WO2017154722A1 - Resin composition, method of manufacturing resin composition, molded article, and vehicle - Google Patents

Abstract

Provided is a resin composition having excellent heat resistance and transparency. Also provided is a method for manufacturing a resin composition, which is excellent in productivity, and by which the resin composition obtained has excellent heat resistance and transparency. The resin composition includes: a copolymer (A), including a methyl (meth)acrylate unit (A1), a (meth)acrylic acid unit (A2) and an anhydrous glutaric acid unit (A3); and a compound (B) represented by general formula (1). In the method for manufacturing the resin composition, monomers including methyl (meth)acrylate (a1) and (meth)acrylic acid (a2) are polymerized to obtain a precursor, and the precursor obtained is melt-kneaded with the compound (B) represented by general formula (1).　

Description

Resin composition, method for producing resin composition, molded article, and vehicle

The present invention relates to a resin composition, a method for producing the resin composition, a molded body, and a vehicle.
This application claims priority on March 7, 2016 based on Japanese Patent Application No. 2016-029441 filed in Japan, the contents of which are incorporated herein by reference.

Polymethyl methacrylate and polycarbonate are widely used in various fields such as optical materials, vehicle parts, lighting materials, and building materials because of their excellent transparency and dimensional stability.
In recent years, molded products of polymethylmethacrylate and polycarbonate have been required to have higher performance as the parts are made thinner and finer. One of the performances is heat resistance. In particular, vehicle parts such as tail lamps and head lamps are required to have better heat resistance because vehicles such as automobiles are used even under high temperature and high humidity.

However, although polymethyl methacrylate has excellent transparency and weather resistance, the heat resistance is not sufficient. Polycarbonate has excellent heat resistance and impact resistance, but has a large birefringence, which is an optical distortion, and causes optical anisotropy in the molded product. In addition, it has molding processability, scratch resistance, and oil resistance. Remarkably inferior.

Therefore, studies are being made to improve the heat resistance of acrylic resins typified by polymethyl methacrylate. For example, Patent Document 1 discloses a method in which a copolymer of methyl methacrylate, methacrylic acid, and methyl-2- (hydroxymethyl) acrylate is subjected to a condensation cyclization reaction with a cyclization catalyst of a phosphate ester compound.

Japanese Patent Laid-Open No. 2002-60424

However, the method disclosed in Patent Document 1 has a problem of coloring because the time required for the condensation cyclization reaction is long and inferior in productivity, and uses a phosphate ester compound as a cyclization catalyst. In addition, a strongly acidic phosphate compound such as methyl phosphate corrodes a metal and is difficult to apply to a continuous production process.

Therefore, an object of the present invention is to solve these problems and provide a resin composition having excellent heat resistance and transparency. Moreover, the objective of this invention is providing the manufacturing method of the resin composition which is excellent in productivity and excellent in the heat resistance of the resin composition obtained, and transparency.

The present invention has the following configuration.
[1] A copolymer (A) comprising a methyl (meth) acrylate unit (A1), a (meth) acrylic acid unit (A2) and a glutaric anhydride unit (A3), and a compound represented by the following general formula (1) ( B).

(R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.)
[2] The resin composition according to [1], wherein at least one of R ₁ , R ₂ and R ₃ of the compound (B) is an aryl group.
[3] The resin composition according to [1] or [2], wherein R ₁ , R ₂ and R _{3 of the} compound (B) are each a cyclic alkyl group or an aryl group.
[4] The compound (B) is at least one selected from the group consisting of triphenylphosphine, diphenylcyclohexylphosphine, parastyryldiphenylphosphine, tris (4-methoxyphenyl) phosphine, and tris (4-fluorophenyl) phosphine. The resin composition according to any one of [1] to [3].
[5] The content of the compound (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A), according to any one of [1] to [4] The resin composition as described.
[6] In 100 mol% of copolymer (A), methyl (meth) acrylate unit (A1) is 70 mol% or more, (meth) acrylic acid unit (A2) is 0.5 mol% or more and 20 mol% or less, anhydrous glutar The resin composition according to any one of [1] to [5], wherein the acid unit (A3) is 0.3 mol% or more and 10 mol% or less.
[7] The resin composition according to any one of [1] to [6], wherein the conversion rate to the glutaric anhydride unit (A3) represented by the following formula (I) is 5% or more and 90% or less.
Conversion rate to glutaric anhydride unit (A3) (%) = {[ratio of glutaric anhydride unit (A3) in copolymer (mol%)] / ([(meth) acrylic in copolymer Ratio of acid unit (A2) (mol%)] + [Proportion of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 (I)
[8] The resin composition according to any one of [1] to [7], wherein the molded piece having a thickness of 2 mm has a haze value of 1 or less.
[9] The resin composition according to any one of [1] to [8], wherein the melt flow rate at a load of 13.65 kgf and a temperature of 230 ° C. is 6 g / 10 min or more.

[10] A monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) is polymerized to obtain a precursor, and the obtained precursor and a compound represented by the following general formula (1) (B) The manufacturing method of the resin composition which melt-kneads.

(R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.)
[11] The method for producing a resin composition according to [10], wherein the polymerization method is suspension polymerization.
[12] The method for producing a resin composition according to [10] or [11], wherein the content of the compound (B) is 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the precursor.
[13] The method for producing a resin composition according to any one of [10] to [12], wherein the melt kneading temperature is 150 ° C. or higher and 270 ° C. or lower.

