a mold without changing the acid value and molecular weight of the unsaturated polyester. An unsaturated polyester composition which is capable of shortening the cycle, is excellent in weather resistance and low-pressure moldability, is capable of suppressing yellowing and is capable of being light-colored, has excellent coloring properties, and has a semi-crystalline state. A sheet-like molding material and a method for producing the same are provided.

[0007]

The present invention provides (A) (1)
α, β-unsaturated polybasic acid or an acid anhydride thereof is contained as an essential component, and its use ratio is a combination of a saturated polybasic acid and an unsaturated polybasic acid, and an acid anhydride and a saturated polybasic ester thereof. (2) Saturated polybasic acid ester is contained as an essential component in an amount of at least 20 mol% with respect to the total amount of the acid component in the mixture, and the ratio of the saturated polybasic acid and unsaturated polybasic acid used in combination is An ester component which is 80 mol% or less based on the total of the basic acid and its acid anhydride and the acid component in the saturated polybasic ester, and (3) a polyhydric alcohol,
Triester of phosphorous acid or triester of phosphoric acid,
0.01 to 1.0% by weight based on the total amount of the acid component and the alcohol component in the acid component and the ester component.
Unsaturated polyester composition containing 0.5% by weight of an unsaturated polyester reacted and (B) a copolymerizable monomer, and a sheet comprising this composition together with a fiber reinforcing material Shape forming material.

In the present invention, an inorganic filler, a curing agent and a thickener are added to the above-mentioned unsaturated polyester composition, and these are present together with a fiber reinforcing material. The present invention relates to a method for producing a sheet-shaped molding material, and a sheet-shaped molding material obtained by the production method.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester used as the component (A) in the present invention comprises (1) an α, β-unsaturated polybasic acid and / or an acid anhydride thereof, and (2) a saturated polybasic acid. It is obtained by reacting an ester with (3) a polyhydric alcohol in the presence of (4) a triester of phosphorous acid or phosphoric acid and a zinc compound. A basic acid can also be reacted. α,
As the β-unsaturated polybasic acid and / or its acid anhydride,
Maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride and the like can be mentioned. These may be used in combination of two or more. Other polybasic acids used as needed include phthalic acid, phthalic anhydride, isophthalic acid,
Terephthalic acid, trimellitic acid, trimellitic anhydride,
Succinic acid, azelaic acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anthracene-maleic anhydride adduct, rosin-maleic anhydride adduct And halogenated polybasic acids, such as, for example, acetic acid, acetic acid, acetic anhydride, tetrachlorophthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic acid and tetrabromophthalic anhydride. These may be used in combination of two or more.

The α, β-unsaturated polybasic acid and / or the acid anhydride thereof is used in combination with the saturated polybasic acid and the unsaturated polybasic acid and the acid component in the acid anhydride and the saturated polybasic ester. Is preferably used in an amount of from 20 mol% to 100 mol%, more preferably from 40 to 80 mol%, and particularly preferably from 50 to 70 mol%. If the amount of these is less than 20 mol%, the strength of the molded article is reduced.

The saturated polybasic acid ester used in the present invention includes alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol, and particularly linear alkylene glycols and dibasic acids such as adipic acid, sebacic acid and terephthalic acid. In particular, there are low molecular weight esters or high molecular weight esters (i.e. saturated polyesters) with dibasic acids having a carboxyl group attached to a linear alkylene or paraphenylene group, for example,
Examples thereof include di (ethylene terephthalate), di (butylene terephthalate), polyethylene terephthalate, polybutylene terephthalate, di (ethylene adipate), di (butylene adipate), polyethylene adipate, and polybutylene adipate. These may be used in combination of two or more. The saturated polyester preferably has a weight-average molecular weight (weight-average molecular weight measured by gel permeation chromatography using a standard polystyrene calibration curve, the same applies hereinafter) of 15,000 or less. These are preferably used in an amount of 80 mol% or less based on the total amount of the saturated polybasic acid and the unsaturated polybasic acid and the acid anhydride and the acid component in the saturated polybasic acid ester used together. It is more preferably used in an amount of from 45 to 45 mol%, particularly preferably from 20 to 40 mol%. If the proportion of this component is less than 5 mol%, the viscosity of the unsaturated polyester obtained will be slow, and it will take time to reach the target viscosity. On the other hand, if it exceeds 80 mol%, the obtained unsaturated polyester composition is crystallized, and the strength of the obtained molded article decreases. Further, the melting point of these unsaturated polybasic acid esters is preferably 230 ° C. or lower, which is the synthesis temperature, more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower.

The polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol,
1,4-butanediol, 2,3-butanediol,
1,5-pentanediol, 1,6-hexanediol, triethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, dihydric alcohols such as hydrogenated bisphenol A, glycerin, trihydric alcohols such as trimethylolpropane, For example, a tetrahydric alcohol such as pentaerythritol is used. Two or more of these may be used in combination.

The reaction between an acid component (including an ester) and an alcohol component is carried out mainly by advancing a condensation reaction.
The reaction proceeds by desorbing low molecular compounds such as water generated when both components react with each other. The acid component and the alcohol component are preferably used in an amount of from 1 to 1.3 equivalents of the alcohol component to 1 equivalent of the acid component.
It is more preferable to use 1.2 equivalents.

The triester of phosphorous acid or phosphoric acid used in the present invention includes, for example, aromatic esters such as phenyl ester and tolyl ester, and alkyl esters such as methyl ester, propyl ester and butyl ester (carbon of alkyl group). The number is preferably 1 to 4). The triester of phosphorous acid or phosphoric acid is preferably used in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.5% by weight, based on the total amount of the acid component and the alcohol component. Is more preferable, and it is particularly preferable to use 0.1 to 0.3% by weight. If this usage is 0.0
If the amount is less than 1% by weight, the releasability of the sheet-like molding material obtained from the mold becomes poor, and the resulting unsaturated polyester composition is unavoidably colored, resulting in poor coloring. On the other hand, if it exceeds 10% by weight, the releasability cannot be improved much.

The zinc compound used in the present invention is:
It is used as a reaction catalyst for a saturated polybasic acid ester, and examples thereof include zinc acetate. The amount of the zinc compound is preferably 0.1 to 1.0% by weight, more preferably 0.05 to 0.5% by weight, based on 100% by weight of the saturated polybasic acid ester. Preferably, it is particularly preferably 0.1 to 0.3% by weight.
When the amount of the zinc compound is less than 0.01% by weight, the reaction does not proceed, and the coloring property of the obtained unsaturated polyester composition deteriorates. When the amount exceeds 1.0% by weight, the effect of shortening the reaction time is obtained. Can not be seen.

The method for producing the unsaturated polyester as the component (A) is not particularly limited. For example, the above-mentioned acid component and alcohol component are subjected to a condensation reaction, and water generated when both components react is discharged out of the system. It is performed by detachment. In order to carry out this reaction, glass, stainless steel or the like is selected, a stirrer, a fractionating device for preventing distillation of the alcohol component due to azeotropy of water and the alcohol component, and heating to increase the temperature of the reaction system. It is preferable to use a reaction apparatus provided with an apparatus, a temperature control apparatus for the heating apparatus, a blowing apparatus for nitrogen and the like.

The reaction temperature is preferably 150 ° C. or higher, and the reaction is preferably carried out while passing an inert gas such as nitrogen or carbon dioxide for preventing a side reaction due to oxidation. The reaction proceeds while heating a system in which an acid component and an alcohol component are mixed, and removing low-molecular-weight compounds such as condensed water generated outside the system. This is preferably carried out by natural or vacuum distillation by passing an inert gas. In order to promote the distillation of condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component. In general, the progress of the reaction can be known by measuring the amount of distillate produced by the reaction, quantifying the terminal functional group, measuring the viscosity of the reaction system, and the like.

Examples of the copolymerizable monomer used as the component (B) in the present invention include styrene, chlorostyrene, divinylbenzene, tertiary butyl styrene, and the like.
Styrene derivatives such as styrene bromide, alkyl esters of methacrylic acid or acrylic acid (hereinafter abbreviated as (meth) acrylic acid) such as methyl methacrylate, ethyl methacrylate, ethyl acrylate, and butyl acrylate; β-hydroxymethacrylic acid Ethyl, hydroxyalkyl esters of (meth) acrylic acid such as ethyl β-hydroxyacrylate, diallyl phthalate, acrylamide, phenylmaleimide and the like are used. Further, polyfunctional (meth) acrylates such as ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate can be used. These may be used in combination of two or more.

(A) Component unsaturated polyester and (B)
The mixing ratio of the copolymerizable monomer of the component is expressed by weight ratio [(A) /
(B)], the range of 25/75 to 80/20 is preferable,
The range of 40/60 to 65/35 is more preferable. When the weight ratio is less than 25/75, the viscosity of the resulting unsaturated polyester composition is too low to be easily applied to a sheet, and the curing shrinkage is large even when the obtained sheet-like molding material is molded. There is a tendency for cracks, cracks and the like to occur in the molded product. On the other hand, if the weight ratio exceeds 80/20, the viscosity tends to be too high, and it tends to be difficult to apply the composition in a sheet form.

