JP2019077808A - Polymer, graft polymer and thermoplastic resin composition - Google Patents

Abstract

To provide a polymer capable of providing a graft polymer high in graft rate even with moderate crosslinking degree, a graft polymer high in graft rate and suitable as a material of a thermoplastic resin composition providing a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance, and the thermoplastic resin composition capable of providing the molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance.SOLUTION: A polymer obtained by polymerizing a mixture containing following (Aa) component, (Ab) component and (Ac) component. (Aa) component: acrylic acid ester. (Ab) component: a branched allyl ether compound having a hydroxyl group and 2 or more allyl groups, in which all carbon-carbon double bonds contained in the compound are derived from the allyl groups. (Ac) component: a reactive compound having a functional group which may react with a hydroxyl group, and one or more kind of functional group selected from a group consisting of a (meth)acryloyl group, a vinyl group and -CH=CH-.SELECTED DRAWING: None

Description

  The present invention relates to polymers, graft polymers and thermoplastic resin compositions.

Thermoplastic resin compositions such as acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylate (ASA) resin, acrylonitrile-ethylene / propylene / nonconjugated diene copolymer-styrene (AES) resin, etc. It is used in a wide range of fields because molded articles excellent in impact resistance, molding processability, secondary processability (plating, coating, etc.) and surface appearance can be obtained.
The thermoplastic resin composition contains a graft polymer and a thermoplastic resin other than the graft polymer (hereinafter, also referred to as "other thermoplastic resin"). The graft polymer is obtained by graft polymerization of a monomer such as a vinyl monomer which imparts compatibility with other thermoplastic resins to a rubbery polymer (hereinafter, also referred to as "rubbery polymer"). It is a polymer obtained by

  Various rubber polymers are used as the graft polymer, and for example, olefin rubbers such as polybutadiene, polybutadiene-styrene copolymer, silicone rubber, acrylic rubber, ethylene-propylene-diene rubber (EPDM), etc. And composite combs and the like obtained by combining these are known. Among these, acrylic rubber obtained by polymerizing an acrylic ester is widely used because it is excellent in light resistance and chemical resistance of a molded article to be obtained and excellent in economical efficiency.

Since the degree of crosslinking of the rubbery polymer in the graft polymer greatly affects the impact resistance of the resulting molded article, it is important to control the degree of crosslinking of the rubbery polymer to have an appropriate degree of crosslinking. .
For example, it is known that molded articles having excellent impact resistance can be obtained from a thermoplastic resin composition containing a graft polymer using EPDM having a specific degree of crosslinking or an acrylic rubber as a rubbery polymer ( For example, refer to patent documents 1-3).

  In addition, as a method of adjusting the degree of crosslinking of acrylic rubber, when producing acrylic rubber, a polyfunctional compound having two or more (meth) acryloyl groups, vinyl groups, allyl groups and the like in the molecule is used as a crosslinking agent There is known a method of copolymerizing the crosslinker with an acrylic ester.

JP, 2012-224670, A Unexamined-Japanese-Patent No. 2002-284823 JP 2012-214734 A

By the way, in the graft polymer, the graft ratio, which is a ratio of the rubber polymer covered with a polymer of a monomer such as a vinyl monomer, also greatly affects various physical properties of the molded article. Generally, the higher the graft ratio, the better the surface appearance and the thermal stability of the molded article.
Furthermore, when molding the thermoplastic resin composition by injection molding or the like, a defect phenomenon such as a decrease in the molding appearance derived from the deformation of the rubbery polymer is likely to occur particularly in a portion susceptible to shearing such as in the vicinity of the gate. Therefore, in order to eliminate the defect phenomenon, it is sufficient to increase the degree of crosslinking of the rubbery polymer to make it difficult to deform during molding, and to increase the grafting ratio of the graft polymer. As a method of increasing the graft ratio, a method of increasing the amount of addition of the polyfunctional compound used when adjusting the degree of crosslinking of the rubbery polymer is generally used.

However, if the degree of crosslinking of the rubber polymer is increased or the graft ratio of the graft polymer is increased in order to improve the surface appearance, molding appearance, and thermal stability of the molded article, the impact resistance of the molded article decreases. Tend to On the other hand, if the degree of crosslinking of the rubber polymer is made appropriate to improve the impact resistance of the molded article, the graft ratio of the graft polymer decreases, and the surface appearance, the molded appearance and the thermal stability of the molded article It tends to decline.
Thus, it is difficult to control the degree of crosslinking of the rubbery polymer and the degree of grafting of the graft polymer in a high degree, and to achieve both the impact resistance of the molded article, the surface appearance, the thermal stability and the molding appearance. there were.

An object of the present invention is to provide a polymer capable of obtaining a graft polymer having a high graft ratio while having an appropriate degree of crosslinking.
Another object of the present invention is to provide a graft polymer having a high graft ratio, which is suitable as a material of a thermoplastic resin composition from which molded articles excellent in impact resistance, surface appearance, thermal stability and molding appearance can be obtained. I assume.
Another object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance.

The present invention includes the following aspects.
[1] A polymer obtained by polymerizing a mixture containing the following (Aa) component, (Ab) component, and (Ac) component.
Component (Aa): acrylic ester.
Component (Ab): A branched allyl ether compound having a hydroxy group and two or more allyl groups, and all carbon-carbon double bonds contained in the allyl ether compound are derived from the allyl group.
(Ac) Component: A reactive compound having a functional group capable of reacting with a hydroxy group, and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group, and -CH = CH-.
[2] The polymer according to [1], wherein the component (Ab) is at least one member selected from the group consisting of pentaerythritol triallyl ether, pentaerythritol diallyl ether, and trimethylolpropane diallyl ether.
[3] The polymer described in [1] or [2] is at least one selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, N-substituted maleimide and maleic acid Graft polymer obtained by graft polymerizing a monomer.
[4] A thermoplastic resin composition comprising the graft polymer according to [3] and a thermoplastic resin other than the graft polymer.

The polymer of the present invention can obtain a graft polymer having a high graft ratio while having an appropriate degree of crosslinking.
Further, the graft polymer of the present invention is suitable as a material of a thermoplastic resin composition from which a molded article having a high graft ratio and excellent in impact resistance, surface appearance, thermal stability and molding appearance can be obtained.
Moreover, according to the thermoplastic resin composition of the present invention, a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance can be obtained.

Hereinafter, the present invention will be described in detail.
The following definitions of terms apply throughout the present specification and claims.
"Molded article" means what is obtained by molding a thermoplastic resin composition.
"(Meth) acrylic" is a generic term for "acrylic" and "methacrylic".
"(Meth) acrylic acid ester" is a generic term for "acrylic acid ester" and "methacrylic acid ester".

