JP6177023B2 - Masterbatch and method for producing resin composition using the same - Google Patents

Description

  The present invention relates to a masterbatch that does not impair the hydrolysis resistance of the resin even when blended with a hydrolyzable resin, and a method for producing a resin composition using the masterbatch.

In recent years, the development of plant-derived materials that do not depend on petroleum resources has been desired due to the growing interest in global environmental problems typified by global warming and the depletion of petroleum resources. This is because carbon neutral, that is, the use of plant-derived materials reduces the amount of oil used, and there is no change in the balance of carbon dioxide (CO ₂ ) in the atmosphere even when it is burned after use. It is based on the concept. Examples of plant-derived materials include polylactic acid-based resins, but their use is expanding from the viewpoint of low heat of combustion during combustion and cost for mass production.

  However, polylactic acid-based resins are easily hydrolyzed, so that there is a problem in water resistance and moist heat resistance of molded products, and improvement of hydrolysis resistance is regarded as a practical problem. In addition, since polylactic acid-based resins are generally hard and brittle materials, improvement in rigidity of polylactic acid-based resin molded products and improvement in mechanical strength such as tensile strength and tensile elastic modulus are also considered as practical issues. Yes.

  For example, Patent Document 1 discloses a biodegradable plastic composition characterized by adjusting a biodegradation rate based on a hydrolysis reaction by blending a biodegradable plastic with a carbodiimide compound.

  Patent Document 2 discloses an aliphatic polyester-based biodegradable resin and a carbodiimide compound having excellent hydrolysis resistance without substantially impairing the biodegradability inherent in the aliphatic polyester-based biodegradable resin. And a disposal method for composting the film.

  Patent Document 3 discloses at least one polyester resin and at least one aromatic monomer carbodiimide as novel persistent bio-based plastics having high hydrolysis resistance, good processability and low level of yellowing. Biobase plastics comprising a combination based on a biobase plastic with a mixture of at least one aromatic oligomer carbodiimide and / or an aromatic polymer carbodiimide, the aromatic polymer carbodiimide and / or aromatic oligomer carbodiimide Biobased plastics with a ratio of aromatic monomer carbodiimide to> 1: 1 are disclosed.

  Patent Document 4 contains polylactic acid, a specific PMMA resin, and a specific ABS resin, which can improve the water resistance and mechanical strength of the molded product in a well-balanced manner and suppress welds during molding. A polylactic acid resin composition is disclosed.

  Patent Document 5 discloses a specific amount of a biodegradable resin, a rubber-reinforced styrene resin, a carbodiimide monomer, which has improved impact resistance and heat resistance of the resin composition and durability under a high temperature and high humidity environment, and A thermoplastic resin composition comprising a carbodiimide polymer is disclosed.

Japanese Patent Laid-Open No. 11-080522 JP 2003-003052 A JP 2012-033691 A JP 2011-246558 A JP 2008-056774 A

  However, even if the above conventional method is used, the hydrolysis resistance of the molded product made of the polylactic acid resin is not sufficiently improved, and the tendency is that a metal oxide is contained in the polylactic acid resin as a colorant or the like. In some cases, it became prominent, and therefore the range of use was limited.

  The present invention has been made in view of the above points, and by providing a masterbatch that does not deteriorate the hydrolysis resistance of a molded product, molding excellent in hydrolysis resistance even when blended with a hydrolyzable resin. The purpose is to be able to manufacture products.

  As a result of earnest research to solve the above problems, the present inventor has found that when an aromatic carbodiimide compound coexists with a metal oxide and is contained in a hydrolyzable resin such as polylactic acid, the hydrolyzable resin is resistant to water. The inventors have found that the decomposability is improved and have completed the present invention.

That is, according to one aspect of the present invention, a master batch containing the following component (A), the following component (B), and the following component (C) is provided.
Component (A): Base resin.
Component (B): an aromatic carbodiimide compound.
Component (C): Metal oxide.

  In the present invention, the term “masterbatch” should be interpreted in a broad sense, and not only a coloring masterbatch prepared for blending a resin with a metal oxide as a colorant but also a metal oxide. A master batch prepared for blending with a resin for purposes other than a colorant such as a filler is also included.

  Moreover, according to the other situation of this invention, the masterbatch of the said invention is mix | blended with the molding resin containing a hydrolyzable resin (D), and the whole resin component 100 derived from the said molding resin and masterbatch 100 The manufacturing method of the resin composition characterized by including the said component (C) 1-30 mass parts with respect to a mass part is provided. The hydrolyzable resin (D) is preferably a polyester resin, and more preferably a polylactic acid resin. The molding resin may be a mixture of a polyester resin and a vinyl resin (E), and is preferably a mixture of a polylactic acid resin and a rubber-reinforced styrene resin from the viewpoint of impact resistance.

  According to the present invention, an aromatic carbodiimide compound is combined with a metal oxide used as a colorant or the like to form a masterbatch, so that this masterbatch is contained in a molding material containing a hydrolyzable resin. Thus, it becomes possible to produce a molded product containing a metal oxide without impairing the hydrolysis resistance. In view of the fact that metal oxides such as titanium oxide have been conventionally considered to promote hydrolysis of hydrolyzable resins, the aromatic carbodiimide compound is used in combination with metal oxides in accordance with the present invention to prevent hydrolysis of the resin. The ability to improve performance is a technical effect that could not be predicted by those skilled in the art. In view of the fact that the hydrolysis resistance of the resin does not improve even when an aliphatic carbodiimide compound and a metal oxide are used in combination, the aromatic carbodiimide compound is used in combination with a metal oxide in accordance with the present invention. It was surprising that the hydrolyzability could be improved.

