WO2014119360A1 - Glass-reinforced resin composition - Google Patents

Abstract

Provided is a glass-reinforced resin composition having excellent mechanical strength, impact strength and moldability. The present invention provides a glass-reinforced resin composition comprising (A) a copolymer which comprises 45 to 85 mass% of an aromatic vinyl monomer unit, 5 to 45 mass% of a (meth)acrylic acid ester monomer unit and 10 to 20 mass% of an unsaturated dicarboxylic acid anhydride monomer unit and (B) a glass which is modified with a cyclic ether having a 3-membered ring structure, wherein the content ratio of the copolymer (A) to the glass (B) is (60 to 95):(5 to 40) by mass.

Description

Glass reinforced resin composition

The present invention relates to a glass reinforced resin composition.

2. Description of the Related Art Conventionally, glass fiber reinforced resin compositions in which glass fiber is blended with a thermoplastic resin have been used to improve mechanical strength and impact strength in household appliances, automobiles, and electronic parts applications (for example, patents). Reference 1).

Japanese Patent Laid-Open No. 9-1111074

In recent years, from the viewpoint of weight reduction of parts, the industry has been demanded to increase the strength of the parts, and the glass fiber reinforced resin composition is also required to be further improved in mechanical strength and impact strength.

In order to improve the mechanical strength and impact strength of the glass fiber reinforced resin composition, the glass fiber content should be increased. However, if the glass fiber content is increased, the fluidity of the resin composition will decrease and the moldability will increase. A new problem will arise that will worsen.

The present invention has been made in view of such circumstances, and provides a glass-reinforced resin composition excellent in mechanical strength, impact strength, and moldability.

According to the present invention, the aromatic vinyl monomer unit is 45 to 85% by mass, the (meth) acrylic acid ester monomer unit is 5 to 45% by mass, and the unsaturated dicarboxylic anhydride monomer unit is 10 to 20% by mass. And a glass (B) modified with a cyclic ether having a three-membered ring structure, and the mass ratio of the copolymer (A) and the glass (B) is from 60 to A glass reinforced resin composition of 95: 5-40 is provided.

The inventors of the present invention have intensively studied to develop a resin composition excellent in mechanical strength, impact strength, and moldability. As described above, the aromatic vinyl monomer unit and (meth) acrylic are obtained. A specific amount of glass modified with a cyclic ether having a three-membered ring structure is blended with a copolymer containing acid ester monomer units and unsaturated dicarboxylic anhydride monomer units in a specific ratio. Thus, it was found that excellent results were obtained in all of mechanical strength, impact strength, and moldability.

The reason why the resin composition having such a characteristic composition exhibits excellent physical properties is not clear, but when various experiments were conducted, (1) the glass was modified with a cyclic ether having a three-membered ring structure, (2) The copolymer contains a specific amount of (meth) acrylic acid ester monomer units, and (3) the copolymer contains a specific amount of unsaturated dicarboxylic anhydride monomer units. If even one of the three conditions is not satisfied, at least one of the mechanical strength, impact strength, and formability has deteriorated. It is presumed that strength, impact strength, and formability are all improved.

Particularly noteworthy is the importance of the copolymer containing a specific amount of (meth) acrylate monomer units. Before conducting the experiment, I imagined that the effect of improving the strength would be achieved even if the copolymer did not contain (meth) acrylate monomer units. As a result, when a glass modified with a cyclic ether having a three-membered ring structure was added to a copolymer containing no (meth) acrylate monomer unit, the mechanical strength and impact strength were There was only a slight improvement. In contrast, when glass modified with a cyclic ether having a three-membered ring structure is added to a copolymer containing a (meth) acrylate monomer unit, mechanical strength and impact strength are increased. Greatly improved. From these results, it was found that it is essential that the copolymer contains a specific amount of (meth) acrylic acid ester monomer units in order to greatly improve the mechanical strength and impact strength.

<Explanation of terms>
In this specification, the symbol “to” means “above” and “below”, for example, the description “A to B” means more than A and less than B.

Hereinafter, embodiments of the present invention will be described in detail.