"Polymer"
The polymer of the present invention (hereinafter, also referred to as “polymer (A)”) is a mixture containing the following (Aa), (Ab) and (Ac) components (hereinafter, “mixture (α) It is obtained by polymerizing. That is, the polymer (A) is a polymer of at least the (Aa) component, the (Ab) component and the (Ac) component, and the (Aa) component unit, the (Ab) component unit and the (Ac) component unit Including. The polymer (A) obtained by polymerizing the mixture (α) tends to be rubbery. The mixture (α) is a monomer other than the components (Aa), (Ab) and (Ac) (hereinafter, also referred to as “other monomers”) depending on the physical properties required for the molded article. May be included.
Component (Aa): acrylic ester.
Component (Ab): A branched allyl ether compound having a hydroxy group and two or more allyl groups, and all carbon-carbon double bonds contained in the allyl ether compound are derived from the allyl group.
(Ac) Component: A reactive compound having a functional group capable of reacting with a hydroxy group, and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group, and -CH = CH-.

  In the polymer (A), it is not always easy to specify how the (Aa) component, the (Ab) component and the (Ac) component are polymerized. That is, there are circumstances (impossible / not practical situations) in which it is impossible or almost impossible to directly identify the polymer (A) by its structure or properties. Therefore, in the present invention, it is more appropriate to define the polymer (A) as "obtained by polymerizing a mixture containing the (Aa) component, the (Ab) component, and the (Ac) component". Be done.

<(Aa) component>
The component (Aa) is an acrylic ester.
Examples of the component (Aa) include acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group; and acrylic acid aryl esters having an aromatic hydrocarbon group such as a phenyl group and a benzyl group.
More specifically, as the component (Aa), methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate , Amyl acrylate, isoamyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, pentyl acrylate, phenyl acrylate, benzyl acrylate and the like Be Among these, n-butyl acrylate, 2-ethylhexyl acrylate and ethyl acrylate are preferred in that the polymer (A) tends to be rubbery.
One of these components (Aa) may be used alone, or two or more thereof may be mixed and used.

  The content of the component (Aa) is 80 to 99.9 based on the total (total mass) of the component (Aa), the component (Ab), the component (Ac) and the other monomer in the mixture (α). % By mass is preferable, and 90.1 to 99.8% by mass is more preferable. If the content of the component (Aa) is at least the above lower limit, the impact resistance of the resulting molded article is further improved, and if it is at the above upper limit or less, the impact resistance, surface appearance, thermal stability, The molding appearance is further improved.

<(Ab) component>
The component (Ab) is a branched allyl ether compound having a hydroxy group and two or more allyl groups. All carbon-carbon double bonds contained in the allyl ether compound are derived from an allyl group.
The number of hydroxy groups may be one in one molecule or two or more.

  The component (Ab) can be obtained, for example, by reacting a branched polyol with allyl alcohol. Examples of branched polyols include pentaerythritol, dipentaerythritol, trimethylol ethane and its dimer, trimethylol propane and its dimer, and triethylol propane and its dimer. Among these, pentaerythritol and trimethylolpropane are preferable.

More specifically, examples of the component (Ab) include pentaerythritol triallyl ether, pentaerythritol diallyl ether, and trimethylolpropane diallyl ether. Among these, pentaerythritol triallyl ether is preferable.
One of these (Ab) components may be used alone, or two or more thereof may be mixed and used.

  The content of the component (Ab) is 0.05 to 5 with respect to the total (total mass) of the components (Aa), (Ab), (Ac) and other monomers in the mixture (α). % By mass is preferable, and 0.1 to 2% by mass is more preferable. When the content of the component (Ab) is equal to or more than the above lower limit, the impact resistance, surface appearance, thermal stability and molding appearance of the resulting molded article are further improved, and when it is less than the above upper limit, the resistance of the molded article Impact resistance is further improved.

<(Ac) component>
The (Ac) component is a reactive compound having a functional group capable of reacting with a hydroxy group, and at least one functional group selected from the group consisting of (meth) acryloyl group, vinyl group, and -CH = CH-. is there.

As a functional group capable of reacting with a hydroxy group, for example, an isocyanate group, a thioisocyanate group, an oxirane group, an oxetane group, a carbodiimide group, a carbodiimide group, a silanol group, an oxazoline group, an aziridine group, an epoxy group, a carboxy group, a dicarboxylic acid anhydride group etc. It can be mentioned. Among these, an isocyanate group, an epoxy group, and a dicarboxylic acid anhydride group are preferable in terms of excellent reactivity.
The number of functional groups capable of reacting with a hydroxy group may be one in one molecule, or two or more, and in the case of two or more, the types of functional groups may be the same or different.
Here, a "dicarboxylic acid anhydride group" is a functional group derived from a dicarboxylic acid anhydride, and specifically represented by -CO-O-CO-.

  The number of one or more functional groups selected from the group consisting of (meth) acryloyl group, vinyl group, and -CH = CH- may be one in one molecule, or two or more, or two or more. In the case of, the types of functional groups may be the same or different.

More specifically, examples of the (Ac) component include 2-acryloyloxyethyl isocyanate, 2-methacroyloxyethyl isocyanate, glycidyl acrylate, glycidyl methacrylate, and maleic anhydride. Among these, 2-acryloyloxyethyl isocyanate, glycidyl methacrylate, and maleic anhydride are preferable.
One of these (Ac) components may be used alone, or two or more thereof may be mixed and used.

  The content of the (Ac) component is 0.05 to 5 with respect to the total (total mass) of the (Aa) component, the (Ab) component, the (Ac) component and the other monomer in the mixture (α). % By mass is preferable, and 0.1 to 2% by mass is more preferable. If the content of the component (Ac) is equal to or more than the above lower limit, the impact resistance and surface appearance of the resulting molded article are further improved, and if it is less than or equal to the above upper limit, the impact resistance of the molded article is further enhanced.

<Other monomer>
When the mixture (α) contains other monomers, the polymer (A) contains (Aa) component units, (Ab) component units, (Ac) component units and other monomer units.
The other monomer is not particularly limited as long as it can be copolymerized with the (Aa) component, the (Ab) component and the (Ac) component, and examples thereof include aromatic vinyl, vinyl cyanide, methacrylic acid ester, N-substituted Maleimide and maleic acid can be mentioned.

Examples of the aromatic vinyl include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, p-t-butylstyrene, ethylstyrene and the like.
Examples of vinyl cyanide include acrylonitrile and methacrylonitrile.
Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, and methacrylate Isoamyl acid, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate and the like can be mentioned.
As N-substituted maleimide, N-cyclohexyl maleimide, N-phenyl maleimide etc. are mentioned, for example.
One of these other monomers may be used alone, or two or more thereof may be mixed and used.

  The content of the other monomer is 19.95 mass with respect to the total (total mass) of the (Aa) component, the (Ab) component, the (Ac) component and the other monomer in the mixture (α). Less than% is preferable, and less than 10% by mass is more preferable. If the content of the other monomer is within the above range, the original performance of the polymer (A) is likely to be exhibited.

<Method of producing polymer (A)>
The polymer (A) is produced, for example, by a known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, emulsion polymerization, miniemulsion polymerization and the like. Among these, emulsion polymerization and miniemulsion polymerization are preferable because the particle diameter of the polymer (A) can be easily controlled and the graft polymer described later can be easily produced.

  As a method of producing the polymer (A) by the emulsion polymerization method, a radical initiator, the components (Aa), (Ab), (Ac) and optionally other monomers are added to an aqueous solvent. And copolymerization in the presence of an emulsifying agent. The method of adding the radical initiator, the component (Aa), the component (Ab), the component (Ac) and the other monomer may be batchwise, divided or continuous.

