JP2000355616A - Impact modifier, its production, and resin composition using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an impact modifier which imparts weather resistance by incorporating a liquid compound having a specified viscosity and selected from a hydrocarbon compound, etc., with a copolymer prepared by grafting a vinyl monomer onto a rubber component comprising a plurality of polyalkyl (meth) acrylate rubber components. SOLUTION: This modifier comprises a liquid compound which is liquid at 25 deg.C and has a viscosity of at most 4,000,000 cSt at 25 deg.C and a liquid- compound-containing copolymer having a particle diameter of 0.01-5 μm and obtained by grafting a vinyl monomer onto a liquid compound-containing acrylic rubber component comprising (B) a polyalkyl (meth)acrylate rubber component comprising (A) an alkyl (meth)acrylate monomer and a crosslinking agent and a polyalkyl (meth)acrylate rubber component comprising component A the same as that constituting component B, an alkyl (meth)acrylate monomer which, when homopolymerized, can give a polymer having a Tg higher than that of the (co)polymer of component A, and a crosslinking agent. The liquid compound is selected from a hydrocarbon compound, an ester, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact strength modifier capable of imparting excellent weather resistance, particularly fading resistance and impact resistance, and a resin composition using the same.

[0002]

2. Description of the Related Art Methacrylic resin, polystyrene resin,
There are many known techniques for improving the impact resistance of general-purpose thermoplastic resins such as acrylonitrile / styrene resins and polycarbonates. For example, Tokiko 4-32
No. 5542 discloses a method for improving the appearance of a product while maintaining impact resistance by adding a specific alcohol to a rubber-like polymer latex. Japanese Patent Application Laid-Open No. 10-101869 discloses a rubber composition having a structure in which an isobutylene-based polymer segment and a vinyl polymer segment cannot be separated from each other. Methods for improving the performance have been proposed.

[0003] In addition, vinyl chloride resin is a highly versatile resin, but has a drawback of poor impact resistance. In order to improve the impact resistance, many methods have been proposed.For example, a vinyl chloride resin is mixed with an MBS resin obtained by graft polymerization of methyl methacrylate, styrene or acrylonitrile on a butadiene rubber-like polymer. There is a way to use it. However, when the MBS resin is used in combination with a vinyl chloride resin, the impact resistance is improved, but the weather resistance is reduced, and the impact resistance is significantly reduced when the molded product is used outdoors. It is considered that the main cause of the decrease in weather resistance is due to ultraviolet degradation of the butadiene unit constituting the MBS resin. Then, methyl methacrylate, styrene, acrylonitrile, and the like are graft-polymerized to a crosslinked alkyl (meth) acrylate rubber polymer composed of an alkyl (meth) acrylate and a crosslinker to improve the weather resistance of the MBS resin and improve the impact resistance. The method of imparting is described in JP-B-51-28.
No. 117 has proposed this.

[0004]

However, the impact resistance of general-purpose thermoplastic resins such as methacrylic resin, polystyrene resin, acrylonitrile / styrene resin and polycarbonate is disclosed in Japanese Patent Publication No. 4-325542 and Japanese Patent Application Laid-Open No. The method disclosed in JP 101869 does not achieve high impact resistance. Also, JP-B-51-2811 for improving the impact resistance of vinyl chloride resin.
In the method using the acrylic graft copolymer disclosed in Japanese Patent Publication No. 7, the molded article produced is excellent in weather resistance and has a small decrease in impact resistance, but is added in a large amount in order to develop impact strength. Therefore, there is a problem that the impact strength developing property, especially the impact strength developing property at low temperature is inferior to the MBS resin.

The present invention has been made in view of the above circumstances, and improves the impact resistance of a resin by adding a small amount thereof, especially the low-temperature impact resistance, and also provides the molded article obtained with a fade resistance, an impact resistance and the like. It is an object of the present invention to obtain an impact strength modifier which maintains the weather resistance of the steel.

[0006]