[14] A molded article obtained by molding the resin composition according to any one of [1] to [9].
[15] A vehicle part including the molded article according to [14].
[16] A vehicle using the vehicle component according to [15].

The resin composition of the present invention is excellent in heat resistance and transparency.
In addition, the method for producing the resin composition of the present invention is excellent in productivity, and by including the unit (A3) accordingly, it has excellent low water absorption, resulting in a decrease in saturated water absorption, and heat resistance under water absorption conditions. Since it is excellent and can reduce silver streaks during molding, a resin composition having excellent transparency can be produced.

(Copolymer (A))
The resin composition of the present invention contains a copolymer (A).
The copolymer (A) comprises a methyl (meth) acrylate unit (A1) (hereinafter sometimes simply referred to as “unit (A1)”), a (meth) acrylic acid unit (A2) (hereinafter simply referred to as “unit ( A2) ”and glutaric anhydride units (A3) (hereinafter sometimes simply referred to as“ units (A3) ”).

(Unit (A1))
The unit (A1) is a methyl (meth) acrylate unit, but the resin composition is excellent in the thermal decomposition resistance of the copolymer (A) while maintaining the original performance of the acrylic resin. It preferably contains both acrylate units.
Methyl (meth) acrylate refers to methyl methacrylate, methyl acrylate, or both.

When the unit (A1) includes both a methyl methacrylate unit and a methyl acrylate unit, the content of the methyl methacrylate unit is preferably 50 mol% or more and 99.9 mol% or less, and 75 mol% or more and 99.99% or less in 100 mol% of the unit (A1). 5 mol% or less is more preferable. A resin composition does not impair the original performance of an acrylic resin as the content rate of a methyl methacrylate unit is 50 mol% or more. Moreover, it is excellent in the thermal decomposition resistance of a copolymer (A) as the content rate of a methylmethacrylate unit is 99.9 mol% or less.

When the unit (A1) contains both a methyl methacrylate unit and a methyl acrylate unit, the content of the methyl acrylate unit is preferably 0.1 mol% or more and 50 mol% or less, and 0.5 mol% or more in 100 mol% of the unit (A1). 25 mol% or less is more preferable. When the content of the methyl acrylate unit is 0.1 mol% or more, the copolymer (A) is excellent in thermal decomposition resistance. Moreover, a resin composition does not impair the original performance of an acrylic resin as the content rate of a methyl acrylate unit is 50 mol% or less.

The content of the methyl (meth) acrylate unit (A1) is preferably from 70 mol% to 99.2 mol%, more preferably from 80 mol% to 99 mol%, and more preferably from 85 mol% to 98.98 mol in 100 mol% of the copolymer (A). 5 mol% or less is still more preferable. When the content of the unit (A1) is 70 mol% or more, the resin composition does not deteriorate the original performance of the acrylic resin, and when it is 99.2 mol% or less, the heat resistance of the resin composition is excellent.

(Unit (A2))
The unit (A2) is a (meth) acrylic acid unit, but is preferably a methacrylic acid unit because the resin composition is excellent in heat resistance.
(Meth) acrylic acid refers to methacrylic acid, acrylic acid or both.

The content of the (meth) acrylic acid unit (A2) is preferably 0.5 mol% or more, more preferably 0.7 mol% or more, and further preferably 1.0 mol% or more in 100 mol% of the copolymer (A). Moreover, 20 mol% or less is preferable, 15 mol% or less is more preferable, and 10 mol% or less is still more preferable. It is excellent in the heat resistance of a resin composition as the content rate of a unit (A2) is 0.5 mol% or more. Moreover, a resin composition does not impair the original performance of an acrylic resin as the content rate of a unit (A2) is 20 mol% or less.

(Unit (A3))
The unit (A3) is a glutaric anhydride unit and is a structural unit represented by the following general formula (2).

R ₄ and R ₅ are each independently hydrogen or a methyl group.

The content of the glutaric anhydride unit (A3) is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, and still more preferably 0.6 mol% or more in 100 mol% of the copolymer (A). Moreover, 10 mol% or less is preferable, 7 mol% or less is more preferable, and 5 mol% or less is still more preferable. When the content of the unit (A3) is 0.3 mol% or more, the water absorption of the resin composition can be reduced, and the dimensional stability of the molded body and the heat resistance of the resin composition under water absorption conditions are excellent. In addition, it is possible to suppress the occurrence of silver streaks when the resin is injection molded. Moreover, a resin composition does not impair the original performance of an acrylic resin as the content rate of a unit (A3) is 10 mol% or less.

(Unit (A4))
In addition to the unit (A1), the unit (A2), and the unit (A3), the copolymer (A) may be referred to as another monomer unit (A4) (hereinafter simply referred to as “unit (A4)”). ) May be included.

The content of the unit (A4) is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 3 mol% or less in 100 mol% of the copolymer (A) because the resin composition does not impair the original performance of the acrylic resin. Is more preferable.