As an emulsifier used for the emulsion polymerization method, an anionic surfactant, nonionic surfactant, an amphoteric surfactant etc. are mentioned, for example.
As the emulsifier, more specifically, sulfates of higher alcohols, alkyl benzene sulfonates, fatty acid sulfonates, phosphates (eg, ammonium monoglyceride phosphate), fatty acid salts (eg, dipotassium alkenyl succinate), Anionic surfactants such as amino acid derivative salts; nonionic surfactants such as alkyl polyethylene glycol alkyl ether type, alkyl ether type, alkyl phenyl ether type, etc. carboxylic acid salt, sulfuric acid ester salt, sulfonic acid salt in the anion part And amphoteric surfactants having a phosphate ester salt and the like and having an amine salt, a quaternary ammonium salt and the like in the cation portion.
One of these emulsifying agents may be used alone, or two or more thereof may be mixed and used.

  10 mass parts or less are preferable with respect to 100 mass parts of mixtures ((alpha)), and, as for the addition amount of an emulsifier, 0.01-10 mass parts is more preferable.

As a radical initiator used in the emulsion polymerization method, known ones can be used. For example, azo polymerization initiator, photo polymerization initiator, inorganic peroxide, organic peroxide, organic peroxide, organic peroxide, transition metal and reducing agent And redox based initiators in combination. Among these, an azo polymerization initiator capable of initiating polymerization by heating, an inorganic peroxide, an organic peroxide, and a redox initiator are preferable.
One of these radical initiators may be used alone, or two or more thereof may be mixed and used.

  As an azo polymerization initiator, for example, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azo Bisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo Formamide, 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis (2-methyl propionate), dimethyl 1,1'-azobis (1-cyclohexane hexacarboxylate) 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (N-butyl-2-methylpropionamide) 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2,4,5 4-trimethylpentane) etc. are mentioned.

  Examples of inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide and the like.

  Examples of the organic peroxide include peroxy ester compounds, and specific examples thereof include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3, 3-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-Butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexano Aate, t-hexylperoxy 2-hexylhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t- Butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluol Nzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2, 2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, α, α '-Bis (t-butylperoxide) diisopropylbenzene, dicumyl peroxide, 2, 5- Methyl-2,5-bis (t-butylperoxy) hexane, t- butyl cumyl peroxide, di -t- butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, etc. t-butyl hydroperoxide and the like.

  The redox initiator is preferably a combination of an organic peroxide and ferrous sulfate, a chelating agent and a reducing agent. For example, those composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate and dextrose, those used in the examples described later, and the like can be mentioned.

  The addition amount of the radical initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the mixture (α).

A chain transfer agent may be added as needed during the production of the polymer (A).
Chain transfer agents include mercaptans such as octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan; allyl sulfonic acid, methallyl sulfonic acid, sodium salts thereof, etc. Allyl compounds of the formula: α-methylstyrene dimer and the like. Among these, mercaptans are preferable from the viewpoint of easy adjustment of molecular weight.
One of these chain transfer agents may be used alone, or two or more thereof may be mixed and used.

The method of adding the chain transfer agent may be batchwise, split or continuous.
2 mass parts or less are preferable with respect to 100 mass parts of mixtures ((alpha)), and, as for the addition amount of a chain transfer agent, 0.01-2 mass parts is more preferable.

In addition, a polymer (A) can be used as composite rubber with the polymer (Hereafter, it is also called "the other rubbery polymer.") Which has rubbers other than a polymer (A).
Other rubbery polymers include, for example, ethylene / propylene rubber (EPR), ethylene / propylene / non-conjugated diene copolymer (EPDM), ethylene-α-olefin copolymer, diene rubber, polyorganosiloxane and the like Be
The composite rubber is obtained, for example, by a known method such as a method of polymerizing the mixture (α) in the presence of another rubbery polymer, a method of co-enlarging the polymer (A) and the other rubbery polymer, Be

<Physical properties>
The swelling degree of the polymer (A) is represented by an increase in the weight of the polymer (A) in which the acetone is not dissolved in acetone, and the higher the degree of swelling, the longer the distance between crosslinking points. It means that the degree is low, and the polymer (A) tends to be a soft rubber. The degree of swelling of the polymer (A) is preferably 6 to 12 times, more preferably 7 to 10 times. If the degree of swelling of the polymer (A) is in the above range, the impact resistance of the resulting molded article tends to be high.
Specifically, the degree of swelling of the polymer (A) can be measured as follows. That is, first, the weighed polymer (A) is immersed in acetone for 20 hours to swell the polymer (A) with acetone until it becomes saturated. Thereafter, the mixture is centrifuged at 14000 rpm to separate into an acetone solution and an insoluble component swollen with acetone, and the mass of the insoluble component swollen with acetone is measured. Next, the insolubles swollen with acetone are vacuum dried, the mass of the dried insolubles is measured, and the degree of swelling of the polymer (A) is determined from the following formula (1).
Degree of swelling (fold) = mass of insoluble matter swollen with acetone (g) / mass of insoluble matter after drying (g) (1)

  The degree of swelling of the polymer (A) can be controlled by adjusting the amounts of the components (Ab) and (Ac) in the production of the polymer (A). For example, when the addition amount of the (Ab) component and the (Ac) component is increased, the degree of swelling decreases. In particular, the degree of swelling tends to decrease as the addition amount of the (Ac) component is increased. The degree of swelling tends to decrease even by increasing the addition amount of the (Ab) component, but the effect is lower than the (Ac) component, and when the addition amount of the (Ab) component is increased, the graft polymer (C) described later The effect of improving the graft ratio of

50-700 nm is preferable, as for the volume average particle diameter of a polymer (A), 80-500 nm is more preferable, and 120-500 nm is more preferable. When the volume average particle diameter of the polymer (A) is at least the above lower limit, the impact resistance and thermal stability of the resulting molded article are further improved, and when it is at the above upper limit or less, the surface appearance of the molded article, molding The appearance tends to be further excellent.
The volume average particle diameter of the polymer (A) can be calculated from the particle diameter distribution obtained by measuring the volume-based particle diameter distribution using a laser diffraction, particle size distribution measuring device of scattering method.

  It does not specifically limit as a method to control the volume average particle diameter of a polymer (A), A well-known method can be used. For example, in the production of the polymer (A), a method of adjusting the addition amount of an emulsifier used at the time of emulsion polymerization or miniemulsion polymerization, a latex of the polymer (A) having a small particle diameter with an acid or acid group-containing copolymer ( There is a method of bloating with the latex of E).

In the case of enlarging with the latex of the acid group-containing copolymer (E), for example, the latex of the acid group-containing copolymer (E) may be mixed with the latex of the small particle polymer (A). At this time, it is more preferable to add a condensation acid salt before mixing the latex of the acid group-containing copolymer (E).
Thus, the polymer (A) of desired volume average particle diameter can be easily obtained by enlarging the polymer (A). Moreover, the ratio of the small particle polymer (A) remaining without enlargement can be reduced by adding the condensed acid salt.