<< Copolymer (A) >>
The constituent unit of the copolymer (A) is 45 to 85% by mass of an aromatic vinyl monomer unit, 5 to 45% by mass of a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride monomer. 10 to 20% by mass, preferably 50 to 80% by mass of aromatic vinyl monomer unit, 8 to 38% by mass of (meth) acrylic acid ester monomer unit, unsaturated dicarboxylic anhydride monomer unit 12 to 18% by mass.

When the aromatic vinyl monomer unit is 45% by mass or more, the thermal stability is improved, and when the resin composition is molded, a molded product having a good appearance is obtained. If it exists, since thermal stability improves further, it is preferable. If the (meth) acrylic acid ester monomer unit is 5% by mass or more, mechanical strength and impact strength are improved by interaction with glass, and if it is 8% by mass or more, mechanical strength and impact strength are further improved. This is preferable. If the unsaturated dicarboxylic acid anhydride monomer unit is 10% by mass or more, the mechanical strength and impact strength are improved by interaction with glass, and if it is 12% by mass or more, the mechanical strength and impact strength are increased. Since it improves further, it is preferable.

If the aromatic vinyl monomer unit is 85% by mass or less, the proportion of the (meth) acrylic acid ester monomer unit and the (meth) acrylic acid ester monomer unit becomes sufficiently large, and the mechanical strength and If the impact strength is improved and it is 80% by mass or less, the mechanical strength and impact strength are further improved, which is preferable. When the (meth) acrylic acid ester monomer unit is 45% by mass or less, the thermal stability is improved, and when the resin composition is molded, a molded product having a good appearance is obtained, and 38% by mass. % Or less is preferable because the thermal stability is further improved. If the unsaturated dicarboxylic acid anhydride monomer unit is 20% by mass or less, the interaction with the glass does not become too large, the fluidity of the resin composition is improved, the moldability is improved, and 18% by mass. The following is preferable because the fluidity of the resin composition is further improved.

Aromatic vinyl monomer units include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, p-tert-butyl styrene, α-methyl styrene, α Examples thereof include units derived from styrene monomers such as -methyl-p-methylstyrene. Of these, styrene units are preferred. These aromatic vinyl monomer units may be one type or a combination of two or more types.

Examples of (meth) acrylic acid ester monomer units include methyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate; Examples include units derived from acrylate monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. Among these, a methyl methacrylate unit is preferable. These (meth) acrylic acid ester monomer units may be one kind or a combination of two or more kinds.

Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from respective anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. Among these, maleic anhydride units are preferable. The unsaturated dicarboxylic acid anhydride monomer unit may be one type or a combination of two or more types.

The copolymer (A) is a copolymerizable vinyl monomer other than an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit. A unit may be included in the copolymer as long as the effect of the invention is not impaired, and is preferably 5% by mass or less. Examples of the copolymerizable vinyl monomer unit include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, and N-ethylmaleimide N-alkylmaleimide monomers such as N-butylmaleimide and N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide Examples are units derived from the body. Two or more types of copolymerizable vinyl monomer units may be used.

The copolymer (A) preferably has a weight average molecular weight (Mw) of 100,000 to 200,000, and more preferably a weight average molecular weight (Mw) of 120,000 to 180,000. If the weight average molecular weight (Mw) is too large, the moldability of the resin composition obtained by blending with the methacrylic resin or the appearance of the molded product may be inferior. If the weight average molecular weight (Mw) is too small, the moldability Or, the strength of the molded product may be inferior. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is a value measured under the measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 series PL gel MIXED-B Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).

The manufacturing method of a copolymer (A) is demonstrated.
The polymerization mode is not particularly limited and can be produced by a known method such as solution polymerization or bulk polymerization, but solution polymerization is more preferable. The solvent used in the solution polymerization is preferably non-polymerizable from the viewpoint that a by-product is difficult to produce and that there are few adverse effects. The type of the solvent is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ethers such as tetrahydrofuran, 1,4-dioxane, toluene, ethylbenzene, xylene, chlorobenzene Aromatic hydrocarbons, etc. are mentioned, but methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of the solubility of the monomer and copolymer and the ease of solvent recovery. The amount of the solvent added is preferably 10 to 100 parts by mass, and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the copolymer to be obtained. If it is 10 parts by mass or more, it is suitable for controlling the reaction rate and the polymerization solution viscosity, and if it is 100 parts by mass or less, it is suitable for obtaining a desired weight average molecular weight (Mw).