(Conversion rate to unit (A3))
The conversion rate to the glutaric anhydride unit (A3) represented by the following formula (I) is preferably 5% or more, and more preferably 10% or more. Moreover, it is preferable that it is 90% or less, and it is more preferable that it is 80% or less.
Conversion rate to glutaric anhydride unit (A3) (%) = {[ratio of glutaric anhydride unit (A3) in copolymer (mol%)] / ([(meth) acrylic in copolymer Ratio of acid unit (A2) (mol%)] + [Proportion of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 (I)
When the conversion rate to the glutaric anhydride unit (A3) is 5% or more, the water absorption of the resin composition can be reduced, the dimensional stability of the molded product, and the heat resistance of the resin composition under water absorption conditions. Excellent. In addition, it is possible to suppress the occurrence of silver streaks when the resin is injection molded. When the conversion rate to the glutaric anhydride unit (A3) is 90% or less, the resin composition does not impair the original performance of the acrylic resin.

(Compound (B))
The resin composition of the present invention includes a compound (B) represented by the following general formula (1).

R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.

Specific examples of the compound (B) include, for example, monophosphine such as methylphosphine, ethylphosphine, n-butylphosphine, tert-butylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, di-n-butylphosphine, Dialkylphosphines such as tert-butylphosphine and dioctylphosphine; trialkylphosphines such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine and trioctylphosphine; phenylphosphine, (p-tolyl) Monoarylphosphine such as phosphine, (o-tolyl) phosphine, (m-tolyl) phosphine; diphenylphosphine, di (p-tolyl) phosphine, di (o-tolyl) phosphine Diarylphosphine such as diphenyl, di (m-tolyl) phosphine, diphenylcyclohexylphosphine, p-styryldiphenylphosphine; triphenylphosphine, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) And triarylphosphine such as phosphine, tris (4-methoxyphenyl) phosphine, and tris (4-fluorophenyl) phosphine. These compounds (B) may be used individually by 1 type, and may use 2 or more types together. Among these compounds (B), since the activity as a cyclization catalyst is high and the transparency of the resin composition is excellent, at least one of R ₁ , R ₂ and R ₃ is an aryl group. Aryl phosphine, diaryl phosphine, and triaryl phosphine are preferable, and R ₁ , R _2, and R ₃ are each a cyclic alkyl group or an aryl group, more preferably monoaryl phosphine, diaryl phosphine, and triaryl phosphine, triphenyl phosphine, diphenyl More preferred are cyclohexylphosphine, parastyryldiphenylphosphine, tris (4-methoxyphenyl) phosphine and tris (4-fluorophenyl) phosphine.

The content of the compound (B) is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the copolymer (A). More preferably, it is 1 to 3 parts by mass. A unit (A3) can be formed efficiently as content of a compound (B) is 0.01 mass part or more. Moreover, it is excellent in transparency of a resin composition as content of a compound (B) is 10 mass parts or less.

(Resin composition)
The weight average molecular weight of the resin composition is preferably 30,000 or more, more preferably 50,000 or more, and still more preferably 70,000 or more. Moreover, 200,000 or less is preferable, 150,000 or less is more preferable, and 130,000 or less is still more preferable. When the mass average molecular weight of the resin composition is 30,000 or more, the mechanical properties are excellent. Moreover, it is excellent in melt fluidity that the mass average molecular weight of a resin composition is 200,000 or less.
The mass average molecular weight of the resin composition is a value measured using gel permeation chromatography using standard polystyrene as a standard sample.
The Vicat softening temperature in the absolutely dry condition of the resin composition is preferably 115 ° C. or higher and 128 ° C. or lower. When the Vicat softening temperature under the absolutely dry condition of the resin composition is 115 ° C. or higher, the resin composition is excellent in heat resistance in the absolutely dry state, and when it is 128 ° C. or less, the resin composition is excellent in low water absorption.
The Vicat softening temperature in the water absorption state of the resin composition is preferably 110 ° C. or higher. When the Vicat softening temperature in the water absorption condition of the resin composition is 110 ° C. or higher, the resin composition is excellent in heat resistance in the water absorption state.
In this specification, the Vicat softening temperature is a value measured according to ISO 306 A50 method.

The saturated water absorption of the resin composition is preferably 3% by mass or less, more preferably 2.5% by mass or less, and further preferably 2% by mass or less. When the saturated water absorption rate of the resin composition is 3% by mass or less, the resin composition is excellent in low water absorption, excellent in the dimensional stability of the molded article and in heat resistance in the water absorption state.

The haze of the resin composition is preferably from 0.1 to 1.0, more preferably from 0.2 to 0.8. When the haze of the resin composition is 0.1 or more, the productivity of the resin composition is excellent, and when it is 1.0 or less, the appearance of the resin composition is excellent.
In the present specification, the haze is a value obtained by molding a resin composition into a molded body having a thickness of 2 mm and measuring in accordance with ISO14782.
The yellow index (YI) of the resin composition is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.5. When the yellow index (YI) of the resin composition is 0.1 or more, the productivity of the resin composition is excellent, and when it is 2.0 or less, the appearance of the resin composition is excellent.
In the present specification, the yellow index (YI) is a value measured in accordance with ISO 17223 after a copolymer is molded into a molded body having a thickness of 2 mm.

The melt flow rate of the resin composition is preferably 6 g / 10 min or more and 20 g / 10 min or less, more preferably 10 g / 10 min or more and 15 g / 10 min or less. When the melt flow rate of the resin composition is 6 g / 10 min or more, the fluidity of the resin composition is excellent, and when it is 20 g / 10 min or less, the mechanical properties of the resin composition are excellent.
In this specification, the melt flow rate is a value measured under conditions of a load of 13.65 kgf and a temperature of 230 ° C.