The condensed acid salts include salts of condensed acids such as phosphoric acid and silicic acid and at least one of alkali metals and alkaline earth metals. Among these, a salt of pyrophosphate which is a condensed acid of phosphoric acid and an alkali metal is preferable, and sodium pyrophosphate or potassium pyrophosphate is particularly preferable.
The addition amount of the condensed acid salt is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass, with respect to 100 parts by mass of the solid content of the small particle polymer (A). If the addition amount of the condensed acid salt is in the above range, the enlargement proceeds sufficiently. In particular, when the addition amount of the condensed acid salt is equal to or less than the above upper limit, the stability of the latex is further enhanced, and the generation of a clot can be suppressed.

  The latex of the acid group-containing copolymer (E) is composed of an acid group-containing monomer, a (meth) acrylic acid alkyl ester monomer and, if necessary, other monomers copolymerizable with water. Obtained by polymerizing a monomer mixture containing

As an acid-group containing monomer, the unsaturated compound which has a carboxy group is mentioned, for example, Specifically, (meth) acrylic acid, itaconic acid, crotonic acid etc. are mentioned. Among these, (meth) acrylic acid is particularly preferable.
One of these acid group-containing monomers may be used alone, or two or more thereof may be mixed and used.

Examples of (meth) acrylic acid alkyl ester-based monomers include esters of (meth) acrylic acid and alcohols having a linear or branched alkyl group having 1 to 12 carbon atoms, and specifically, acrylic Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate n -Butyl, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned. Among these, (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms are particularly preferable.
One of these (meth) acrylic acid alkyl ester-based monomers may be used alone, or two or more thereof may be mixed and used.

Another monomer used for producing a latex of the acid group-containing copolymer (E) is a monomer copolymerizable with the acid group-containing monomer and the (meth) acrylic acid alkyl ester type monomer And a monomer excluding an acid group-containing monomer and a (meth) acrylic acid alkyl ester-based monomer.
Other monomers include the other monomers described above in the description of the polymer (A).
One of these other monomers may be used alone, or two or more thereof may be mixed and used.

The ratio of each monomer unit to the total mass of all monomer units constituting the acid group-containing copolymer (E) is as follows.
5-40 mass% is preferable, and, as for the ratio of an acidic radical containing monomer unit, 8-30 mass% is more preferable.
60-95 mass% is preferable, and, as for the ratio of a (meth) acrylic-acid alkylester type monomer unit, 70-92 mass% is more preferable.
48 mass% or less is preferable, and, as for the ratio of another monomer unit, 30 mass% or less is more preferable.
If the ratio of the acid group-containing monomer unit is equal to or more than the above lower limit value, the enlargement capacity becomes better, and if it is equal to or less than the above upper limit value, at the time of producing the latex of the acid group containing copolymer Clumps are less likely to occur.

0 degreeC or less is preferable, and, as for the glass transition temperature of a polymer (A), -80 to 0 degreeC is more preferable. If the glass transition temperature of the polymer (A) is in the above range, the impact resistance of the resulting molded article tends to be further excellent.
The glass transition temperature of the polymer (A) is a value determined by dynamic viscoelasticity measurement (DMTA). Specifically, it is obtained when the temperature is raised from -100 ° C to 5 ° C / min at a frequency of 1 Hz. The temperature at the time of the maximum peak of the tangent loss (tan δ) is defined as the glass transition temperature.

<Function effect>
The polymer (A) of the present invention described above is obtained by polymerizing a mixture (α) containing the (Aa) component, the (Ab) component and the (Ac) component. Therefore, the polymer (A) of the present invention can obtain a graft polymer having a high graft ratio while having an appropriate degree of crosslinking. Although the reason is not clear, it is considered as follows.
The allyl group of the component (Ab) is low in the reactivity of the radical addition reaction, but it tends to cause hydrogen abstraction by radicals and tends to be the initiation point of polymerization. Therefore, when the (Aa) component and the (Ab) component are polymerized, the (Ab) component tends to be the molecular terminal of the polymer of the (Aa) component (that is, polyacrylate), and the hydroxy group of the (Ab) component is It will be present at the molecular end. On the other hand, the (Ac) component tends to cause a radical addition reaction and is easily incorporated into the molecular chain of the polymer of the (Aa) component. Then, the hydroxyl group of the (Ab) component at the molecular end and the functional group capable of reacting with the hydroxyl group among the functional groups of the incorporated (Ac) component in the molecular chain react to form a crosslinked structure Therefore, the proportion of the polymer of the component (Aa) not involved in the crosslinked structure is reduced, and the polymer (A) having an appropriate degree of crosslinking can be obtained.
Further, since the allyl group of the component (Ab) has low reactivity, it is difficult to consume the allyl group at the production of the polymer (A), and the pendant allyl group tends to remain in the polymer (A). Therefore, when using the polymer (A) of this invention for manufacture of a graft polymer, it exists in the tendency for graft polymerization to advance easily by using a pendant allyl group as a polymerization point. Therefore, the graft polymer obtained by using the polymer (A) of the present invention has a high graft ratio.
As described above, by using the (Aa) component, the (Ab) component, and the (Ac) component in combination, a structure having many graft points can be obtained while having an appropriate degree of crosslinking.

"Graft polymer"
The graft polymer of the present invention (hereinafter, also referred to as “graft polymer (C)”) may be added to the polymer (A) of the present invention, such as aromatic vinyl, vinyl cyanide, (meth) acrylate, N- It is obtained by graft polymerization of one or more monomers (hereinafter also referred to as “monomer (B)”) selected from the group consisting of substituted maleimide and maleic acid. That is, the graft polymer (C) is composed of a polymer (A) portion and a polymer (B) portion obtained by polymerizing the monomer (B).

  In addition, in the graft polymer (C), it is difficult to specify how the monomer (B) is polymerized to the polymer (A). For example, as the polymer (B), those bonded to the polymer (A) and those not bonded to the polymer (A) exist. Moreover, it is also difficult to specify the molecular weight of the polymer (B) bonded to the polymer (A), the ratio of the structural units, and the like. That is, there are circumstances (impossible / not practical situations) that it is impossible or almost impossible to directly identify the graft polymer (C) by its structure or properties. Therefore, in the present invention, it is more appropriate to define the graft polymer (C) as “the one obtained by graft polymerization of the monomer (B) to the polymer (A)”.

<Polymer (A)>
Since the polymer (A) is the polymer (A) of the present invention described above, the description thereof is omitted.
A polymer (A) may be used individually by 1 type, and may mix and use 2 or more types.

<Monomer (B)>
The monomer (B) is at least one monomer selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester, N-substituted maleimide and maleic acid.
A monomer (B) can be selected according to the compatibility with the below-mentioned other thermoplastic resin (D), and the objective of a molded article. For example, when aromatic vinyl is used as the monomer (B), moldability tends to be good. If vinyl cyanide is used, the chemical resistance and impact resistance of the molded article, and the compatibility with other thermoplastic resins (D) having polarity can be improved. By using a methacrylic acid ester, the surface hardness and the surface appearance of the resulting molded article can be improved. The heat resistance can be improved by using an N-substituted maleimide.