The object of the present invention is to provide a chemical compound represented by a chemical formula C
a hydrocarbon compound including a compound represented by _n H _{(2n + 2)} (where n is an integer), a chemical formula-[(CH ₂ -CH ₂ ) _x (CH ₂
-CHR _a ) _y ]-(where x and y are integers, R _a is H or an alkyl group), a hydrocarbon compound including a compound having a repeating unit represented by the formula:-(CH ₂ -CXCOO)
R _b ) — (where X is H or CH ₃ , R _b is an alkyl group), a compound containing a (meth) acrylate oligomer having a repeating unit represented by the formula: aliphatic monobasic acid ester, aliphatic At least one selected from dibasic acid esters, dihydric alcohol esters, oxyacid esters, phthalic acid esters, phosphoric acid esters, trimetic acid esters, epoxy fatty acid esters, epoxidized oil and fat compounds, and polyorganosiloxane oil compounds A compound which is liquid at 25 ° C. and has a viscosity of 4 at 25 ° C.
A liquid compound [A] containing a compound having a molecular weight of not more than 0,000 cs, an alkyl (meth) acrylate monomer (B _a ), a crosslinking agent and / or a graft crosslinking agent (B
_g ) and the same alkyl (meth) acrylate monomer (B _a ) as that constituting the polyalkyl (meth) acrylate rubber component [B]. ) And the above-mentioned alkyl (meth) acrylate monomer (B
_a ) one or more alkyl (meth) acrylate monomers (C _a ) selected to be above the glass transition temperature of the (co) polymer of ( _a ), and a crosslinking agent and / or a graft cross-linking agent (C _g ) And a polyalkyl (meth) acrylate-based rubber component [C] comprising a liquid compound-containing acrylic rubber component and one or more vinyl-based monomers [D] having an average particle diameter of 0. The problem can be solved by an impact strength modifier characterized by containing a liquid compound-containing graft copolymer having a particle size of from 1 to 5 μm.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The liquid compound [A] used in the present invention has a chemical formula of C _n H
_{(2n + 2)} (where n is an integer) a hydrocarbon compound containing a compound represented by the chemical formula-[(CH ₂ -CH ₂ ) _x (CH
_2- CHR _a ) _y ]-(where x and y are integers, and _Ra is H
Or a hydrocarbon compound containing a compound having a repeating unit represented by the formula (CH ₂ -CXC)
OOR _b ) — (wherein X is H or CH ₃ , R _b is an alkyl group) A compound including a (meth) acrylate oligomer having a repeating unit represented by the formula: aliphatic monobasic acid ester, aliphatic At least one selected from dibasic acid esters, dihydric alcohol esters, oxyacid esters, phthalic acid esters, phosphoric acid esters, trimetic acid esters, epoxy fatty acid esters, epoxidized oil and fat compounds, and polyorganosiloxane oil compounds A compound which is liquid at 25 ° C. and has a viscosity at 25 ° C. of 4,000,000 cs or less.
These compounds can be used alone or in combination of two or more. 60% by weight of these compounds in the liquid compound [A]
It is preferable that the above content be included because the resulting impact strength modifier and the resin composition using the same have excellent impact resistance and weather resistance. The liquid compound [A] may include compounds other than those described above, for example, alkylbenzenes such as ethylbenzene, and ethers as long as these properties are not impaired.
These are preferably contained in a range of less than 40% by weight in the liquid compound [A].

The hydrocarbon compound containing the compound represented by the chemical formula C _n H _{(2n + 2)} (where n is an integer) may be a mixture as long as it contains the compound represented by this chemical formula.
A compound containing 60% by weight or more thereof is preferred. For example, liquid paraffin or the like is used. Chemical formula - [(CH ₂ -C
A hydrocarbon compound including a compound having a repeating unit represented by H ₂ ) _x (CH ₂ —CHR _a ) _y ]-(where x and y are integers, _Ra is H or an alkyl group) A mixture may be used as long as it contains a compound having a unit, but a compound containing 60% by weight or more thereof is preferable. For example, an ethylene-propylene copolymer compound is used. Chemical formula-(CH ₂ -CXCOOR _b )-(where X is H
Or a compound containing a (meth) acrylate oligomer having a repeating unit represented by CH ₃ or R _b is an alkyl group), which includes a low-molecular-weight polymer having the repeating unit, and usually has a molecular weight of 500-800
About 0 is preferable. A mixture of such compounds may be used, but a compound containing 60% by weight or more of a (meth) acrylate oligomer is preferred. Also,
The (meth) acrylate-based oligomer is preferably non-crosslinked. For example, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, 2
Alkyl acrylates such as ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate and hexyl methacrylate;
-Ethylhexyl methacrylate, n-lauryl methacrylate, stearyl methacrylate, and other compounds containing low molecular weight oily polymers (oligomers) of alkyl methacrylate.

In addition, the liquid compound [A] includes butyl oleate and glycerin monooleate as aliphatic monobasic acid esters, and dibutyl sebacate and dibudi-2 sebacate as aliphatic dibasic acid esters.
-Ethylhexyl, diisodecyl succinate, dioctyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dihydric alcohol esters such as diethylene glycol dibenzoate, and oxyacid esters such as methyl acetyl ricinoleate And butyl acetyl ricinoleate. Examples of the phthalate include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, and octyl decyl phthalate. And the like. Phosphate esters include tributyl phosphate, tricresyl phosphate, and the like. There are ter-based compounds, epoxidized oil-based compounds and the like, and other trimetate esters such as trioctyl trimellitate, and polyorganosiloxane-based oil compounds such as dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil, and others. Examples thereof include silicone oils such as modified silicone oils containing organic groups, and liquid polymers mainly containing organosiloxanes, but are not limited to these specific examples.

The compound used as the liquid compound [A] is liquid at 25 ° C. and has a viscosity of 4 at 25 ° C.
It is a compound of not more than, 000,000 cs,
More preferably, it is 000 cs or less. If the viscosity at 25 ° C. exceeds 4,000,000 cs, the impact resistance of the resulting impact strength modifier and the resin composition using the same are undesirably reduced. The compound used for the liquid compound [A] exhibits fluidity, does not exhibit rubber elasticity, and is not an elastomer. These compounds may or may not have a functional group such as an allyl group, an alkoxy group, an acyloxy group, an amino group, an amide group, a mercapto group, an epoxy group, and an alkenyloxy group.