The unsaturated polyester composition of the present invention comprises:
If necessary, a reinforcing material (fiber reinforced material), a low-shrinking agent, a filler, a thickener, a curing agent, a release agent, a stabilizer and the like can be contained. Examples of the reinforcing material include glass fiber, carbon fiber, polyimide fiber (Kepler fiber), vinylon fiber and the like, and glass fiber is generally used. These reinforcing materials are used in the form of continuous fibers, woven fabrics, non-woven fabrics, etc., and roving-like ones cut to an appropriate length, preferably about 25 mm, and the number of glass fibers bundled is 400 or less. Are preferred, and 100 to 200
This focus is more preferred. In addition, the glass fiber is 1
It is preferably from 0 to 50 g / m, more preferably from 25 to 35 g / m.

As the low contraction agent, polymethyl methacrylate, polystyrene, polycaprolactone, polyvinyl acetate, polyethylene, butadiene rubber and the like are used.
This amount is determined in consideration of the shrinkage, surface smoothness, and surface gloss of the molded product, and is not particularly limited.

As the filler, silica sand, calcium carbonate,
Examples include inorganic fillers such as talc and clay, and organic fillers such as wood powder, polyethylene powder, and pulverized products of various FRP molded products. Of these, calcium carbonate, particularly heavy calcium carbonate, is preferred. The amount of the filler used is determined in consideration of physical properties such as the strength of the molded article, the viscosity of the unsaturated polyester composition, and fluidity, and is 100 to 180 parts by weight based on 100 parts by weight of the unsaturated polyester composition. And more preferably 105 to 125 parts by weight. If the amount is less than 100 parts by weight, it may settle in the composition.
If the amount exceeds 80 parts by weight, the viscosity of the composition may be too high to stir. The particle size of the calcium carbonate used is preferably 0.1 to 10 microns, more preferably 0.4 to 1.5 microns. If the particle size is less than 0.1 micron, the viscosity will increase, and if it exceeds 0 micron, the fluidity will be poor.

Examples of the curing agent include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters and the like. The amount of the curing agent is determined not only in the molding cycle but also in the storage stability of the material, color unevenness, and the like. From the viewpoint of the preservability of the material and the molding cycle, the amount is preferably 0.5 to 5% by weight, more preferably 1 to 2% by weight, based on the unsaturated polyester composition.

As the thickener, for example, magnesium oxide, magnesium hydroxide, potassium oxide, potassium hydroxide and the like are used, but generally, magnesium oxide is used. The amount of the thickener is determined according to the workability of molding, and is preferably 0.5 to 5% by weight, more preferably 0.7 to 2% by weight, based on the unsaturated polyester composition. If the thickener is less than 0.5% by weight, the viscosity of the unsaturated polyester composition may not increase, and if it exceeds 5% by weight, the viscosity may increase too much to control.

As the release agent, zinc stearate, calcium stearate and the like are used. The amount of the release agent is preferably from 1 to 10% by weight, more preferably from 2 to 4% by weight, based on the unsaturated polyester composition. If the amount of the release agent is less than 1% by weight, the molded article sticks to the mold, it is difficult to remove the molded article, and the molded article may be cracked. If it exceeds 10% by weight,
The strength of the molded product may be reduced.

The viscosity of the unsaturated polyester composition of the present invention is determined by the molded product,
0 Pa · s, preferably 1500 to 15000 Pa
S, more preferably 3500 to 12000 Pa
・ S is particularly preferred. This viscosity is 1000Pa · s
If it is less than 1, scumming is likely to occur on the surface of the molded article, and if it exceeds 18000 Pa · s, the mold clamping time will be long and the molding cycle may be extended. However, the above viscosity is measured at 40 ° C.

[0027] The sheet-shaped molding material of the present invention can be produced by a conventional SM.
It can be manufactured using a C manufacturing apparatus. For example,
The unsaturated polyester as the component (A) is dissolved in the copolymerizable monomer as the component (B), and a curing agent, a polymerization inhibitor such as p-benzoquinone, naphthoquinone, tolquinone, hydroquinone, or mono-t-butylhydroquinone is added thereto. , Dissolving additives such as thickeners, and further mixing thermoplastic resins and fillers such as polystyrene, polyethylene, and polyvinyl acetate as necessary, and obtaining the resulting unsaturated polyester composition, such as a polyethylene film. It is applied to a uniform thickness on a release film, and a reinforcing agent such as glass fiber of a predetermined length is evenly sprayed thereon, and another film coated with the unsaturated polyester composition is further applied thereon. The scattered reinforcing material is overlapped so as to be sandwiched by the unsaturated polyester composition, wound up on a roll, and aged as necessary to form a sheet-shaped molding material. Rukoto can. When a thickener is added to the unsaturated polyester composition, the room temperature to 6
It is preferred to heat to a temperature of 0 ° C. for aging. The sheet-shaped molding material of the present invention is molded by compression molding, transfer molding, or the like, and can be used for molding a wide range of FRP molded products.