Examples of the aromatic vinyl, vinyl cyanide and N-substituted maleimide include aromatic vinyl, vinyl cyanide and N-substituted maleimide among the other monomers exemplified above in the description of the polymer (A). Be
Examples of the (meth) acrylic acid ester include the component (Aa) exemplified above in the description of the polymer (A), and methacrylic acid esters among other monomers.
One of these monomers (B) may be used alone, or two or more thereof may be mixed and used.

<Method of producing graft polymer (C)>
The graft polymer (C) is obtained by graft polymerization of the monomer (B) to the polymer (A).
In the graft polymer (C), 40 to 90% by mass of the polymer (A) and 10 to 60% by mass of the monomer (B) (however, the total of the polymer (A) and the monomer (B) is 100) It is preferable that it is what is obtained by graft-polymerizing. The proportion of the polymer (A) is more preferably 45 to 70% by mass, and the proportion of the monomer (B) is more preferably 30 to 55% by mass. If the ratio of the polymer (A) to the monomer (B) is within the above range, the productivity of the thermoplastic resin composition obtained by blending the graft polymer (C) or the graft polymer (C) And the impact resistance, surface appearance and thermal stability of the resulting molded article tend to be further improved.

The method of graft polymerizing the monomer (B) to the polymer (A) is not particularly limited, but the method of polymer (A) production is preferably emulsion polymerization or mini-emulsion polymerization, so emulsion graft polymerization is preferable. Is preferred.
As a method of emulsion graft polymerization, a method of radically polymerizing the monomer (B) in a batch, continuously or intermittently in the presence of the emulsion of the polymer (A) can be mentioned. In addition, at the time of graft polymerization, a chain transfer agent is used for the purpose of controlling the molecular weight of the graft polymer (C) or controlling the grafting rate, or a known inorganic electrolyte or the like for controlling the viscosity or pH of the latex. You may use it. In the emulsion graft polymerization, various emulsifiers and radical initiators can be used as needed.
There are no particular restrictions on the type and amount of chain transfer agent, emulsifier, and radical initiator. Moreover, as a chain transfer agent, an emulsifier, and a radical initiator, the chain transfer agent, the emulsifier, and the radical initiator which were illustrated above in description of a polymer (A) are mentioned.

The graft polymer (C) obtained by emulsion graft polymerization is in the state of being dispersed in an aqueous medium.
As a method for recovering the graft polymer (C) from the aqueous dispersion containing the graft polymer (C), for example, a precipitation agent is added to the aqueous dispersion, heated and stirred, and then the precipitation agent is separated and precipitated. The precipitation method which water-washes, dehydrates, and dries the graft polymer (C) is mentioned.
Examples of the precipitation agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate and the like.
One of these precipitation agents may be used alone, or two or more thereof may be mixed and used.

<Physical properties>
The graft ratio of the graft polymer (C) is preferably 40 to 150%, more preferably 50 to 120%, and still more preferably 60 to 100%. If the graft ratio of the graft polymer (C) is not less than the above lower limit value, the surface appearance, the thermal stability and the molding appearance of the resulting molded article are further improved. On the other hand, if the graft ratio of the graft polymer (C) is not more than the above upper limit value, the productivity of the thermoplastic resin can be favorably maintained. In addition, when the thermoplastic resin composition contains a certain amount of the polymer (A), it is necessary to increase the blending amount of the graft polymer (C), but the blending amount of the graft polymer (C) is Even if the number is increased, the original performance of the thermoplastic resin can be sufficiently exhibited.
The grafting ratio of the graft polymer (C) can be specifically measured as follows. That is, the graft polymer (C) is added to acetone, heated and refluxed at 65 to 70 ° C. for 3 hours, and the obtained suspended acetone solution is centrifuged at 14000 rpm to separate into acetone and acetone insolubles. Do. Subsequently, the acetone insoluble matter is dried under vacuum, and the mass of the acetone insoluble matter after drying is measured, and the graft ratio of the graft polymer (C) is determined from the following formula (2). P in the formula (2) is the mass (g) of the acetone insolubles after drying, and Q is the mass (g) of the polymer (A) used in the production of the graft polymer (C) is there.
Graft ratio (%) = {(P−Q) / Q} × 100 (2)

  The graft ratio of the graft polymer (C) can be controlled by adjusting the addition amount of the (Ab) component and the (Ac) component in the production of the polymer (A). For example, when the polymer (A) produced by increasing the addition amount of the (Ab) component and the (Ac) component is used, the graft ratio of the graft polymer (C) tends to be high. In particular, the grafting ratio tends to increase as the addition amount of the component (Ab) is increased. The grafting ratio tends to increase even by increasing the addition amount of the (Ac) component, but the effect is lower than the (Ab) component, and the polymer (A) swells when the addition amount of the (Ac) component is increased. The effect of reducing the degree is greater. When the addition amount of the (Ac) component is excessively increased in order to increase the graft ratio of the graft polymer (C), the degree of swelling of the polymer (A) is too low, and the impact resistance of the resulting molded article is It may decrease.

<Function effect>
The graft polymer (C) of the present invention described above is obtained by graft polymerization of the monomer (B) onto the above-described polymer (A) of the present invention, and the polymer (A) The part of) has a high degree of grafting while having an appropriate degree of crosslinking. Therefore, the graft polymer (C) of the present invention is suitable as a material of a thermoplastic resin composition from which a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance is obtained.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention comprises the graft polymer (C) of the present invention and a thermoplastic resin other than the graft polymer (C) (hereinafter also referred to as "other thermoplastic resin (D)"). including.
The thermoplastic resin composition of the present invention may contain optional components such as various additives, as needed, as long as the effects of the present invention are not impaired.

<Graft polymer (C)>
The graft polymer (C) contained in the thermoplastic resin composition is the above-described graft polymer (C) of the present invention, and thus the description thereof is omitted.
As the graft polymer (C), one type may be used alone, or two or more types may be used in combination.

<Other Thermoplastic Resin (D)>
There is no restriction in particular as other thermoplastic resin (D), for example, acrylic resin (PMMA), acrylonitrile-styrene copolymer (AS resin), polycarbonate resin, polybutylene terephthalate (PBT resin), methyl methacrylate-styrene copolymer Polymerized resin (MS resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester resin, polyethylene resin, Examples thereof include polypropylene resin, fluorine resin, and polyamide resin (nylon).
One of these other thermoplastic resins (D) may be used alone, or two or more thereof may be mixed and used.

<Optional component>
As various additives, for example, lubricants, pigments, dyes, fillers (carbon black, silica, titanium oxide etc.), heat resisting agents, oxidation deterioration inhibitors, weathering agents, mold release agents, plasticizers, antistatic agents, etc. It can be mentioned.

<Content of each component>
The content of the graft polymer (C) is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass, with respect to the total mass of the graft polymer (C) and the other thermoplastic resin (D). . If content of a graft polymer (C) is more than the said lower limit, the impact resistance of the molded article obtained will be further excellent. On the other hand, when the content of the graft polymer (C) is equal to or less than the above upper limit value, the function originally possessed by the other thermoplastic resin (D) is easily exhibited sufficiently. For example, when an acrylic resin is used as the other thermoplastic resin (D), the hardness of the molded article tends to be high. When a polycarbonate resin is used as another thermoplastic resin (D), the heat resistance of the molded article tends to be high.