The present invention will be described in detail below.
In this specification, “(meth) acryl” means acryl or methacryl, “(meth) acrylate” means acrylate or methacrylate, “(meth) acryloyl group” means acryloyl group or methacryloyl group, “Polymer” means a homopolymer or a copolymer.

Component (A): Base resin The base resin is not particularly limited as long as it is a resin that can be mixed with the component (B) and the component (C), and may be any of a hydrolyzable resin and a non-hydrolyzable resin. Well, preferably a thermoplastic resin can be used. As the thermoplastic resin, for example, polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin, polycarbonate resin, polyamide resin, fluorine resin, and vinyl resin can be used. Moreover, when using the masterbatch of this invention for the manufacturing method of the resin composition by this invention, it is preferable that the resin for bases (A) is the same kind of resin as molding resin to mix, or resin with high compatibility. . Therefore, the base resin (A) preferably contains at least one of a hydrolyzable resin (D) and a vinyl resin (E). A polyester resin can be used as the hydrolyzable resin (D). From the viewpoint of production stability of the masterbatch, the base resin (A) is preferably a vinyl resin (E), and selected from the group consisting of the following components (E1), (E2) and (E3). More preferably, it is at least one. When the molding resin contains a polyester resin and a rubber-reinforced styrene resin, an acrylic resin of the following component (E3) having high compatibility with these two resins should be used as the base resin (A). Is also preferable.

Component (B): Aromatic carbodiimide compound The aromatic carbodiimide compound which is the component (B) of the present invention has a carbodiimide group, that is, a compound having at least one group represented by -N = C = N- in one molecule. It is. Such a carbodiimide compound may be any conventionally known compound and is not particularly limited.

  As an aromatic carbodiimide compound, Preferably, the carbodiimide compound shown by following formula (1) is mentioned.

(However, R ¹ and R ² may be the same or different and each represents a monovalent aromatic hydrocarbon group which may have a substituent, and R ³ may be the same or different. It represents a divalent aromatic hydrocarbon group which may have a substituent, and n represents an integer of 0 or more.)

In the formula (1), R ¹ and R ² each represents a monovalent aromatic hydrocarbon group which may have a substituent.

Examples of the monovalent aromatic hydrocarbon group represented by R ¹ and R ² in the formula (1) include an aryl group or an aralkyl group having 6 to 20 carbon atoms, particularly 6 to 14 carbon atoms. Preferable specific examples include phenyl group, benzyl group, phenethyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, A 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, and the like can be given.

  The monovalent aromatic hydrocarbon group described above may have 1 to 4 substituents. Preferable substituents include electron donating groups, and examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms.

Of the monovalent aromatic hydrocarbon groups exemplified as R ¹ and R ² , phenyl group, 2,6-diisopropylphenyl group, and 2,4,6-triisopropylphenyl group are particularly preferable. By using an aromatic carbodiimide compound having these groups in the presence of a metal oxide, the hydrolysis resistance of the hydrolyzable resin is particularly improved.

Preferred examples of the divalent aromatic hydrocarbon group exemplified as R ^{3 in the} formula (1) include an arylene group having 6 to 20 carbon atoms, particularly 6 to 14 carbon atoms. Specifically, o-phenylene group, m-phenylene group, p-phenylene group and the like are preferable.

  Each of the divalent aromatic hydrocarbon groups described above may have 1 to 4 substituents. Preferable substituents include electron donating groups such as linear or branched alkyl groups having 1 to 6 carbon atoms.

Of the above R ³ , particularly preferred are a phenylene group, a 2,6-diisopropylphenylene group, and a 2,4,6-triisopropylphenylene group. By using a carbodiimide compound having these groups in the presence of a metal oxide, the hydrolysis resistance of the hydrolyzable resin is particularly improved.

  In the formula (1), n is an integer of 0 or more, preferably 1 to 1000, more preferably 1 to 100, and still more preferably 5 to 50. When n is an integer of 1 or more, the productivity of the thermoplastic resin composition is excellent.

  Among the aromatic carbodiimide compounds described above, those of n = 0 are bis (2,6-diisopropylphenyl) carbodiimide, tetramethylxylylene carbodiimide, N, N′-dimethylphenylcarbodiimide, N, N Preferred examples include '-di-2,6-diisopropylphenylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-bis (2,2'-6,6'-tetraisopropyldiphenyl) carbodiimide. These may be used alone or in combination of two or more. Among these, bis (2,6-diisopropylphenyl) carbodiimide is particularly preferable.

（式（２）及び（３）中、i-Prはイソプロピル基を表わし、ｎは式（２）の化合物が分子量３０００〜４０００の範囲を満たす値である。） The production of the aromatic carbodiimide compound may be performed according to a conventionally known method. For example, a method of carbodiimidizing a diisocyanate compound by decarboxylation condensation reaction in the presence of a carbodiimidization catalyst in the absence of a solvent or in a predetermined solvent is used. Moreover, as an aromatic carbodiimide compound, a commercial item can be used suitably. Specific examples thereof include trade names “Stabaxol-P” (aromatic polycarbodiimide represented by the following formula (2)) and “Stabaxol-I” (fragment represented by the following formula (3), manufactured by Rhein Chemie. Group monocarbodiimide) and the like.

(In formulas (2) and (3), i-Pr represents an isopropyl group, and n is a value in which the compound of formula (2) satisfies the molecular weight range of 3000 to 4000.)