The resin composition of the present invention may contain other additives in addition to the copolymer (A) and the compound (B).
Examples of other additives include ultraviolet absorbers, antioxidants, plasticizers, light diffusing agents, matting agents, lubricants, mold release agents, antistatic agents, and coloring agents such as pigments. These other additives may be used alone or in combination of two or more.
In order to suppress deterioration of the copolymer due to ultraviolet rays such as sunlight, it is preferable that the resin composition contains an ultraviolet absorber.
In order to suppress thermal degradation of the copolymer during melt kneading or melt molding, it is preferable that an antioxidant is contained in the resin composition.

(Production method of resin composition)
The resin composition of the present invention can be obtained through the following steps.
A monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) is polymerized to obtain a precursor of copolymer (A). The resulting precursor and the following general formula (1) The compound (B) functions as a catalyst for the condensation cyclization reaction, and the unit (A3) is formed from the unit (A1) and the unit (A2). The resin composition of this invention containing a copolymer (A) and a compound (B) can be obtained.

R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.

Methyl (meth) acrylate (a1) is methyl methacrylate, methyl acrylate or both, but the resin composition is excellent in the thermal decomposition resistance of the copolymer (A) while maintaining the original performance of the acrylic resin. It is preferable to contain both methyl methacrylate and methyl acrylate.

When methyl (meth) acrylate (a1) contains both methyl methacrylate and methyl acrylate, the content of methyl methacrylate is preferably 50 mol% or more and 99.9 mol% or less in 100 mol% of methyl (meth) acrylate (a1), 75 mol% or more and 99.5 mol% or less are more preferable. When the content of methyl methacrylate is 50 mol% or more, the resin composition does not impair the original performance of the acrylic resin. Moreover, it is excellent in the thermal decomposability | decomposability of a copolymer (A) as the content rate of methyl methacrylate is 99.9 mol% or less.

When methyl (meth) acrylate (a1) contains both methyl methacrylate and methyl acrylate, the content of methyl acrylate is preferably 0.1 mol% or more and 50 mol% or less in 100 mol% of methyl (meth) acrylate (a1), 0.5 mol% or more and 25 mol% or less are more preferable. When the content of methyl acrylate is 0.1 mol% or more, the copolymer (A) is excellent in thermal decomposition resistance. Further, when the content of methyl acrylate is 50 mol% or less, the resin composition does not impair the original performance of the acrylic resin.

The content of methyl (meth) acrylate (a1) is preferably from 70 mol% to 99.5 mol%, more preferably from 80 mol to 99.3 mol%, more preferably from 85 mol% to 99.0 mol%, based on 100 mol% of all monomers. The following is more preferable. When the content of methyl (meth) acrylate (a1) is 70 mol% or more, the resin composition does not impair the original performance of the acrylic resin, and when it is 99.5 mol% or less, the heat resistance of the resin composition is excellent.

(Meth) acrylic acid (a2) is methacrylic acid, acrylic acid, or both, and methacrylic acid is preferred because the resin composition is excellent in heat resistance.

The content of (meth) acrylic acid (a2) is preferably 0.5 mol% or more, more preferably 0.7 mol% or more, and even more preferably 1.0 mol% or more in 100 mol% of all monomers. Moreover, 20 mol% or less is preferable, 15 mol% or less is more preferable, and 10 mol% or less is still more preferable. When the content of (meth) acrylic acid (a2) is 0.5 mol% or more, the resin composition is excellent in heat resistance. Moreover, a resin composition does not impair the original performance of an acrylic resin as the content rate of (meth) acrylic acid (a2) is 20 mol% or less.

The monomer may contain other copolymerizable monomer (a4) in addition to methyl (meth) acrylate (a1) and (meth) acrylic acid (a2).

Examples of the other monomer (a4) include ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth) acrylate. , Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and other (meth) acrylates other than methyl (meth) acrylate; (meth) acrylonitrile; (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (Meth) acrylamide compounds such as (meth) acrylamide; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether; vinyl carboxylates such as vinyl acetate and vinyl butyrate; olefins such as ethylene, propylene, butene and isobutene Is mentioned. These other monomers may be used individually by 1 type, and may use 2 or more types together.
(Meth) acrylate refers to acrylate, methacrylate, or both.

The content of the other monomer (a4) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 3 mol% or less in 100 mol% of all monomers because the resin composition does not impair the original performance of the acrylic resin. % Or less is more preferable.

Examples of the monomer polymerization method include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these polymerization methods, block polymerization, suspension polymerization, and solution polymerization are preferable because of excellent transparency of the resin composition, and block polymerization and suspension polymerization are preferable because of excellent productivity of the copolymer (A). Is more preferable, and suspension polymerization is more preferable.

What is necessary is just to set suitably the polymerization temperature in the superposition | polymerization of a monomer, a polymerization initiator kind, and the amount of polymerization initiators according to the polymerization method to be used and the copolymer (A) to be obtained.

In order to adjust the mass average molecular weight of the copolymer (A), a chain transfer agent may be used in the polymerization of the monomers.
Examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycol. Mercaptan compounds such as phthalate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakisthiopropionate Α-methylstyrene dimer; terpinolene and the like. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together. Among these chain transfer agents, the mercaptan compound is preferable because the adjustment of the mass average molecular weight of the copolymer (A) is easy and the productivity of the copolymer (A) is excellent, and the monofunctional alkyl mercaptan compound is more preferable. preferable.