  The content of the other thermoplastic resin (D) is preferably 30 to 95% by mass, preferably 50 to 90% by mass, based on the total mass of the graft polymer (C) and the other thermoplastic resin (D). More preferable. If content of another thermoplastic resin (D) is more than the said lower limit, the function which another thermoplastic resin (D) originally has will be fully exhibited easily. On the other hand, if content of other thermoplastic resin (D) is below the said upper limit, the impact resistance of the molded article obtained will be further excellent.

  The total content of the graft polymer (C) and the other thermoplastic resin (D) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, based on the total mass of the thermoplastic resin composition. preferable.

<Method of producing thermoplastic resin composition>
The thermoplastic resin composition can be produced by a known method using a known apparatus, using the graft polymer (C), the other thermoplastic resin (D) and optionally, optional components. For example, a melt mixing method is mentioned as a general method, and an extruder, a Banbury mixer, a roller, a kneader etc. are mentioned as an apparatus used by this method. Either a batch system or a continuous system may be adopted for mixing. Moreover, there is no restriction | limiting in particular also in the order of mixing of each component, etc., and all the components should just be mixed uniformly.
In addition, you may add an arbitrary component, when shape | molding a thermoplastic resin composition.

<Function effect>
The thermoplastic resin composition of the present invention described above contains the above-described graft polymer (C) of the present invention and the other thermoplastic resin (D), so that it has impact resistance, surface appearance, and heat stability. It is possible to obtain a molded article having excellent properties and molded appearance.

"Molding"
A molded article is obtained by molding the thermoplastic resin composition of the present invention by a known molding method.
Examples of the molding method include an injection molding method, an injection compression molding machine method, an extrusion method, a blow molding method, a vacuum molding method, a pressure forming method, a calendar molding method, and an inflation molding method. Among them, injection molding method and injection compression molding method are preferable because they are excellent in mass productivity and can obtain molded products with high dimensional accuracy.
The molded article obtained by the present invention is excellent in impact resistance, surface appearance and thermal stability.

Hereinafter, an Example is shown concretely. However, the present invention is not limited to these examples.
"%" Described below means "mass%", and "part" means "mass part".
The various measurement and evaluation methods in the following examples are as follows.

"Measurement and evaluation"
<Method of measuring volume average particle diameter>
The volume average particle diameter (MV) of the polymer (A) was measured using Microtrac (“Nanotrac 150” manufactured by Nikkiso Co., Ltd.) and pure water as the measurement solvent.

<Method of measuring swelling degree>
The latex of the polymer (A) was coagulated with methanol and sulfuric acid, washed with methanol and then vacuum dried. The dried polymer (A) was weighed and immersed in acetone for 20 hours to swell the polymer (A) with acetone until it became saturated. Thereafter, the mixture was centrifuged at 14000 rpm to separate into an acetone dissolved component and an insoluble component swollen with acetone, and the mass of the insoluble component swollen with acetone was measured. Next, the insolubles swollen with acetone were dried under vacuum, the mass of the insolubles after drying was measured, and the degree of swelling of the polymer (A) was determined from the following formula (1). The higher the degree of swelling, the lower the degree of crosslinking.
Degree of swelling (fold) = mass of insoluble matter swollen with acetone (g) / mass of insoluble matter after drying (g) (1)

<Method of measuring graft rate>
The graft polymer (C) was washed with methanol, added to acetone, and heated under reflux at 65 ° C. for 3 hours. The resulting suspended acetone solution was centrifuged at 14000 rpm to separate into an acetone-dissolved fraction and an acetone-insoluble fraction. Subsequently, the acetone insoluble matter was dried under vacuum, the mass of the acetone insoluble matter after drying was measured, and the graft ratio of the graft polymer (C) was determined from the following formula (2). P in the formula (2) is the mass (g) of the acetone insolubles after drying, and Q is the mass (g) of the polymer (A) used in the production of the graft polymer (C) is there.
Graft ratio (%) = {(P−Q) / Q} × 100 (2)

<Evaluation of impact resistance>
Pellets of the thermoplastic resin composition were molded at 230 ° C. to obtain a molded article (i) having a length of 80 mm, a width of 10 mm and a thickness of 4 mm.
The obtained molded product (i) was subjected to a Charpy impact test (with a V notch having a thickness of 4 mm) at 23 ° C. in accordance with the ISO 179 standard, and the Charpy impact strength was measured.

<Evaluation of surface appearance>
Pellets of the thermoplastic resin composition were injection molded at 230 ° C. and an injection speed of 40 g / sec to obtain a molded article (ii) having a length of 100 mm, a width of 100 mm and a thickness of 2 mm.
About the obtained molded article (ii), the reflectance (%) of the surface of the molded article (ii) at an incident angle of 60 ° and a reflection angle of 60 ° was measured using a gloss meter. The higher the reflectance, the better the surface appearance.

<Evaluation of thermal stability>
After retaining the pellets of the thermoplastic resin composition at 230 ° C. for 20 minutes in an injection molding machine, injection molding of a molded article of 100 mm long, 100 mm wide and 2 mm thickness is continuously performed at 230 ° C. and an injection speed of 40 g / sec. The fifth shot was obtained as a molded article (iii).
About the obtained molded article (iii), the reflectance (%) of the surface of the molded article (iii) at an incident angle of 60 ° and a reflection angle of 60 ° is measured using a gloss meter, and the gloss is maintained from the following formula (3) The rate was determined. The higher the gloss retention, the better the thermal stability.
Gloss retention (%) = (reflectance of molded article (iii) / reflectance of molded article (ii)) × 100 (3)

<Evaluation of molding appearance>
The pellets of the thermoplastic resin composition were injection molded at 230 ° C. and an injection speed of 40 g / sec to obtain a molded article (iv) having a length of 100 mm, a width of 100 mm and a thickness of 2 mm.
Using a colorimeter ("CM-508D" manufactured by Konica Minolta Japan Co., Ltd.), the difference between L ^* in the central part of the obtained molded product (iv) and L ^* in the central part and the gate part (ΔL ^* ) Was measured. From the L ^* and the difference (ΔL ^* ) in the central portion, the molding appearance was evaluated according to the following evaluation criteria. Pass と and 合格.
◎: L ^* ≦ 8 and 0 ≦ ΔL ^* ≦ 0.5, and the molded article (iv) is uniformly black as a whole.
〇: L ^* ≦ 8 and 0.5 <ΔL ^* ≦ 1, and the molded article (iv) is entirely black, but the gate part is somewhat white.
Δ: 8 <L ^* or 1 <ΔL ^* , and the molded article (iv) is entirely white or the gate portion is white.
X: 8 <L ^* and 1 <ΔL ^* , the molded article (iv) is entirely white and the gate portion is whiter.