[0028]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Example 1 (1) Synthesis of unsaturated polyester Polyethylene terephthalate (weight average molecular weight 11,0
00) 1260 parts, 476 parts of propylene glycol, 312 parts of neopentyl glycol, 9 parts of triphenylphosphophosphate and 0.6 parts of zinc acetate were mixed with 3 liters equipped with a thermometer, a nitrogen blowing tube, a rectification column and a stirrer. Was heated using a mantle heater, and the temperature was raised to 200 ° C. in 3 hours. Thereafter, when the temperature was maintained at 200 ° C. for 5 hours, the mixture was cooled, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. for 5 hours. Then, 21
After cooling to 0 ° C and keeping the temperature for 8 to 12 hours, the acid value becomes 24.
When it became, it was cooled to complete the reaction.

(2) Preparation of unsaturated polyester composition 620 parts of the unsaturated polyester obtained in the above (1) was dissolved in 380 parts of styrene as a copolymerizable monomer, and then hydroquinone 0.02 was used as a polymerization inhibitor. Parts were dissolved.
The viscosity at 25 ° C. of the obtained unsaturated polyester composition was 1.54 Pa · s, and the hue was 1 or less in Gardner number. Obtained unsaturated polyester composition 800
Part and a solution of 60 parts of polystyrene having a number average molecular weight of 80,000 in 140 parts of styrene, 200 parts of t-butyl perbenzoate (Perbutyl Z manufactured by NOF Corporation)
10 parts (using trade name), 1250 parts of calcium carbonate (using NS # 200 (trade name) manufactured by Nitto Powder Chemical Co., Ltd.) and 40 parts of zinc stearate are added, and a Cowles-type wing is sufficiently used. Mixed. The viscosity of this mixture is 2
It was 36 Pa · s at 5 ° C. 8.5 parts of magnesium oxide was added to this mixture, stirred well, and aged at 40 ° C. for 24 hours to prepare a compounded unsaturated polyester composition. This compounded unsaturated polyester composition has a viscosity of 345 at 40 ° C.
It was 0 Pa · s.

(3) Preparation of sheet-shaped molding material Using the compounded unsaturated polyester composition prepared in the above (2), the content of glass was adjusted to 30% by weight by a dual wire mesh type SMC manufacturing apparatus, and a release film was prepared. Was formed into a sheet using a 50 μm thick polypropylene film, and aged in an aging furnace at 40 ° C. for 3 days to prepare a sheet-shaped molding material. The viscosity of the formed sheet-shaped molding material was 11500 Pa · s at 40 ° C.

(4) Measurement of Releasability In order to examine the releasability of the sheet-like molding material obtained in the above (3), the aluminum peel strength was measured by the following method. Release the release film from the sheet-like molding material, so that the glossy surface of the aluminum foil is in contact with the sheet-like molding material,
Using a 150 ton press, sandwich the plate between aluminum foils of 300 x 250 mm, apply a surface pressure of 5.0 MPa, and raise the mold temperature to 140
The temperature was set to 130 ° C. and the lower temperature was set to 130 ° C., and heating and pressing were performed for 5 minutes to form a flat molded product. The dimensions of the flat molded product were a flat surface of 300 × 280 mm and a thickness of 6 mm. Next, 50 mm wide and 150 mm long were placed on the aluminum foil on the surface of the flat molded product.
Make a notch in the shape of a strip, and grasp one end in the length direction.
When the aluminum peel strength was measured by peeling at 0 mm / min, the aluminum peel strength was 11 N / m.

(4) Measurement of Yellowing Degree of Molded Article In order to examine the weather resistance of the sheet-shaped molding material, the yellowing degree of the molded article was measured by the following method. The release film is peeled off from the sheet-shaped molding material obtained in the above (3), the surface pressure is set to 5.0 MPa, the mold temperature is set to 140 ° C. at the upper side and 130 ° C. at the lower side using a 150-ton press, and the molding time is 5 minutes. Then, heating and pressing were performed to produce a flat plate molded product. The size of the flat molded product is 300
× 280 mm, thickness 6 mm. JIS
When a 200-hour exposure test was performed in the WS-type accelerated exposure test described in A1415-1994, the yellowing degree (Δ
E) was 2.