  Although content of a component (B) will not be specifically limited if it is the quantity which can prevent the hydrolysis of the molding resin mixed with the masterbatch of this invention, Usually, a component (A) was 100 mass parts. In this case, it is preferably 3 to 50 parts by mass, more preferably 4 to 35 parts by mass, and further preferably 5 to 25 parts by mass. When content of a component (B) will be less than 3 mass parts, the improvement of the hydrolysis resistance of the resin composition mixed with the masterbatch of this invention may become inadequate. On the other hand, when the content of the component (B) exceeds 50 parts by mass, the production of the masterbatch may be difficult, or the miscibility of the masterbatch with the molding resin may be reduced.

Component (C): Metal Oxide The metal oxide as the component (C) of the present invention includes magnesium oxide, aluminum oxide, silicon oxide, aluminum oxide / silicon oxide composite, calcium oxide, titanium oxide, vanadium oxide, oxidation. Examples thereof include chromium, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. Of these, an oxide of a Group 4 metal is preferable, and titanium oxide is particularly preferable.

  Titanium oxide particles are not particularly limited as long as they are used as fillers, colorants, and the like, and anatase type, rutile type titanium oxide can be used, but from the viewpoint of thermal stability and weather resistance. Therefore, it is preferable to use rutile type titanium oxide. The volume average particle diameter of the titanium oxide particles is usually 0.01 to 2 μm, preferably 0.05 μm to 1.8 μm, and more preferably 0.1 μm to 1.5 μm. When the volume average particle diameter is less than 0.01 μm, the dispersibility of the titanium oxide particles is deteriorated. In the present invention, the volume average particle diameter of the titanium oxide particles is calculated based on the particle size distribution of primary particles measured with an image diffraction apparatus (for example, Luzex IIIU) based on a transmission electron micrograph. .

  The content of the component (C) in the master batch of the present invention is preferably 5 to 120 parts by mass, more preferably 10 to 110 parts by mass, when the component (A) is 100 parts by mass. More preferably, it is 30-100 mass parts. When content of a component (C) will be less than 5 mass parts, the improvement effect of hydrolysis resistance may become inadequate. On the other hand, when the content of the component (C) exceeds 120 parts by mass, the production of the masterbatch may be difficult, or the miscibility between the masterbatch and the molding resin may be reduced. When component (C) is used as a color pigment, the content of component (C) must be greater than the lower limit in order to achieve sufficient coloration, and the component in the masterbatch of the present invention When (A) is 100 parts by mass, it is preferably 15 to 120 parts by mass, more preferably 25 to 110 parts by mass, and even more preferably 40 to 100 parts by mass. If the content of the component (C) is less than 15 parts by mass, the resulting molded product may be insufficiently colored or the concealability may be insufficient. On the other hand, when the content of the component (C) exceeds 120 parts by mass, the production of the masterbatch may be difficult, or the miscibility between the masterbatch and the molding resin may be reduced.

  Further, the mass ratio of the component (C) to the component (B) (component (C) / component (B)) is preferably 0.1 to 15, more preferably 0.5 to 10, Even more preferably, it is 1.5 to 6.5. When the mass ratio is in this range, the balance between the hydrolysis resistance improving effect of the masterbatch and the mechanical strength of the obtained molded article is good.

  The method for producing a masterbatch of the present invention is not particularly limited as long as the component (B) and the component (C) can be mixed with the base resin (A). For example, the master batch of the present invention is a mixture of the base resin (A), the component (B) and the component (C), and is mixed with a known melt kneader such as a Banbury mixer, roll mill, single screw extruder, twin screw extruder or the like. And kneading.

The master batch of the present invention may contain other additives as long as the effects of the present invention are not impaired. Examples of the additives include impact resistance imparting agents, antioxidants, anti-aging agents, ultraviolet absorbers, weathering stabilizers, plasticizers, fillers, antistatic agents, antibacterial agents, fungicides, and other colorants. Is mentioned.
The master batch of the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired.

Production Method of Resin Composition According to the present invention, a resin composition can be produced by blending a predetermined amount of the master batch of the present invention with a molding resin containing a hydrolyzable resin (D). As a result, although the component (B) and the component (C) are dispersed in the obtained resin composition and the component (C) that is considered to deteriorate the hydrolysis resistance is present, A resin composition with improved degradability can be obtained. Furthermore, it is possible to impart performance such as colorability derived from the component (C) to the molding resin.

Component (D): Hydrolyzable Resin The hydrolyzable resin which is the component (D) of the present invention refers to a polymer whose physical weight is reduced due to a decrease in molecular weight due to cleavage of the main chain by hydrolysis. The component (D) of the present invention can be used without particular limitation as long as it is a resin exhibiting such hydrolyzability. The hydrolyzable resin includes not only a resin that is degraded by microorganisms but also a resin that is degraded by simple chemical (ie, non-enzymatic) hydrolysis without using microorganisms. Examples of such hydrolyzable resins include polyester resins having an ester bond in the main chain (including polycarbonate), polysaccharides having a glycoside bond in the main chain, polyamide resins having an amide bond in the main chain, Examples thereof include a polyether resin having an ether bond and a polyurethane resin having a urethane bond in the main chain. Among these, the masterbatch of the present invention is excellent in hydrolysis resistance when blended with a polyester resin, and a polyester resin is preferably used as the component (D) of the present invention. In the present invention, the polyester resin includes polycarbonate unless otherwise specified.

  As the polyester resin, any of an aliphatic polyester resin and an aromatic polyester resin can be used. In the present invention, an aliphatic polyester resin is preferably used.

  Specific examples of the aliphatic polyester resin include polylactic acid resin, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate, polyethylene succinate, polybutylene succinate carbonate, polyglycolic acid, Examples include polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, hydroxybutyric acid / hydroxyvaleric acid copolymer, and the like. Of these, polylactic acid resins, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate, and polyethylene succinate are preferable, and polylactic acid resin and polybutylene succinate are particularly preferable.