"Example 1"
<Production of Polymer (A)>
In a reaction vessel equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 300 parts of deionized water, 1 part of dipotassium alkenyl succinate, 0.2 parts of t-butyl hydroperoxide, and (Aa) component 99.2 parts of butyl acrylate as a component, 0.5 parts of pentaerythritol triaryl ether as a component (Ab) and 0.3 parts of 2-acryloyloxyethyl isocyanate as a component (Ac) After substituting for 1 hour, the temperature was raised to 55.degree.
Then, 0.3 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate heptahydrate, 0.0003 parts of disodium ethylenediaminetetraacetate, and 10 parts of deionized water are added to a reaction vessel, The polymerization was started. After the heat of polymerization was confirmed, the jacket temperature was raised to 75 ° C., the polymerization was continued until the heat of polymerization was not confirmed, and the polymer was kept for 1 hour to obtain a latex of the polymer (A1).
The volume average particle diameter of the obtained polymer (A1) was 112 nm, and the degree of swelling was 8 times.

<Production of Graft Polymer (C)>
In a reaction vessel equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 230 parts of deionized water, 50 parts of the latex of the polymer (A1) in terms of solid content, and 0.5% dipotassium alkenyl succinate Parts and 0.3 parts of sodium formaldehyde sulfoxylate were charged, the inside of the reaction vessel was replaced with nitrogen for 1 hour, and the temperature was raised to 70 ° C. while stirring. In addition, the mass of deionized water in the latex of the polymer (A1) is also included in the charged amount of deionized water.
Next, the temperature of the mixture was raised to 80 ° C. while a mixture consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.5 parts of t-butyl hydroperoxide was dropped into the reaction vessel over 100 minutes. After completion of the dropwise addition, the resultant was maintained at 80 ° C. and cooled to obtain a latex of a graft polymer (C1). Next, the latex of the graft polymer (C1) was coagulated with a 1.5% aqueous sulfuric acid solution, dehydrated, washed and dried to obtain a powdery graft polymer (C1).
The graft ratio of the obtained graft polymer (C1) was 73%.

<Production of Thermoplastic Resin Composition>
40 parts of a graft polymer (C1), 60 parts of an acrylonitrile-styrene copolymer ("GM 31B", made by UMG ABS Co., Ltd.) as another thermoplastic resin (D), 1 part of ethylene bis stearylamide, carbon Melt-kneaded black (Mitsubishi Chemical Co., Ltd., “# 960”) and 0.8 parts at 220 ° C. using a twin-screw extruder (“TEX-28V” manufactured by Japan Steel Works, Ltd.) The thermoplastic resin composition of
The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Table 1.

"Example 2"
<Production of acid group-containing copolymer (E)>
200 parts of deionized water, 2 parts of potassium oleate, 4 parts of sodium dioctyl sulfosuccinate, and 0 parts of ferrous sulfate heptahydrate in a reaction container equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. .03 parts, 0.009 parts of disodium ethylenediaminetetraacetic acid, and 0.3 parts of sodium formaldehyde sulfoxylate were charged under a nitrogen stream, and the temperature was raised to 60 ° C. At 60 ° C., a mixture consisting of 82 parts of butyl acrylate, 18 parts of methacrylic acid and 0.5 parts of cumene hydroperoxide was continuously added dropwise over 120 minutes. The mixture was allowed to react at 60 ° C. for 2 hours and cooled to obtain a latex of the acid group-containing copolymer (E). The volume average particle diameter of the obtained acid group-containing copolymer (E) was 150 nm.

<Production of Polymer (A)>
(First stage)
In a reaction vessel equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 240 parts of deionized water, 1 part of dipotassium alkenyl succinate, 0.16 parts of t-butyl hydroperoxide, and (Aa) component Add 79.36 parts of butyl acrylate as a component, 0.4 parts of pentaerythritol triallyl ether as a component (Ab), 0.24 parts of 2-acryloyloxyethyl isocyanate as a component (Ac), and add nitrogen in the reaction vessel After substituting for 1 hour, the temperature was raised to 55.degree.
Then, 0.3 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate heptahydrate, 0.0003 parts of disodium ethylenediaminetetraacetate, and 10 parts of deionized water are added to a reaction vessel, The polymerization was started. After the heat of polymerization was confirmed, the jacket temperature was raised to 75 ° C., the polymerization was continued until the heat of polymerization was not confirmed, and the reaction was allowed to proceed for another hour. To this, 1 part of 5% sodium pyrophosphate aqueous solution in solid content is added, and further, 2.5 parts of solid content of the latex of the acid group-containing copolymer (E) is added and stirred for 30 minutes (bloating step) , Obtained latex.

(2nd stage)
To the resulting latex was added 60 parts of deionized water, 0.03 parts of sodium formaldehyde sulfoxylate, 0.002 parts of ferrous sulfate heptahydrate, and 0.006 parts of disodium ethylenediaminetetraacetate . Next, 19.84 parts of butyl acrylate as the component (Aa), 0.1 parts of pentaerythritol triaryl ether as the component (Ab), 0.06 parts of 2-acryloyloxyethyl isocyanate as the component (Ac) and t-butylhydro A mixed solution consisting of 0.02 part of peroxide was added dropwise over 1 hour and reacted to obtain a latex of the polymer (A2).
The volume average particle diameter of the obtained polymer (A2) was 310 nm, and the degree of swelling was 8 times.

<Production of Graft Polymer (C)>
In a reaction vessel equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 230 parts of deionized water, 50 parts of the latex of the polymer (A2) in terms of solid content, and 0.5% of dipotassium alkenyl succinate Parts and 0.3 parts of sodium formaldehyde sulfoxylate were charged, the inside of the reaction vessel was replaced with nitrogen for 1 hour, and the temperature was raised to 70 ° C. while stirring. In addition, the mass of deionized water in the latex of a polymer (A2) is also included in the preparation amount of deionized water.
Next, the temperature of the mixture was raised to 80 ° C. while a mixture consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.5 parts of t-butyl hydroperoxide was dropped into the reaction vessel over 100 minutes. After completion of the dropwise addition, the resultant was maintained at 80 ° C., and cooled to obtain a latex of a graft polymer (C2). Next, the latex of the graft polymer (C2) was coagulated with a 1.5% aqueous sulfuric acid solution, dehydrated, washed and dried to obtain a powdery graft polymer (C2).
The graft ratio of the obtained graft polymer (C2) was 68%.

<Production of Thermoplastic Resin Composition>
40 parts of a graft polymer (C2), 60 parts of an acrylonitrile-styrene copolymer (“GMS ABS Co., Ltd.,“ AXS resin 202N ”) as another thermoplastic resin (D), and 1 part of ethylene bis stearylamide And 0.8 parts of carbon black ("Mitsubishi Chemical Co., Ltd.,"# 960 ") is melt-kneaded at 220 ° C using a twin-screw extruder (" TEX-28V ", manufactured by Nippon Steel Works, Ltd.) A pellet-like thermoplastic resin composition was obtained.
The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Table 1.

"Example 3"
A polymer (A3) was obtained in the same manner as in Example 2 except that 3 parts of a 5% aqueous solution of sodium pyrophosphate in solid content and 3 parts of a latex of acid group-containing copolymer (E) were used in solid content. . The volume average particle size and the degree of swelling of the polymer (A3) were measured. The results are shown in Table 1.
A graft polymer (C3) was obtained in the same manner as in Example 2 except that the obtained polymer (A3) was used. The grafting rate was measured for the graft polymer (C3). The results are shown in Table 1.
A thermoplastic resin composition was obtained in the same manner as in Example 2 except that the obtained graft polymer (C3) was used. The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Table 1.