The polymerization process may be any of a batch polymerization method, a semi-batch polymerization method, and a continuous polymerization method, but the batch polymerization method is suitable for obtaining a desired molecular weight range and transparency.

The polymerization method is not particularly limited, but is preferably a radical polymerization method from the viewpoint that it can be produced with high productivity by a simple process. The polymerization initiator is not particularly limited. For example, dibenzoyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxy Known organic compounds such as isopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate Known azo compounds such as peroxides, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, and the like can be used. Two or more of these polymerization initiators can be used in combination. Of these, organic peroxides having a 10-hour half-life temperature of 70 to 110 ° C. are preferably used.

In addition, regarding a method for obtaining a copolymer having a preferable weight average molecular weight (Mw) in the range of 100,000 to 200,000, in addition to adjustment of polymerization temperature, polymerization time, and polymerization initiator addition amount, addition amount of solvent And it can obtain by adjusting chain transfer agent addition amount. The chain transfer agent is not particularly limited. For example, a known chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene is used. Can do.

After the polymerization is completed, the polymerization solution is optionally provided with a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, a sulfur compound, a light resistant stabilizer such as a hindered amine compound, a benzotriazole compound, Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be added. The addition amount is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all monomer units. These additives may be used alone or in combination of two or more.

The method for recovering the copolymer (A) from the polymerization liquid is not particularly limited, and a known devolatilization technique can be used. For example, a method of continuously feeding the polymerization liquid to a twin-screw devolatilizing extruder using a gear pump and devolatilizing a polymerization solvent, an unreacted monomer and the like can be mentioned. The devolatilizing component including the polymerization solvent, unreacted monomer, etc. is condensed and recovered using a condenser, etc., and the polymerization solvent can be reused by purifying the condensate in a distillation tower. .

<< Glass (B) >>
The glass (B) of the present invention is modified with a cyclic ether having a three-membered ring structure (hereinafter simply referred to as “cyclic ether”). In the present specification, “modified with cyclic ether” means a state in which a functional group containing a cyclic ether having a three-membered ring structure exists on glass. For example, a glass modified with a cyclic ether can be produced by applying a modifier having such a functional group on the glass. Further, since glass fibers modified with cyclic ether are commercially available, commercially available products (eg, manufactured by JEOL Glass Co., Ltd .: ECS 03 T-120, ECS 03 T-717) may be used.

The degree of modification is not particularly limited. For example, the modification is preferably performed so that the cyclic ether is 0.01 parts by mass or more with respect to 100 parts by mass of the glass (B). This is because if it is less than this, the effect of improving the mechanical strength and impact strength may not be sufficient. The upper limit of the mass part of the cyclic ether is, for example, 10 parts by mass. This is because it is not possible to expect further improvement in mechanical strength and impact strength even if it is excessively modified. Further, the mass part of the cyclic ether in 100 parts by mass of the glass (B) modified with the cyclic ether is, for example, 0.01 to 10, preferably 0.01 to 1, and preferably 0.01 to 0.07. 0.03-0.07 is more preferable. This is because it has been experimentally verified that the impact strength is remarkably improved when the mass part of the cyclic ether is 0.07 or less.

The glass (B) is preferably a glass fiber, and the diameter and length of the glass fiber are not particularly limited as long as the size can be used for reinforcing the mechanical strength of the resin. The diameter of the glass fiber is, for example, 1 to 100 μm, preferably 2 to 50 μm, more preferably 5 to 15 μm. The average fiber length of the glass fiber is, for example, 0.5 to 10 mm, and preferably 1 to 5 mm. In addition, plate shape may be sufficient as glass (B). The thickness of the glass plate is not particularly limited, but is preferably 0.1 to 1.5 μm, and more preferably 0.2 to 0.7 μm. Furthermore, the copolymer (A) can be used by being laminated with glass.