Comparative Example 1 In the synthesis of the unsaturated polyester described in Example 1 (1), t-butyl titanate was used instead of zinc acetate.
Unsaturated polyester was synthesized in the same manner as in Example 1 except that 6 parts were used and the reaction was terminated at an acid value of 25. Hereinafter, in the same manner as in Example 1, an unsaturated polyester composition, a compounded unsaturated polyester composition, and a sheet-shaped molding material were produced, and the aluminum peel strength and the yellowing degree were measured. As a result, the unsaturated polyester composition 2
The viscosity at 5 ° C. was 1.5 Pa · s, and the hue was 1 to 2 in Gartner number. The viscosity of the mixture during the preparation process of the unsaturated polyester composition was 35 Pa · s at 25 ° C., and the viscosity of the unsaturated polyester composition was 40 Pa · s.
The viscosity at 3 ° C. was 3650 Pa · s, and the viscosity of the sheet-shaped molding material was 12000 Pa · a at 40 ° C. Further, the aluminum peel strength is 18 N / m and the yellowing degree (ΔE) is 7
Met.

Comparative Example 2 In the synthesis of the unsaturated polyester described in Example 1 (1), except that 996 parts of terephthalic acid and 372 parts of ethylene glycol were used instead of polyethylene terephthalate, and that zinc acetate was not added. Using the same material, the temperature was raised to 230 ° C. in 5 hours using a mantle heater. Thereafter, it was rapidly cooled to 220 ° C., kept warm for 10 hours, and cooled when the acid value reached 11. So far 1
Spent 5 hours. Thereafter, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. for 5 hours. Then 210
C. and kept for 12 hours. When the acid value reached 26, the reaction was terminated by cooling, and an unsaturated polyester was obtained.
Except that this unsaturated polyester was used, an unsaturated polyester composition, a compounded unsaturated polyester composition, and a sheet-like molding material were produced in the same manner as in Example 1, and the aluminum peel strength and the degree of yellowing were measured. Was done. As a result, the viscosity at 25 ° C. of the unsaturated polyester composition was 1.51 Pa · s, and the hue was 4 to 5 in Gartner number.
Met. The viscosity of the mixture in the preparation process of the compounded unsaturated polyester composition is 30 Pa · s at 25 ° C., the viscosity of the compounded unsaturated polyester composition at 40 ° C. is 3650 Pa · s, and the viscosity of the sheet-shaped molding material is , 40
It was 13200 Pa · a at ° C. Further, the aluminum peel strength was 22.3 N / m, and the yellowing degree (ΔE) was 9 in 200 hours.

[0036]

The unsaturated polyester composition of the present invention comprises:
The coloring property is good because it is lightened, and when it is made into a sheet-shaped molding material, the mold releasability from the mold after curing is good, and further, the yellowing of the obtained molded product is suppressed, and the weather resistance is improved. It is possible to provide a molded article excellent in quality. Further, since the sheet-shaped molding material according to the present invention is excellent in low-pressure moldability and mold release properties, the molding cycle can be shortened, and it is effective for efficient production of molded articles having excellent weather resistance. .

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/524 C08K 5/524 7/02 7/02

Claims (4)

[Claims] (A) (1) An α, β-unsaturated polybasic acid or an acid anhydride thereof is contained as an essential component, and its use ratio is such that a saturated polybasic acid and an unsaturated polybasic acid are used in combination. And an acid component that is at least 20 mol% with respect to the total amount of the acid anhydride and the acid component in the saturated polybasic acid ester, and (2) a saturated polybasic acid ester as an essential component. And (3) a polyhydric alcohol which is not more than 80 mol% with respect to the total amount of the saturated polybasic acid and unsaturated polybasic acid and the acid anhydride and the acid component in the saturated polybasic acid ester. , (4) a phosphoric acid triester or a phosphoric acid triester in an amount of 0.01 to the total of the acid component, the acid component and the alcohol component in the ester component.
To 1.0% by weight, and (5) 0.01 to 0.5% by weight of a zinc compound relative to the saturated polybasic acid ester. An unsaturated polyester composition comprising a monomer. 2. A sheet-like molding material comprising the unsaturated polyester composition according to claim 1 together with a fiber reinforcing material. 3. The unsaturated polyester composition according to claim 1, further comprising an inorganic filler, a curing agent, and a thickener, which are present together with the fiber reinforcement, and heated to room temperature to 60 ° C. to increase the viscosity. A method for producing a sheet-shaped molding material, comprising: 4. A sheet-shaped molding material obtained by the production method according to claim 3.