The amount of the chain transfer agent used is preferably 0.1 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.25 parts by mass or more and 0.45 parts by mass or less with respect to 100 parts by mass of all monomers. It is excellent in the melt fluidity of a resin composition as the usage-amount of a chain transfer agent is 0.1 mass part or more. Moreover, it is excellent in the mechanical characteristic of a resin composition as the usage-amount of a chain transfer agent is 0.5 mass part or less.

Examples of the melt-kneading method of the precursor and the compound (B) include a method of mixing a solid precursor and the compound (B) and heating and kneading with an extruder or a kneader; the precursor and the compound (B) Can be dissolved in a solvent, heated and stirred. Among these melt-kneading methods, a method of mixing a solid precursor and the compound (B) and heating and kneading with an extruder or a kneader is preferable because the resin composition is excellent in productivity.

The content of the compound (B) is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the precursor, and 0.2 parts by mass. More preferred is 3 parts by mass or less. A unit (A3) can be formed efficiently as content of a compound (B) is 0.01 mass part or more. Moreover, it is excellent in transparency of a resin composition as content of a compound (B) is 10 mass parts or less.

The melt-kneading temperature of the precursor and the compound (B) is preferably 150 ° C. or higher and 270 ° C. or lower, more preferably 180 ° C. or higher and 270 ° C. or lower, and further preferably 210 ° C. or higher and 250 ° C. or lower. When the melt kneading temperature is 150 ° C. or higher, the unit (A3) can be efficiently formed. Moreover, it is excellent in transparency of a resin composition as melt-kneading temperature is 270 degrees C or less.

The melt-kneading time of the precursor and the compound (B) is preferably from 10 seconds to 3000 seconds, and more preferably from 30 seconds to 1000 seconds. When the melt kneading time is 10 seconds or longer, the unit (A3) can be formed efficiently. Moreover, it is excellent in transparency of a resin composition as melt-kneading time is 3000 second or less.

(Molded body)
The molded product of the present invention is obtained by molding the resin composition of the present invention.

Examples of a molding method for obtaining a molded body include injection molding, extrusion molding, and pressure molding. Further, the obtained molded body may be further subjected to secondary molding such as pressure molding or vacuum molding.

The molding temperature is preferably 200 ° C. or higher and 270 ° C. or lower, and more preferably 210 ° C. or higher and 260 ° C. or lower. When the molding temperature is 200 ° C. or higher, the melt flowability of the resin composition is excellent, and the appearance of the molded article is excellent. Moreover, thermal decomposition of a resin composition can be suppressed as molding temperature is 270 degrees C or less.

Since the molded body of the present invention is excellent in heat resistance and transparency, it can be used for optical materials, vehicle parts, lighting materials, building materials, etc., and is particularly suitable for automotive vehicle parts, It is suitable for a vehicle using the vehicle component.

Examples of automotive vehicle parts include a rear lamp outer cover, an optical member inside the rear lamp, an inner lens for a headlight (sometimes referred to as a projector lens or a PES lens), a meter cover, a door mirror housing, a pillar cover ( Sash cover), license garnish, front grille, fog garnish, emblem and the like.

(Mass average molecular weight)
10 mg of the resin compositions obtained in Examples and Comparative Examples were dissolved in 10 ml of tetrahydrofuran and filtered through a 0.5 μm membrane filter to obtain a sample solution. The obtained sample solution was measured for mass average molecular weight using gel permeation chromatography (model name “HLC-8320 GPC Eco SEC”, manufactured by Tosoh Corporation). Two separation columns “TSKgel SuperHZM-H” (trade name, manufactured by Tosoh Corporation, inner diameter 4.6 mm × length 15 cm), tetrahydrofuran as solvent, differential refractometer as detector, standard sample Standard polystyrene was used under the conditions of a flow rate of 0.6 ml / min, a measurement temperature of 40 ° C., and an injection amount of 0.1 ml.

(Content of each unit in the resin composition)
The resin compositions and heavy dimethyl sulfoxide obtained in Examples and Comparative Examples were supplied to a 20 ml Schlenk tube equipped with a stirrer and heated to 80 ° C. with stirring to dissolve the resin composition. Then, it cooled to 23 degreeC, benzylamine was supplied to the Schlenk pipe | tube, and it heated at 80 degreeC, stirring. After reacting for 1 hour, the reaction solution was taken out, and ¹ H-NMR measurement was performed using a nuclear magnetic resonance apparatus (manufactured by varian, 270 MHz) under the conditions of a measurement temperature of 80 ° C. and an integration count of 32 times.
From the obtained ¹ H-NMR measurement results, the integrated value of the unreacted benzylamine of the unreacted benzylamine at the singlet peak present near 3.7 ppm and the benzyl proton of the glutaric acid benzylamide at the singlet peak present near 4.2 ppm. From the ratio of the integrated value, the content of the unit (A3) in the resin composition was calculated. Moreover, the integral value of the proton derived from the unit (A1) of the singlet peak existing in the vicinity of 3.5 ppm, the integral value of the proton derived from the unit (A1) and the unit (A2) present in the vicinity of 0.5 ppm to 2.5 ppm. The ratio of the unit (A1) and the unit (A2) in the resin composition was calculated by taking the ratio with the integral value of the benzyl protons of the unreacted benzylamine of the singlet peak existing in the vicinity of 3.7 ppm. .