<< Mixing / Lamination >>
A copolymer (A) and glass (B) can be mixed and it can be set as a glass reinforced resin composition. The mixing method of the copolymer (A) and the glass (B) is not particularly limited. For example, the copolymer (A) and the glass (B) are mixed using a Henschel mixer and then melt blended with an extruder. Can be done. Moreover, when glass is plate shape, it can be set as a glass reinforced resin composition by laminating | stacking glass (B) and a copolymer (A).
The mass ratio of the copolymer (A) and the glass (B) is 60 to 95: 5 to 40, and preferably 70 to 90:10 to 30. This is because if the amount of the glass (B) is too large, the moldability is deteriorated, and if it is too small, the mechanical strength and the like are not sufficiently improved.

In the resin composition, stabilizers, plasticizers, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, colorants, and the like may be blended within a range that does not impair the effects of the present invention.

The glass reinforced resin composition of the present invention includes an injection molded body, an injection compression molded body, an injection press molded body, a gas assist injection molded body, a foam molded body (including a method of injecting a supercritical fluid), an insert molded body, It can be used as a molded body such as a mold coating molded body, a heat-insulating mold molded body, a rapid heating / cooling mold molded body, a two-color molded body, a sandwich molded body, and an ultra-high speed injection molded body.

Hereinafter, the present invention will be described in more detail with reference to examples. Moreover, these are all illustrative and do not limit the contents of the present invention. In addition, the measuring method of various properties is as follows.
(1) Impact strength: Unnotched Charpy impact strength was measured according to JIS K 7111-1: 2006.
(2) Fluidity: According to JIS K 7210: 1999, the melt flow rate (MFR) was measured at a temperature of 220 ° C. and a load of 98 N.
(3) Rigidity: Flexural modulus was measured according to JIS K 7171: 2008.
(4) Determination of glass fiber modifier (cyclic ether having a three-membered ring structure):
Dissolve the resin adhering to the glass fiber with chloroform and acetic acid, add tetraammonium bromide acetic acid solution to the solution, generate hydrogen halide (HBr) from perchloric acid and quaternary ammonium salt, and react with epoxy group. It was. Details of the measurement method are shown below.
A glass fiber sample (15 g) was weighed into a 300 ml stoppered Erlenmeyer flask, added with 100 ml of chloroform and allowed to stand for 24 hours for dissolution. Next, 100 ml of acetic acid and 10 ml of tetraethylammonium bromide acetic acid solution were added, and further a crystal violet acetic acid solution was added as an indicator. The mixture was titrated with 0.1M perchloric acid acetic acid solution. The end point is determined when the indicator color changes to blue-green and the state is maintained. Thereafter, from the following formula 1, the amount of cyclic ether having a three-membered ring structure (mass part) relative to 100 parts by mass of the glass fiber sample was determined.

Cyclic ether with a three-membered ring structure (parts by mass)
= {(SA-Bt) × 44 × 0.1 / 1000} × {100 / sample mass (g)} Equation 1
SA: 0.1 M perchloric acid acetic acid solution amount (ml) required for sample titration
Bt: 0.1M perchloric acid acetic acid solution amount (ml) required for blank titration
44: Molecular weight of cyclic ether having a three-membered ring structure 0.1: Molar concentration (mol / L) of perchloric acid acetic acid solution

Moreover, the copolymer and glass fiber used in Examples and Comparative Examples were prepared as follows.

<Example of production of copolymer (A-1)>
20% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 20% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass. A 2% t-butyl peroxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization.
A 120 liter autoclave equipped with a stirrer was charged with 2.8 kg of a 20% maleic anhydride solution, 24 kg of styrene, 10.4 kg of methyl methacrylate, and 40 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining 88 ° C. after the temperature rise, 2.1% / hour of 20% maleic anhydride solution and 375 g / hour of 2% t-butylperoxy-2-ethylhexanoate solution were respectively added. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a temperature rising rate of 8 ° C./hour while maintaining the addition rate of 2.1 kg / hour as it was. The addition of the 20% maleic anhydride solution was stopped when the addition amount reached 25.2 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization solution is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, extruded into strands, and cut into pellets. A copolymer (A-1) was obtained. The obtained copolymer (A-1) was subjected to composition analysis by C-13 NMR method. The composition analysis results are shown in Table 1.