  The polylactic acid-based resin is not particularly limited as long as the main structural unit is an L-lactic acid unit and / or a D-lactic acid unit. The (total) content of these lactic acid units is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.

  In addition, as another structural unit which the said polylactic acid-type resin can contain, the structural unit which has a functional group which can form two or more ester bonds is mentioned, for example, dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid And structural units derived from cyclic esters and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.

  Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. And aromatic polyhydric alcohols such as compounds in which ethylene oxide is added to bisphenol.

  Hydroxycarboxylic acids include glycolic acid, 2-hydroxycaproic acid, 6-hydroxycarboxylic acid, 2-hydroxy-2-methylcaproic acid, 2-hydroxy-2-ethylcaproic acid, 2-hydroxybutyric acid, 2-hydroxy- 2-methylbutyric acid, 2-hydroxy-2-ethylbutyric acid, 4-hydroxybutyric acid, 2-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxyheptanoic acid, 2-hydroxy-2-ethylheptanoic acid, 2-hydroxy Examples include octanoic acid, 7-hydroxyheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxy-2-methylpropionic acid, and 3-hydroxypropionic acid.

  Examples of the cyclic ester include lactone, glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

The molecular weight and molecular weight distribution of the polylactic acid-based resin are not particularly limited as long as the composition has molding processability, but the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). And preferably from 10,000 to 400,000, more preferably from 50,000 to 400,000, and even more preferably from 100,000 to 400,000. The MFR (temperature 190 ° C., load 10 kg) corresponding to Mw is preferably 3 to 100 g / 10 minutes, more preferably 5 to 100 g / 10 minutes, and further preferably 7 to 100 g / 10 minutes.
In the composition of the present invention, the component (D) may be composed of one kind alone, or may be composed of a combination of two or more kinds.

Component (E): Vinyl-based resin The molding resin used in the present invention is a vinyl-based resin which is the component (E) of the present invention in addition to the hydrolyzable resin (D) in order to improve mechanical strength. A resin may be contained.
A preferred specific example of the vinyl resin (E) is a graft copolymer obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl monomer in the presence of the rubber polymer (a). Polymer (E1) (excluding the following component (E3)), (co) polymer (E2) of the vinyl monomer (b2) (excluding the following component (E3)), or acrylic Resin (E3) is mentioned. These components (E1), (E2) and (E3) may be used singly or in combination of two or more. Among these, from the viewpoint of impact resistance, as the molding resin, the above component (E1) or a mixture of the above component (E1) and the above component (E2), that is, a so-called rubber-reinforced styrene resin is used. Is preferred.

  The component (E1) is a graft copolymer obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl monomer in the presence of a rubbery polymer. The component (E1) usually includes a graft component obtained by graft copolymerization of the vinyl monomer (b1) onto the rubber polymer (a) and an ungrafted component that is not grafted onto the rubber polymer (a) (that is, In the same form as the (co) polymer (E2)). The component (E1) may further contain a rubbery polymer (a) in which the vinyl monomer (b1) is not graft-polymerized.

  The rubbery polymer (a) may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C. Furthermore, the rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

The rubbery polymer (a) may be a diene rubber or a non-diene rubber.
Specific examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene and polychloroprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / styrene / Styrene / butadiene copolymer rubber such as butadiene copolymer; Styrene / isoprene copolymer rubber such as styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer; Examples include natural rubber. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The diene rubber can be used singly or in combination of two or more.

  Specific examples of the non-diene rubber include ethylene / α-olefin copolymer rubbers containing ethylene units and α-olefin units having 3 or more carbon atoms; urethane rubbers; acrylic rubbers; silicones Examples include rubbers; silicone / acrylic IPN rubbers; polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds (however, the hydrogenation rate is 50% or more). These copolymers may be block copolymers or random copolymers. The non-diene rubber can be used alone or in combination of two or more.

  The vinyl monomer (b1) contains an aromatic vinyl compound as an essential component. If desired, a vinyl cyanide compound, a (meth) acrylic ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group You may contain 1 type (s) or 2 or more types, such as a containing unsaturated compound, a hydroxyl group containing unsaturated compound, and an oxazoline group containing unsaturated compound.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinyl. And naphthalene. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

  Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like.

  Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- ( 4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the hydroxyl group-containing unsaturated compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy- α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl- 1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p- Vinylbenzyl Arco , 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, etc. In addition, hydroxyalkyl esters of (meth) acrylic acid can be mentioned. Specific examples of hydroxyalkyl esters of (meth) acrylic acid include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 3-hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate And compounds obtained by adding ε-caprolactone to 2-hydroxyethyl (meth) acrylate. These compounds can be used alone or in combination of two or more.

  In the present invention, the vinyl monomer (b1) preferably contains a vinyl cyanide compound in addition to the aromatic vinyl compound.

  The lower limit of the content of the aromatic vinyl compound is preferably 40% by mass, more preferably 50% by mass, and still more preferably 60% by mass when the total amount of the vinyl monomer (b1) is 100% by mass. %. The upper limit is usually 100% by mass.

  In addition, when the vinyl monomer (b1) contains an aromatic vinyl compound and a vinyl cyanide compound, the content of both is, when the sum of both is 100% by mass, moldability and molding From the viewpoint of the heat resistance, chemical resistance and mechanical strength of the product, they are usually 40 to 90% by mass and 10 to 60% by mass, preferably 55 to 85% by mass and 15 to 45% by mass, respectively.