(Heat resistance evaluation)
The resin compositions obtained in the Examples and Comparative Examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), and 80 mm × 8 mm × 4 mm. A molded body of was obtained. The obtained 80 mm × 8 mm × 4 mm molded body was cut to obtain a 40 mm × 8 mm × 4 mm molded body, and then annealed at 80 ° C. for 16 hours, and the obtained molded body was evaluated for heat resistance under absolutely dry conditions. It was used as a test piece. Moreover, a part of the test piece which was completely dried was left to stand at 25 ° C. and a humidity of 50% for 1 week, and used as a test piece for heat resistance evaluation under water absorption conditions.
For heat resistance evaluation, HDT / VICAT tester (model name “No. 148-HAD heat distortion tester”, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) is used, and a Vicat softening temperature test is conducted in accordance with ISO 306 A50 method. The Vicat softening temperature was measured.
In addition, each copolymer 3 times Vicat softening temperature test was done, and the average value was made into Vicat softening temperature.

(Water absorption evaluation)
The resin compositions obtained in Examples and Comparative Examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), and molded to 80 mm × 8 mm × 4 mm. Got the body. The obtained molded body of 80 mm × 8 mm × 4 mm was used as a test piece for water absorption evaluation.
The obtained test piece was dried in a vacuum dryer at 80 ° C. for 16 hours, and the mass at the time of drying was precisely weighed. Thereafter, the test piece was allowed to stand in a small environmental tester (model name “SH-241”, manufactured by ESPEC Corporation) set to 60 ° C. and relative humidity 90%. It was judged that saturated water was absorbed at the time of the test period of 60 days, and the mass at the time of saturated water absorption was precisely weighed. The saturated water absorption was calculated by the following formula (II).
Saturated water absorption (%) = {([mass when saturated water absorption] − [mass when drying]) / [mass when drying]} × 100 (II)
In addition, each copolymer was tested 3 times and the average value was made into the saturated water absorption.

(Appearance evaluation)
-Transparency The resin compositions obtained in Examples and Comparative Examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), 100 mm × A molded body of 50 mm × 2 mm was obtained. The obtained molded body of 100 mm × 50 mm × 2 mm was used as a test piece for transparency evaluation.
As a transparency evaluation, a haze meter (model name “NDH-2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) was used, and the haze of a molded product having a thickness of 2 mm was measured in accordance with ISO14782.
Each copolymer was tested three times, and the average value was defined as haze.
Color The resin compositions obtained in the examples and comparative examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), 100 mm × A molded body of 50 mm × 2 mm was obtained. The obtained molded body of 100 mm × 50 mm × 2 mm was used as a test piece for evaluation of color.
As a color evaluation, an instantaneous multi-photometry system (model name “MCPD-3000”, manufactured by Otsuka Electronics Co., Ltd.) was used, and the yellow index (YI) of a 2 mm-thick molded article was measured in accordance with ISO 17223.
Each copolymer was tested three times, and the average value was taken as the yellow index (YI).

(Mechanical property evaluation)
The resin compositions obtained in the Examples and Comparative Examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), and 80 mm × 8 mm × 4 mm. A molded body of was obtained. The obtained 80 mm × 8 mm × 4 mm molded body was used as a test piece for mechanical property evaluation.
As a mechanical property evaluation, a Tensilon universal testing machine (model name “RTC-1250A-PL”, manufactured by Orientec Co., Ltd.) was used, a three-point bending test was performed in accordance with ISO178, and the flexural modulus was measured.
Each copolymer was subjected to a five-point three-point bending test, and the average value was defined as the flexural modulus.

(Liquidity assessment)
The resin compositions obtained in Examples and Comparative Examples were supplied to a melt indexer (model name “Melt Indexer L244”, manufactured by Techno Seven Co., Ltd.), and the melt flow rate of the resin composition was measured. The test was conducted under the conditions of a temperature of 230 ° C. and a load of 13.65 kg, and the test cut-off interval was set to 10 seconds or longer and 120 seconds or shorter according to the fluidity of the resin composition.
Each resin composition was tested five times, and the average value was taken as the melt flow rate.

(Formability evaluation)
The resin compositions obtained in the examples and comparative examples were injection molded at a molding temperature of 250 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), and 100 mm × 50 mm × 2 mm A molded body was obtained.
The 10 molded bodies obtained were visually confirmed, and “A” indicates that no silver streak was confirmed in all the molded bodies, and 1 to 5 molded body silver streaks were confirmed. “B” and five or more molded bodies in which silver streaks were confirmed were evaluated as “C”.

[Production Example of Dispersant]
Supply 900 parts by weight of deionized water, 60 parts by weight of sodium 2-sulfoethyl methacrylate, 10 parts by weight of potassium methacrylate and 12 parts by weight of methyl methacrylate to a flask equipped with a stirrer, a thermometer and a condenser, and supply nitrogen. While discharging, the flask was heated to an internal temperature of 50 ° C. Thereafter, 0.08 part by mass of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was supplied, and the flask was heated so that the internal temperature of the flask became 60 ° C. Thereafter, methyl methacrylate was added dropwise at a rate of 0.24 parts by mass / min for 75 minutes using a dropping pump. Then, it hold | maintained for 6 hours and obtained the dispersing agent (10 mass% of solid content).