<Example of production of copolymer (A-2)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as A-1.
A 120 liter autoclave equipped with a stirrer was charged with 2 kg of a 20% maleic anhydride solution, 24 kg of styrene, 12 kg of methyl methacrylate, 40 g of t-dodecyl mercaptan, and 5 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining 88 ° C. after the temperature rise, a 20% maleic anhydride solution was added at a rate of 1.5 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a temperature rising rate of 8 ° C./hour while maintaining the addition rate of 1.5 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the addition amount reached 18 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, extruded into a strand, and cut into pellets. A copolymer (A-2) was obtained. The obtained copolymer (A-2) was subjected to composition analysis in the same manner as in A-1. The composition analysis results are shown in Table 1.

<Example of production of copolymer (A-3)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as A-1.
A 120 liter autoclave equipped with a stirrer was charged with 3.8 kg of a 20% maleic anhydride solution, 24 kg of styrene, 8.4 kg of methyl methacrylate, and 32 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining 88 ° C. after the temperature rise, a 20% maleic anhydride solution was added at a rate of 2.85 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 300 g / hour. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated up to 120 ° C. over 4 hours at a heating rate of 8 ° C./hour while maintaining the addition rate of 2.85 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the amount of addition reached 34.2 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, extruded into a strand, and cut into pellets. A copolymer (A-3) was obtained. The composition of the obtained copolymer (A-3) was analyzed in the same manner as in A-1. The composition analysis results are shown in Table 1.

<Example of production of copolymer (A-4)>
10% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 10% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass A 2% t-butylperoxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization.
A 120 liter autoclave equipped with a stirrer was charged with 2 kg of a 10% maleic anhydride solution, 24 kg of styrene, 14 kg of methyl methacrylate, 48 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas. The temperature was raised to 90 ° C. over 40 minutes with stirring. While maintaining 90 ° C. after the temperature rise, a 10% maleic anhydride solution was added at a rate of 1.5 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 300 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 10% maleic anhydride solution and methyl methacrylate were heated to 120 ° C. over 4 hours at a temperature rising rate of 7.5 ° C./hour while maintaining the addition rate of 1.5 kg / hour as they were. The addition of the 10% maleic anhydride solution was stopped when the addition amount reached 18 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, extruded into a strand, and cut into pellets. A copolymer (A-4) was obtained. The obtained copolymer (A-4) was subjected to composition analysis in the same manner as in A-1. The composition analysis results are shown in Table 1.

<Example of production of copolymer (A-5)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as A-1.
A 120 liter autoclave equipped with a stirrer was charged with 5 kg of a 20% maleic anhydride solution, 24 kg of styrene, 6 kg of methyl methacrylate, and 32 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 88 ° C over a period of minutes. While maintaining 88 ° C. after the temperature rise, a 20% maleic anhydride solution was added at a rate of 3.75 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 300 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated up to 120 ° C. over 4 hours at a heating rate of 8 ° C./hour while maintaining the addition rate of 3.75 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the addition amount reached 45 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization solution is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, extruded into strands, and cut into pellets. A copolymer (A-5) was obtained. The obtained copolymer (A-5) was subjected to composition analysis in the same manner as in A-1. The composition analysis results are shown in Table 1.

<Copolymer (B-1)>
Dilark D-332 manufactured by Nova Chemical Japan was used. The copolymer B-1 was subjected to composition analysis in the same manner as A-1. The composition analysis results are shown in Table 1.

<Glass fiber (C-1)>
ECS 03 T-120 manufactured by Nippon Electric Glass Co., Ltd. modified with a cyclic ether having a three-membered ring structure was used.
<Glass fiber (C-2)>
ECS 03 T-717 manufactured by Nippon Electric Glass Co., Ltd. modified with a cyclic ether having a three-membered ring structure was used.
<Glass fiber (C-3)>
ECS 03 T-351 manufactured by Nippon Electric Glass Co., Ltd. which was not modified with a cyclic ether having a three-membered ring structure was used.
Glass fibers (C-1), (C-2), and (C-3) all had a fiber length of 3 mm and a fiber diameter of 13 μm. Table 2 shows (C-1), (C-2), and (C-3).