  The method for producing the component (E1) is not particularly limited, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used. In these polymerization methods, appropriate polymerization initiators, chain transfer agents (molecular weight regulators), emulsifiers and the like can be used as appropriate.

  The graft ratio of component (E1) is usually 10 to 150%, preferably 15 to 120%, more preferably 20 to 100%, and particularly preferably 30 to 80%. When the graft ratio of the component (E1) is within the above range, the impact resistance and moldability of the resin composition are favorable, which is preferable.

The graft ratio can be determined by the following mathematical formula (1).
Graft rate (mass%) = ((S−T) / T) × 100 (1)
In the above formula, 1 g of component (E1) is added to 20 ml of acetone (acetonitrile when the rubbery polymer (a) is an acrylic rubber) for 2 hours under a temperature condition of 25 ° C. with a shaker. After shaking, the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate the insoluble matter and the soluble matter. T is the mass (g) of the rubbery polymer (a) contained in 1 gram of the component (E1). The mass of the rubbery polymer (a) can be obtained by a method of calculating from the polymerization prescription and the polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The graft ratio is, for example, the type and amount of chain transfer agent used during the production of component (E1), the type and amount of polymerization initiator, the method and time of addition of monomer components during polymerization, the polymerization temperature, etc. Can be adjusted by appropriately selecting.

  The intrinsic viscosity (30 ° C. in methyl ethyl ketone) of the acetone-soluble component (E1) (acetonitrile-soluble component when the rubbery polymer (a) is an acrylic rubber) is usually 0.1 to 1.5 dl / g, preferably 0.15 to 1.2 dl / g, more preferably 0.15 to 1.0 dl / g. When the intrinsic viscosity of the component (E1) is in the above range, the impact resistance and moldability of the resin composition are favorable, which is preferable.

  The intrinsic viscosity [η] of the acetone-soluble component (E1) (acetonitrile-soluble component when the rubbery polymer (a) is an acrylic rubber) was measured by the following method. First, an acetone-soluble component (E1) (when the rubbery polymer (a) is an acrylic rubber, acetonitrile-soluble component) was dissolved in methyl ethyl ketone to prepare five components having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.

  The intrinsic viscosity [η] is, for example, the type and amount of chain transfer agent used during the production of component (E1), the type and amount of polymerization initiator, the method of adding the monomer component during polymerization, and the addition time. It can adjust by selecting superposition | polymerization temperature etc. suitably. Moreover, it can adjust by selecting suitably and mix | blending the component (E2) which has different intrinsic viscosity [(eta)].

  The component (E2) is a (co) polymer of the vinyl monomer (b2), and is obtained by polymerizing the vinyl monomer (b2) in the absence of the rubbery polymer (a). It is done. As the polymerization method, the method described above for the vinyl monomer (b1) can be used.

  In addition, as the vinyl monomer (b2), any of those described above as the vinyl monomer (b1) can be used. The vinyl monomer (b2) contains an aromatic vinyl compound as an essential component, and was selected from a vinyl cyanide compound and a (meth) acrylic acid ester compound (including a hydroxyalkyl ester of (meth) acrylic acid). It is preferable to contain at least one of them.

  The component (E2) may be a single compound or a mixture of two or more compounds.

  In addition, when the vinyl monomer (b2) contains an aromatic vinyl compound and a vinyl cyanide compound, the content of both is, when the sum of both is 100% by mass, moldability and molding From the viewpoint of the heat resistance, chemical resistance and mechanical strength of the product, they are usually 40 to 90% by mass and 10 to 60% by mass, preferably 55 to 85% by mass and 15 to 45% by mass, respectively.

The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component (E2) is preferably 0.2 to 0.9 dl / g, more preferably 0.25 to 0.5 from the viewpoint of molding processability and impact resistance. 0.85 dl / g, more preferably 0.3 to 0.8 dl / g.
Here, the intrinsic viscosity [η] can be obtained in the following manner.
The above component (E2) is dissolved in methyl ethyl ketone, five different concentrations are prepared, and the reduced viscosity of each concentration solution is measured at 30 ° C. using an Ubbelohde viscosity tube. Desired.

  In the method for producing a resin composition of the present invention, the component (E2) is used by mixing with the component (E1), but the amount of the component (E2) is appropriately selected according to the properties to be imparted to the resin composition. can do. When the component (E) is used, the content of the rubbery polymer (a1) in the resin composition is such that the entire resin component derived from the molding resin and the master batch (usually the components (A), (D) and When the total of (E) is 100% by mass, the amount is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. When the content of the rubbery polymer (a1) is in the above range, the mechanical strength of the molded product made of the resin composition produced in the present invention is further improved.

  In the present invention, when the molding resin comprises a polyester resin and a rubber-reinforced styrene resin, an acrylic resin (E3) having high compatibility with these two resins is used as the vinyl resin (E). It is also preferable to do. The acrylic resin (E3) may be used alone or in combination with the component (D) and another component (E) other than the component (E3).

  Here, the acrylic resin (E3) is generally a structural unit derived from a (meth) acrylic acid ester compound (including a hydroxyalkyl ester of (meth) acrylic acid), based on the entire resin as 100% by mass. Mass%, preferably 80-100% by mass.

  As the (meth) acrylic acid ester compound and the hydroxyalkyl ester of (meth) acrylic acid, all of the above can be used. The acrylic resin (E3) may contain a rubber component, or may be a polymer obtained by graft polymerization of a (meth) acrylic acid ester compound to the rubber component. Preferable specific examples of the acrylic resin (E3) include polymethyl (meth) acrylate (PMMA) and methyl acrylate-butyl acrylate copolymer, which are (co) polymers mainly composed of methyl (meth) acrylate. Can be mentioned.