[Production Example 1]
2000 parts by mass of deionized water and 4.2 parts by mass of sodium sulfate were supplied to a separable flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, and stirred for 15 minutes at a stirring speed of 320 rpm. Thereafter, methyl methacrylate (96 mol%) (trade name “Acryester M”, manufactured by Mitsubishi Rayon Co., Ltd.) 1351.6 parts by mass, methyl acrylate (1 mol%) 12.1 parts by mass, methacrylic acid (3 mol%) 3 parts by mass, 2,2′-azobis-2-methylbutyronitrile (polymerization initiator, trade name “V-59”, manufactured by Wako Pure Chemical Industries, Ltd.) 2.8 parts by mass and n-octyl mercaptan ( A chain transfer agent, manufactured by Tokyo Chemical Industry Co., Ltd. (4.2 parts by mass) was supplied to a separable flask and stirred for 5 minutes. Thereafter, 6.72 parts by mass of the dispersant produced by the method shown in the production example of the dispersant was supplied to a separable flask and stirred to disperse the monomer mixture in the separable flask in water. Thereafter, nitrogen gas was discharged for 15 minutes.
Then, it heated so that the internal temperature of a separable flask might be 75 degreeC, and the temperature was hold | maintained until the polymerization exothermic peak was observed. After the polymerization exothermic peak was observed, the separable flask was heated to an internal temperature of 90 ° C. and held for 60 minutes to complete the polymerization. Thereafter, the mixture in the separable flask was filtered, and the filtrate was washed with deionized water and dried at 80 ° C. for 16 hours to obtain a bead-like precursor (1).
The composition ratio in the monomer mixture is shown in Table 1.

[Production Examples 2 to 3]
Except that the composition ratio in the monomer mixture was changed as shown in Table 1, the same operations as in Production Example 1 were performed to obtain bead-like precursors (2) to (3).

[Example 1]
100 parts by mass of the precursor (1) obtained in Production Example 1 and 0.3 part by mass of triphenylphosphine as the compound (B) were mixed, and the kneading temperature was determined using a twin-screw kneading extruder (manufactured by Werner & Pfleiderer, 30 mmφ). Melting and kneading was performed at 250 ° C. for 60 seconds to form a glutaric anhydride unit (A3) to obtain a pellet-shaped resin composition.
The evaluation results of the obtained resin composition are shown in Table 2.

[Examples 2 to 10]
Except having changed the kind of compound (B), the usage-amount of a compound (B), and melt-kneading time as shown in Table 2, operation similar to Example 1 was performed and the resin composition was obtained.
The evaluation results of the obtained resin composition are shown in Table 2.

[Comparative Example 1]
A resin composition was obtained in the same manner as in Example 1 except that only the precursor (1) was melt kneaded without using the compound (B).
The evaluation results of the obtained resin composition are shown in Table 2.

[Comparative Example 2]
Instead of using the compound (B), a mixture of stearyl phosphate and distearyl phosphate (trade name “ADK STAB AX-71”, manufactured by ADEKA Corporation) as a phosphate ester compound is mixed and melt-kneaded. Performed the same operation as Example 1, and obtained the resin composition.
The evaluation results of the obtained resin composition are shown in Table 2.

[Comparative Example 3]
A resin composition was obtained in the same manner as in Example 1 except that lithium acetate as a metal salt was mixed and melt-kneaded instead of using the compound (B).
The evaluation results of the obtained resin composition are shown in Table 2.

The resin compositions obtained in Examples 1 to 10 were excellent in transparency. In addition, since the resin compositions obtained in Examples 1 to 10 contain units (A3) correspondingly, they are excellent in low water absorption, resulting in a decrease in saturated water absorption and good heat resistance under water absorption conditions. It has become.
The resin composition obtained in Comparative Example 1 contains almost no unit (A3), is inferior in low water absorption, and has low heat resistance under water absorption conditions.
Since the resin composition obtained in Comparative Example 2 used a phosphate ester compound, the resin composition became cloudy, and the transparency of the resin composition was lowered. Moreover, the unit (A3) can hardly be formed, the water absorption is inferior, and the heat resistance under water absorption conditions is lowered.
The resin composition obtained in Comparative Example 3 was cloudy because it used a metal salt compound, and was inferior in transparency. Further, since the metal salt itself is water-soluble, the water absorption of the resin composition after kneading is deteriorated, and the heat resistance under water absorption conditions is reduced. Furthermore, the fluidity of the resin composition was inferior.

[Example 11]
100 parts by mass of the precursor (2) obtained in Production Example 2 and 0.1 part by mass of triphenylphosphine as a compound (B) were mixed, and a kneading temperature was obtained using a twin-screw kneading extruder (manufactured by Werner & Pfleiderer, 30 mmφ). Melting and kneading was performed at 250 ° C. for 60 seconds to form a glutaric anhydride unit (A3) to obtain a pellet-shaped resin composition.
Table 3 shows the evaluation results of the obtained resin composition.

[Examples 12 to 16]
Except having changed the kind of compound (B), the usage-amount of a compound (B), and melt-kneading time as shown in Table 3, operation similar to Example 11 was performed and the resin composition was obtained.
Table 3 shows the evaluation results of the obtained resin composition.