The copolymer described in Table 1 and the glass fiber described in Table 2 were mixed using a Henschel mixer at the ratio (mass%) described in Table 3, and then mixed into a single screw extruder (MS-40 manufactured by IKG). Then, it was melt-kneaded at a cylinder temperature of 240 ° C. and pelletized to obtain a resin composition.
Table 3 shows the evaluation results of the resin composition.

From the results of Examples, Comparative Examples, and Reference Examples, the following became clear.
Comparing Example 1, Comparative Example 1 and Reference Example 1, the comparative example 1 in which the glass fiber not modified with the cyclic ether was added to the copolymer (A-1) was compared with the reference example 1 in flexural elasticity. In Example 1, where the glass fiber modified with cyclic ether was added to the copolymer (A-1), the impact strength and the flexural modulus were increased. Both got higher. The MFR value was also a value that could ensure sufficient fluidity during molding.
In Example 2, glass fibers having different cyclic ether modification amounts were used, but in Example 2, the impact strength was lower than in Example 1. This result shows that when the cyclic ether modification amount is excessively increased, the impact strength is decreased, and the mass part of the cyclic ether in 100 parts by mass of the glass fiber is particularly preferably 0.07 or less.
In Example 3, the copolymer (A-2) having a relatively large ratio of MMA units and a relatively small ratio of MAH units was used, and in Example 4, the ratio of MMA units was relatively small and the ratio of MAH units. A copolymer (A-3) having a relatively large value was used. In each of Examples 3 to 4, both the impact strength and the flexural modulus are high, and the MFR is a value that can ensure good moldability. In Example 3, the MFR value is particularly large. In Example 4, the impact strength was particularly high.

In Comparative Example 2, when the copolymer (A-4) having a MAH unit ratio of 10% by mass or less was used, the impact strength was low.
In Comparative Example 3, when the copolymer (A-5) having a MAH unit ratio of 25% by mass or more was used, the MFR value was very small.
In Comparative Example 4, when the copolymer (B-1) containing no MMA unit was used, the impact strength, MRF, and flexural modulus were all low. Of particular note, as can be seen from a comparison between Example 1 and Reference Example 1, when glass fiber modified with cyclic ether is added to copolymer (A-1), the impact strength is greatly improved. As can be seen from a comparison between Example 4 and Reference Example 2, when glass fiber modified with cyclic ether is added to the copolymer (B-1) containing no MMA unit, the impact strength is slightly improved. It was only. This result shows that it is essential for the copolymer to contain MMA units in order to significantly improve the impact strength.
As described above, the results of Comparative Examples 2 to 4 indicate that it is essential that the copolymer contains both the MMA unit and the MAH unit in a specified amount.

In Comparative Example 5, when the content ratio of the glass fiber modified with the cyclic ether was less than 5% by mass of the entire resin composition, both the impact strength and the flexural modulus were low.
In Comparative Example 6, when the content ratio of the glass fiber modified with cyclic ether exceeded 40% by mass of the entire resin composition, the fluidity was remarkably low and molding was impossible.

Claims (5)

A copolymer comprising 45 to 85% by weight of aromatic vinyl monomer units, 5 to 45% by weight of (meth) acrylic acid ester monomer units, and 10 to 20% by weight of unsaturated dicarboxylic acid anhydride monomer units ( A) and glass (B) modified with a cyclic ether having a three-membered ring structure,
The glass-reinforced resin composition, wherein a mass ratio of the copolymer (A) and the glass (B) is 60 to 95: 5 to 40. The copolymer (A) has an aromatic vinyl monomer unit of 50 to 80% by mass, a (meth) acrylic acid ester monomer unit of 8 to 38% by mass, an unsaturated dicarboxylic acid anhydride monomer unit of 12 to The glass reinforced resin composition according to claim 1, comprising 18% by mass. The glass-reinforced resin composition according to claim 1 or 2, wherein a mass ratio of the copolymer (A) and the glass (B) is 70 to 90:10 to 30. The glass-reinforced resin composition according to any one of claims 1 to 3, wherein the glass (B) is a glass fiber. A molded article comprising the resin composition according to any one of claims 1 to 4.