  The content of the acrylic resin (E3) is the entire resin component derived from the molding resin and the masterbatch (usually component (A), component (D), from the viewpoint of the compatibility of the resin composition and the appearance of the molded product. And the sum of the components (E) is 100% by mass, preferably 10 to 40% by mass, and more preferably 20 to 35% by mass.

  The weight average molecular weight of the acrylic resin (E3) used in the present invention is usually 30,000 to 500,000, preferably 50,000 to 250,000, and more preferably 70,000 to 150,000. If the weight average molecular weight is less than 30,000, the strength of the resulting molded product may be reduced. On the other hand, if it exceeds 300,000, the fluidity of the resin composition may decrease. When two or more kinds of acrylic resins having different molecular weights are used in combination as the acrylic resin (E3), the weight average molecular weight means an average value thereof.

  The content of components (D) and (E) in the resin composition produced in the present invention is the entire resin component derived from the molding resin and masterbatch (usually component (A), component (D) and component ( When the sum of E) is 100% by mass, it is preferably 25 to 100% by mass and 0 to 75% by mass, respectively, and from the viewpoint of mechanical strength, 25 to 55% by mass and 45 to 75% by mass, respectively. It is more preferable that it is 25-40 mass% and 60-75 mass%, respectively. In addition, the content of the component (D) and (E) here includes the amount of the same component derived from the component (A) of the masterbatch.

  The content of the component (C) in the resin composition produced according to the present invention is such that, for example, when a metal oxide such as titanium oxide is used as the white pigment as the component (C), the L value of the molded product is 50 or more. It is preferable that the amount is sufficient, and a master batch of an amount sufficient to contain such an amount of the component (C) in the resin composition may be added to the molding resin.

  In the production method of the present invention, the resin composition can be produced by mixing the masterbatch of the present invention that has been produced in advance and the raw material of the molding resin, and melting and kneading the resin components. . In kneading, conventionally known kneading devices may be used, for example, a twin screw extruder, a single screw extruder, a heatable twin or single screw feeder, a feeder ruder, a Banbury mixer, a roll mill, etc. Can do.

The resin composition obtained by the production method of the present invention is injected into an injection molding apparatus, sheet extrusion molding apparatus, profile extrusion molding apparatus, hollow molding apparatus, compression molding apparatus, vacuum molding apparatus, foam molding apparatus, blow molding apparatus, injection compression. A molded product can be produced by processing with a known molding apparatus such as a molding apparatus, a gas assist molding apparatus, or a water assist molding apparatus.
On the other hand, without producing the resin composition of the present invention before molding, the masterbatch and molding resin are mixed and supplied by an injection molding machine, a sheet extrusion molding machine, etc., and melt-kneaded in the molding machine. It can also be manufactured.
The master batch of the present invention may contain other additives as long as the effects of the present invention are not impaired. Examples of the additives include impact resistance imparting agents, antioxidants, anti-aging agents, ultraviolet absorbers, weathering stabilizers, plasticizers, fillers, antistatic agents, antibacterial agents, fungicides, and other colorants. Is mentioned.

  In the case of producing a sheet-like or film-like molded product with the resin composition obtained in the present invention, a method that can be used for the production of a thermoplastic film, such as a solution casting method, a melt extrusion method, a coextrusion method, a melting method. It can be manufactured by a press method or the like. The melt extrusion method is excellent for large-scale production, but the solution cast method and the melt press method are also useful for small-scale, special purpose, or quality evaluation purposes. In the melt extrusion method, a T-die method or an inflation method is used. In the melt press method, a calendar method is used. The sheet-like or film-like molded article may be a single-layer article or a laminate, but when the molded article is a laminate, it can be produced by, for example, a coextrusion method.

In the T-die method, there is an advantage that it can be produced at a high speed. In that case, the resin temperature at the time of molding is not lower than the melting temperature and lower than the decomposition temperature of the resin, and is generally a temperature of 150 to 250 ° C. Is appropriate.
The specifications and molding conditions of the inflation molding machine are not limited, and conventionally known methods and conditions can be used. For example, the diameter of the extruder is 10 to 600 mm, and the ratio L / D of the diameter D and the length L from the bottom of the hopper to the tip of the cylinder is 8 to 45. The die has a shape generally used for inflation molding, and has a flow path shape such as a spider type, a spiral type, or a stacking type, and has a diameter of 1 to 5000 mm.
As the calender method molding machine, for example, any of a series type, an L type, an inverted L type, a Z type, etc. can be used.

  Further, when the sheet-like or film-like molded product is a laminate, a method of forming a single-layer film by, for example, T-die molding or inflation molding, and then performing thermal lamination or extrusion lamination, a T-die multilayer extruder is used. It can be manufactured by the method used.

When the obtained film or sheet is used as a substrate for a label or an adhesive tape, a corona treatment or various undercoating treatments can be carried out in advance when applying an adhesive. The pressure-sensitive adhesive may be a solvent type, or a solventless type such as an emulsion type, a hot melt type, or an ultraviolet irradiation type. For example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a polyester-based pressure-sensitive adhesive And polyurethane-based pressure-sensitive adhesives.
In addition, in order to provide the designability to the obtained film or sheet, printing by a gravure method, a flexographic method, a silk screen method, etc. can also be performed as needed.