[Comparative Example 4]
A resin composition was obtained in the same manner as in Example 11 except that only the precursor (2) was melt kneaded without using the compound (B).
Table 3 shows the evaluation results of the obtained resin composition.

The resin compositions obtained in Examples 11 to 16 were excellent in transparency. In addition, since the resin compositions obtained in Examples 11 to 16 contain units (A3) correspondingly, they are excellent in low water absorption, as a result, the saturated water absorption is decreased, and the heat resistance under water absorption conditions is good. It has become. In addition, silver streaks during molding could be reduced.
The resin composition obtained in Comparative Example 4 contains almost no units (A3), is inferior in low water absorption, and has low heat resistance under water absorption conditions. Further, silver streaks occurred in the molded body.

[Example 17]
100 parts by mass of the precursor (3) obtained in Production Example 3 and 0.1 part by mass of triphenylphosphine as the compound (B) were mixed, and the kneading temperature was determined using a twin-screw kneading extruder (manufactured by Werner & Pfleiderer, 30 mmφ). Melting and kneading was performed at 250 ° C. for 60 seconds to form a glutaric anhydride unit (A3) to obtain a pellet-shaped resin composition.
Table 4 shows the evaluation results of the obtained resin composition.

[Examples 18 and 19]
Except having changed the usage-amount of the compound (B) like Table 4, operation similar to Example 17 was performed and the resin composition was obtained.
Table 4 shows the evaluation results of the obtained resin composition.

[Comparative Example 5]
A resin composition was obtained in the same manner as in Example 17 except that only the precursor (3) was melt kneaded without using the compound (B).
Table 4 shows the evaluation results of the obtained resin composition.

The resin compositions obtained in Examples 17 to 19 were excellent in transparency. In addition, since the resin compositions obtained in Examples 11 to 16 contain units (A3) correspondingly, they are excellent in low water absorption, as a result, the saturated water absorption is decreased, and the heat resistance under water absorption conditions is good. It has become. In addition, silver streaks during molding could be reduced.
The resin composition obtained in Comparative Example 4 contains almost no units (A3), is inferior in low water absorption, and has low heat resistance under water absorption conditions. Further, silver streaks occurred in the molded body. Furthermore, the fluidity of the resin composition was inferior.

The present invention can provide a resin composition having excellent productivity, heat resistance and transparency. Moreover, this invention can provide the manufacturing method of the said resin composition.

Claims (16)

1. A copolymer (A) comprising a methyl (meth) acrylate unit (A1), a (meth) acrylic acid unit (A2) and a glutaric anhydride unit (A3), and a compound (B) represented by the following general formula (1): A resin composition comprising:
   

   

   (R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.)
2. The resin composition according to claim 1, wherein at least one of R ₁ , R ₂ and R ₃ of the compound (B) is an aryl group.
3. The resin composition according to claim 1 or 2, wherein R ₁ , R ₂ and R _{3 of the} compound (B) are each a cyclic alkyl group or an aryl group.
4. The compound (B) is at least one selected from the group consisting of triphenylphosphine, diphenylcyclohexylphosphine, parastyryldiphenylphosphine, tris (4-methoxyphenyl) phosphine and tris (4-fluorophenyl) phosphine. Item 4. The resin composition according to any one of Items 1 to 3.
5. The resin composition according to any one of claims 1 to 4, wherein the content of the compound (B) is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the copolymer (A). .
6. In 100 mol% of copolymer (A), methyl (meth) acrylate units (A1) are 70 mol% or more, (meth) acrylic acid units (A2) are 0.5 mol% or more and 20 mol% or less, glutaric anhydride units ( The resin composition according to any one of claims 1 to 5, wherein A3) is 0.3 mol% or more and 10 mol% or less.
7. The resin composition according to any one of claims 1 to 6, wherein the conversion rate to a glutaric anhydride unit (A3) represented by the following formula (I) is 5% or more and 90% or less.
   Conversion rate to glutaric anhydride unit (A3) (%) = {[ratio of glutaric anhydride unit (A3) in copolymer (mol%)] / ([(meth) acrylic in copolymer Ratio of acid unit (A2) (mol%)] + [Proportion of glutaric anhydride unit (A3) in copolymer (mol%)])} × 100 (I)
8. The resin composition according to any one of claims 1 to 7, wherein the molded piece having a thickness of 2 mm has a haze value of 1 or less.
9. The resin composition according to any one of claims 1 to 8, wherein the melt flow rate at a load of 13.65 kgf and a temperature of 230 ° C is 6 g / 10 min or more.
10. A monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) is polymerized to obtain a precursor, and the resulting precursor and compound (B) represented by the following general formula (1) And a method for producing a resin composition.
    

    

    (R ₁ , R ₂ and R ₃ are each independently hydrogen, linear, branched, cyclic alkyl group or aryl group.)
11. The method for producing a resin composition according to claim 10, wherein the polymerization method is suspension polymerization.
12. The manufacturing method of the resin composition of Claim 10 or 11 whose content of a compound (B) is 0.01 mass part or more and 10 mass or less with respect to 100 mass parts of precursors.
13. The method for producing a resin composition according to any one of claims 10 to 12, wherein the melt-kneading temperature is 150 ° C or higher and 270 ° C or lower.
14. A molded body obtained by molding the resin composition according to any one of claims 1 to 9.
15. A vehicle part including the molded body according to claim 14.
16. A vehicle using the vehicle component according to claim 15.