"Examples 4 to 6, 8 to 11"
The compounds of the types shown in Tables 1 and 2 as the (Ab) component and the (Ac) component were used, and the preparation amounts of the (Aa) component, the (Ab) component and the (Ac) component were changed as shown in Tables 1 and 2. Polymers (A4) to (A6) and (A8) to (A11) were obtained in the same manner as in Example 2 except for the above. The volume average particle size and the degree of swelling of the polymers (A4) to (A6) and (A8) to (A11) were measured. The results are shown in Tables 1 and 2.
Graft polymers (C4) to (C6) and (C8) to (C11) were prepared in the same manner as in Example 2 except that the obtained polymers (A4) to (A6) and (A8) to (A11) were used. Got). The graft ratio was measured about graft polymer (C4)-(C6) and (C8)-(C11). The results are shown in Tables 1 and 2.
A thermoplastic resin composition was obtained in the same manner as in Example 2 except that the obtained graft polymers (C4) to (C6) and (C8) to (C11) were used. The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Tables 1 and 2.

"Example 7"
The procedure of Example 1 was repeated except that 1 part of dipotassium alkenyl succinate was changed to 1.2 parts of sodium dodecylbenzene sulfonate and 2-acryloyloxyethyl isocyanate was changed to maleic anhydride as the (Ac) component. It obtained union (A7). The volume average particle size and the degree of swelling of the polymer (A7) were measured. The results are shown in Table 1.
A graft polymer (C7) was obtained in the same manner as in Example 1 except that the obtained polymer (A7) was used and the 1.5% aqueous sulfuric acid solution was changed to a 5% aqueous solution of calcium chloride. The grafting rate was measured for the graft polymer (C7). The results are shown in Table 1.
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that the obtained graft polymer (C7) was used. The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Table 1.

"Comparative Examples 1 to 7"
It is carried out except using the types of compounds shown in Table 3 as the (Ab) component and the (Ac) component and changing the preparation amounts of the (Aa) component, the (Ab) component and the (Ac) component as shown in Table 3. In the same manner as in Example 2, polymers (A12) to (A18) were obtained. The volume average particle size and the degree of swelling of the polymers (A12) to (A18) were measured. The results are shown in Table 3.
Graft polymers (C12) to (C18) were obtained in the same manner as in Example 2 except that the obtained polymers (A12) to (A18) were used. The graft ratio was measured about graft polymer (C12)-(C18). The results are shown in Table 3.
A thermoplastic resin composition was obtained in the same manner as in Example 2 except that the obtained graft polymers (C12) to (C18) were used. The impact resistance, the surface appearance, the thermal stability and the molding appearance were evaluated for molded articles obtained by injection molding the obtained thermoplastic resin composition. The results are shown in Table 3.

The abbreviations in Tables 1 to 3 are as follows.
Ab-1: pentaerythritol triallyl ether Ab-2: trimethylolpropane diallyl ether Ab-3: pentaerythritol diallyl ether Ab-4: trimethylolpropane triallyl ether Ab-5: pentaerythritol triacrylate Ab-6: allyl methacrylate, Ac-1: 2-acryloyloxyethyl isocyanate, Ac-2: glycidyl methacrylate, Ac-3: maleic anhydride, Ac-4: butyl isocyanate, Ac-5: 2-hydroxyethyl acrylate

As apparent from Tables 1 and 2, the polymer (A) obtained in each example had a suitable degree of crosslinking. Moreover, the graft polymer (C) obtained using the polymer (A) of each Example had a high graft ratio. Furthermore, the molded articles obtained in each Example were excellent in impact resistance, surface appearance, thermal stability and molded appearance.
Thus, according to the present invention, it is possible to obtain a polymer (A) capable of achieving a high graft ratio when grafted while having an appropriate crosslinked structure.

On the other hand, as apparent from Table 3, although the graft polymer (C) having a high graft ratio was obtained from the polymer (A) of Comparative Example 1 in which the (Ac) component was not used, the polymer (A) The degree of crosslinking was low. Further, the molded product obtained in Comparative Example 1 was inferior in impact resistance.
From the polymer (A) of Comparative Example 2 using branched trimethylolpropane triallyl ether having no hydroxy group as the component (Ab), a graft polymer (C) having a high graft ratio can be obtained. However, the degree of crosslinking of the polymer (A) was low. Moreover, the molded article obtained in Comparative Example 2 was inferior in impact resistance and molding appearance.
From the polymer (A) of Comparative Example 3 using a branched pentaerythritol triacrylate having no allyl group but having an acryloyl group as the component (Ab), a graft polymer having a high graft ratio (C) Was not obtained. Further, the molded article obtained in Comparative Example 3 was inferior in impact resistance, thermal stability and surface appearance.
Polymer of Comparative Example 4 using butyl isocyanate having no one or more functional groups selected from the group consisting of (meth) acryloyl group, vinyl group, and -CH = CH- as the (Ac) component (A Although the graft polymer (C) having a high graft ratio was obtained from the above, the degree of crosslinking of the polymer (A) was low. Moreover, the molded article obtained in Comparative Example 4 was inferior in impact resistance and molding appearance.
From the polymer (A) of Comparative Example 5 using 2-hydroxyethyl acrylate having no functional group capable of reacting with a hydroxy group as the component (Ac), a graft polymer (C) having a high graft ratio is obtained. However, the degree of crosslinking of the polymer (A) was low. Moreover, the molded article obtained in Comparative Example 5 was inferior in impact resistance and molding appearance.
The molded articles obtained in Comparative Examples 6 and 7 in which allyl methacrylate having no hydroxyl group and having one allyl group were used as the (Ab) component and the (Ac) component was not used were the impact resistance and heat resistance. It was not possible to balance stability.
Thus, in the case of each comparative example, it was difficult to increase the graft ratio of the graft polymer (C) while giving the polymer (A) a suitable degree of crosslinking.

  The polymer of the present invention can obtain a graft polymer having a high graft ratio while having an appropriate degree of crosslinking. Therefore, the graft polymer obtained from the polymer of the present invention is suitable as a material of a thermoplastic resin composition from which a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance is obtained. According to the thermoplastic resin composition of the present invention, a molded article excellent in impact resistance, surface appearance, thermal stability and molding appearance can be obtained.

Claims (4)

The polymer obtained by polymerizing the mixture containing the following (Aa) component, (Ab) component, and (Ac) component.
Component (Aa): acrylic ester.
Component (Ab): A branched allyl ether compound having a hydroxy group and two or more allyl groups, and all carbon-carbon double bonds contained in the allyl ether compound are derived from the allyl group.
(Ac) Component: A reactive compound having a functional group capable of reacting with a hydroxy group, and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group, and -CH = CH-.   The polymer according to claim 1, wherein the component (Ab) is at least one member selected from the group consisting of pentaerythritol triallyl ether, pentaerythritol diallyl ether, and trimethylolpropane diallyl ether.   The polymer according to claim 1 or 2 is graft-polymerized with one or more monomers selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester, N-substituted maleimide and maleic acid. Graft polymers obtained by   A thermoplastic resin composition comprising the graft polymer according to claim 3 and a thermoplastic resin other than the graft polymer.