  The obtained film or sheet is, for example, a refrigerator, a washing machine, a vacuum cleaner, a fan, a dryer, an air conditioner, a telephone, an electric kettle, a rice cooker, a dishwasher, a dish dryer, a microwave oven, a mixer, a VTR, and a television. , Watches, stereos, tape recorders, photocopiers, printers, office automation equipment, etc., vehicle-related interior and exterior, sundry items such as housing parts, miscellaneous goods, sanitary goods such as toilets, various medical equipment, various containers, sports equipment, daily necessities, It can be suitably used as a film in the field used for rubber-reinforced styrene-based resin molded products such as building materials, optical equipment, fountain pens, mechanical pencils, ballpoint pens, etc., such as laminate films, labels, or adhesive tape substrates.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In Examples and Comparative Examples, parts and% are based on mass unless otherwise specified.

1. Evaluation Method Measurement methods for various evaluation items in the following Examples and Comparative Examples are shown below.

1-1. It calculated from the composition at the time of raw material preparation of the rubber content of the resin composition .

1-2. Thickness The thickness of the film is measured using a thickness gauge (“ID-C1112C” manufactured by Mitutoyo Corporation), and the film is cut out after 1 hour from the start of film production. Measurements were taken at 10 mm intervals, and the average value was adopted. In addition, the value of the measurement point in the range of 20 mm from the edge part of a film was removed from calculation of the said average value.

1-3. The evaluation by the following criteria were performed at the time of film formation the film film.
Evaluation criteria:
○: A film can be stably formed, and a beautiful film with a uniform surface can be obtained.
X: A film cannot be stably formed, and a beautiful film with a nonuniform surface cannot be obtained.

1-4. Hydrolysis resistance (holding breaking stress)
A test piece of 150 mm (MD) × 15 mm (TD) was cut out from the center in the width direction of the film one hour after the start of film production, and left to stand at a temperature of 85 ° C. and a humidity of 85%, and then an AG2000 tensile tester. (Shimadzu Corporation) was used, and the breaking stress of the test piece was measured based on JIS K7127. The distance between chucks at the time of sample setting was 100 mm, and the tensile speed was 300 mm / min.

The hydrolysis resistance was evaluated according to the following criteria based on the obtained retention rate of the breaking stress. The longer the period during which the breaking stress is maintained, the better the hydrolysis resistance.
Evaluation criteria:
A: The number of days for which the retention rate of the breaking stress can be maintained at 80% or more is 14 days or more.
◯: The number of days that the retention rate of the breaking stress can be maintained at 80% or more is 12 days or more and less than 14 days.
(Triangle | delta): The days which can hold | maintain 80% or more of the retention rate of a rupture stress are 7 days or more and less than 12 days.
X: The number of days that the retention rate of the breaking stress can be maintained at 80% or more is less than 7 days.

2. Production method
2-1. Raw materials used
2-1-1. Production of rubber-reinforced resin (A1-1) A glass flask equipped with a stirrer was charged with 35 parts of ion-exchanged water, 0.25 parts of potassium rosinate, 0.15 parts of tert-dodecyl mercaptan, and average particle diameter in a nitrogen stream. 120 parts of latex containing 48 parts of 300 nm polybutadiene rubber (gel content 80%), 30 parts of latex containing 12 parts of styrene / butadiene copolymer rubber (styrene unit amount 30%) having an average particle diameter of 600 nm, 9 parts of styrene and acrylonitrile 3 parts were accommodated and heated with stirring. When the internal temperature reached 40 ° C., a solution in which 0.15 part of sodium pyrophosphate, 0.007 part of ferrous sulfate heptahydrate and 0.22 part of glucose was dissolved in 5 parts of ion-exchanged water was added. . Thereafter, 0.05 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 30 minutes, 30 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 20 parts of styrene, 8 parts of acrylonitrile, 0.1 part of tert-dodecyl mercaptan and 0.07 part of cumene hydroperoxide were added for 3 hours. Over time. Thereafter, the polymerization was further continued for 1 hour, and 0.15 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and wash it with water. Then, it wash | cleaned and neutralized using potassium hydroxide aqueous solution, Furthermore, after washing with water, it dried and obtained rubber-reinforced resin (A1-1). The rubber-reinforced resin (A1-1) had a graft ratio of 50% and an intrinsic viscosity of acetone-soluble component of 0.35 dl / g.

2-2-1. Production of Acrylonitrile / Styrene Copolymer (A2-1) A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution in which 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, is dissolved in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was carried out at 140 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the acrylonitrile / styrene copolymer. The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acrylonitrile / styrene copolymer (A2-1) was 0.60 dl / g.

2-3-1. Acrylic resin (A3-1)
Acrylic resin “Acrypet VH001” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used. This product is a copolymer of methyl methacrylate and methyl acrylate, and the weight average molecular weight (Mw) by GPC is 97,000.

2-4-1. Polyester (polylactic acid) resin (A4)
As a component (A4), polylactic acid “Ingeo Biopolymer 2003D” (trade name) manufactured by NatureWorks was used. MFR (temperature 210 ° C., load 2.16 kg) is 6 g / 10 min.

2-5-1. Carbodiimide (A5-1)
Aromatic polycarbodiimide “Stabaxol-P” (trade name) manufactured by Rhein Chemie was used.
2-5-2. Carbodiimide (A5-2)
An aromatic monocarbodiimide “Stabaxol-I” (trade name) manufactured by Rhein Chemie was used.
2-5-3. Carbodiimide (A5-3)
An aliphatic polycarbodiimide “LA-1” (trade name) manufactured by Nisshinbo Chemical Co., Ltd. was used.
2-5-4. Carbodiimide (A5-4)
An aliphatic polycarbodiimide “HMV-15CA” (trade name) manufactured by Nisshinbo Chemical Co., Ltd. was used.

2-6-1. Metal oxide (A6-1)
Titanium oxide “Taipeg CR-60-2” (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used. The rutile type had a number average particle size of 0.21 μm.
2-6-2. Metal oxide (A6-2)
Titanium oxide “Typaig CR-58-2” (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used. The rutile type had a number average particle size of 0.28 μm.

2-7-1. Barium sulfate “BARIACE B-30” (trade name) manufactured by Barium Sulfate Chemical Co., Ltd. was used. The number average particle diameter was 0.3 μm.

3. Production of masterbatch The raw materials described in Table 1 or 2 are mixed with a Henschel mixer, and then this mixture is supplied to a twin-screw extruder “BT40” (model name) manufactured by Plastics Engineering Laboratory, melt-kneaded, and pelletized. A master batch was obtained. In addition, the cylinder setting temperature at the time of melt-kneading was 220 degreeC.

4). Production of resin composition and film (Examples 1 to 13 and Comparative Examples 1 to 7)
A film forming machine equipped with a T-die (die width: 1600 mm, lip interval 1 mm) and an extruder with a screw diameter of 115 mm was used, and the masterbatch and molding resin raw materials shown in Table 1 or 2 were used for the extruder. Or it supplied with the compounding quantity shown in 2, and resin was discharged from the T die at the melting temperature of 220 ° C. to obtain a film. Thereafter, the film is brought into close contact with a cast roll (roll surface temperature 70 ° C.) with an air knife, cooled and solidified, and the operating conditions of the extruder and the cast roll are adjusted, whereby the films having the thicknesses described in Table 1 or 2 are used. The film-forming property, hydrolysis resistance, concealing property, color tone, film impact, and heat shrinkage rate were evaluated. The results are shown in Tables 1 and 2.

The following can be seen from the results in Table 1.
Since Examples 1-13 used the masterbatch of the present invention in which an aromatic carbodiimide and titanium oxide were used in combination, the hydrolysis resistance of the resin composition was improved. Conventionally, in view of the fact that when titanium oxide is added alone to a hydrolyzable resin, a phenomenon that promotes hydrolysis of the resin has been observed, when titanium oxide is used in combination with an aromatic carbodiimide according to the present invention, the resistance of the resin composition is reduced. It can be said that the person skilled in the art could never expect that the hydrolyzability was improved. In addition, when titanium oxide is used in combination with aliphatic carbodiimide, the hydrolysis resistance is not improved. On the other hand, it is surprising that the hydrolysis resistance is specifically improved by using in combination with aromatic carbodiimide. Furthermore, the rubber-reinforced styrene resin has an excellent effect of improving hydrolysis resistance despite the possibility that a substance that lowers hydrolysis resistance remains in the production process. Yes.

In contrast, the results in Table 2 show the following.
Comparative Example 1 is an example in which an aliphatic carbodiimide is used alone and has poor hydrolysis resistance. Comparative Examples 2 and 3 are examples in which an aromatic carbodiimide is used alone, and the hydrolysis resistance is poor. Comparative Example 4 is an example in which aromatic carbodiimide and barium sulfate are used in combination, and the hydrolysis resistance is remarkably inferior. Comparative Examples 5 to 6 are examples in which aliphatic carbodiimide and titanium oxide are used in combination, and the hydrolysis resistance is remarkably inferior. Comparative Example 7 is an example in which titanium oxide is used alone, and the hydrolysis resistance is remarkably inferior.

  The masterbatch of the present invention can be suitably used for providing a molding material having excellent hydrolysis resistance in the field of molded products made of a hydrolyzable resin.

Claims (8)

A masterbatch containing the following component (A), the following component (B) and the following component (C) is blended with the molding resin containing the following component (D) or the following component (D) and the following component (E). , 1 to 30 parts by mass of the component (C), 25 to 75.5 parts by mass of the component (D), and 100 parts by mass of the resin component derived from 100 parts by mass of the molding resin and the master batch. 24.5 to 75 parts by mass of (E), the mass ratio of the component (C) to the component (B) (component (C) / component (B)) is 0.1 to 15, and the predetermined amount The component (E) contains a rubber-reinforced styrene-based resin.
Component (A): Base resin containing at least one of the following component (D) and the following component (E).
Component (B): an aromatic carbodiimide compound.
Component (C): Metal oxide.
Component (D): polylactic acid resin .
Component (E): Vinyl resin.   Graft copolymer (E1) obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl monomer in the presence of the rubbery polymer (a). Or the manufacturing method of Claim 1 which is a mixture of the said graft copolymer (E1) and the (co) polymer (E2) of a vinyl-type monomer (b2). The aromatic carbodiimide compound (B) is represented by the following formula (1):

(However, R ¹ and R ² may be the same or different and each represents a monovalent aromatic hydrocarbon group which may have a substituent, and R ³ may be the same or different. It represents a divalent aromatic hydrocarbon group which may have a substituent, and n represents an integer of 0 or more.)
The manufacturing method of Claim 1 represented by these. The production method according to claim 3 , wherein R ¹ and R ² are at least one selected from the group consisting of a phenyl group, a 2,6-diisopropylphenyl group, and a 2,4,6-triisopropylphenyl group. . The production method according to claim 3 or 4 , wherein R ³ is at least one selected from the group consisting of a phenylene group, a 2,6-diisopropylphenylene group, and a 2,4,6-triisopropylphenylene group. The component (C) is The method according to any one of claims 1 to 5 which is an oxide of a group 4 metal. The production method according to claim 6 , wherein the component (C) is titanium oxide. The above masterbatch, when the component (A) is 100 parts by mass, any of claims 1 to 7 containing the above components (B) 3 to 50 parts by weight of the component (C) 5 to 100 parts by weight The manufacturing method according to claim 1.