When a compound having a melting point is used as the liquid compound [A], the melting point is preferably 10 ° C. or lower, more preferably 0 ° C. or lower. If the melting point exceeds 10 ° C., the resulting impact strength modifier and the resin composition using the same may sometimes have a low impact strength at low temperatures. When a compound having a pour point is used as the liquid compound [A], the pour point is preferably 15 ° C. or lower. If the pour point exceeds 15 ° C., the resulting impact strength modifier and the resin composition using the same may sometimes have a low impact strength at low temperatures. Furthermore, when a compound having a glass transition temperature is used as the liquid compound [A], the glass transition temperature is preferably 10 ° C. or lower, more preferably 0 ° C. or lower. When the glass transition temperature exceeds 10 ° C., the resulting impact strength modifier and the resin composition using the same may have a low impact strength at low temperatures. When a compound having a boiling point is used as the liquid compound [A], the boiling point at 1013 hPa is preferably 130 ° C. or higher, more preferably 160 ° C. or higher. If the boiling point is lower than 130 ° C,
During molding of the resin composition using the obtained impact strength modifier, the liquid compound [A] may evaporate, resulting in poor appearance of the molded product.

The polyalkyl (meth) used in the present invention
The acrylate rubber component [B] is composed of an alkyl (meth) acrylate monomer (B _a ) and a crosslinking agent and / or a graft crossing agent (B _g ). Examples of the alkyl (meth) acrylate monomer ( _Ba ) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4- Alkyl acrylates such as hydroxybutyl acrylate and hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, alkyl methacrylates such as stearyl methacrylate, and the like, and these can be used alone or in combination of two or more kinds . Among these, it is preferable that at least one of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, n-lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate be a component. . Furthermore, it is more preferable that at least one of 2-ethyl acrylate, n-lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate is a constituent component, and when using stearyl methacrylate or the like having crystallinity near room temperature, Is used by mixing with a monomer that dissolves Further, these alkyl (meth) acrylate monomer (B _a), styrene,
Copolymerization of aromatic alkenyl compounds such as α-methylstyrene and vinyltoluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and various vinyl monomers such as methacryl group-modified silicone in a range of 30% by weight or less. It may be included as a component.

A crosslinking agent and / or a graft crosslinking agent (B)
_g ) includes, for example, crosslinking agents such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and polyfunctional methacryl group-modified silicone. Silicone and the like, as the grafting agent, allyl methacrylate, triallyl cyanurate,
Triallyl isocyanurate and the like can be mentioned. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and / or graft crossing agents (B _g ) can be used alone or in combination of two or more. The total amount of the crosslinking agent and / or the graft crosslinking agent (B _g ) used is preferably 0.001 to 10% by weight in the polyalkyl (meth) acrylate rubber component [B]. If the amount is less than 0.001% by weight, the processability of the resin composition using the obtained impact strength modifier at the time of molding may be reduced, and the appearance of the molded product may be impaired. If it exceeds 10% by weight, the rubber elasticity may be reduced, and the impact resistance of the obtained impact strength modifier and the resin composition using the same may be reduced.

The glass transition temperature of the polyalkyl (meth) acrylate rubber component [B] is preferably lower than that of a homopolymer of n-butyl acrylate. When the glass transition temperature of the polyalkyl (meth) acrylate rubber component [B] is lower than the glass transition temperature of the homopolymer of n-butyl acrylate, the resulting impact strength modifier can impart more impact resistance. preferable. Here, the glass transition temperature of the polymer is measured as a transition point of Tan δ measured by a dynamic mechanical property analyzer (hereinafter, DMA). The glass transition temperature of an n-butyl acrylate homopolymer, which is measured by the presence or absence and degree of crosslinking, varies.Here, the fact that the glass transition temperature is lower than the glass transition temperature of the homopolymer of n-butyl acrylate means that When n-butyl acrylate is used as a component in a component, the glass transition temperature of the component alone is compared with the glass transition temperature of the other component alone. , N-butyl acrylate is preferably lower than the glass transition temperature of the component used, when n-butyl acrylate is not used, the monomer of each component is replaced with n-butyl acrylate, a crosslinking agent Or, when a graft cross-linking agent is used, the mole fraction of these and the monomer to be cross-linked is set to be the same, and polymerization is performed. When comparing the glass transition temperature of each polymer with each other which means that it is preferable to satisfy the above conditions.

The polyalkyl (meth) used in the present invention
The acrylate rubber component [C] was polymerized singly with the same alkyl (meth) acrylate monomer (B _a ) as used to form the polyalkyl (meth) acrylate rubber component [B]. If the B _a (co) polymer a glass transition temperature higher than become so selected alkyl (meth) acrylate monomer and (C _a), consists of a cross-linking agent and / or graft-linking agent (C _g) Is what is done. That is, the polyalkyl (meth) acrylate rubber component [C] is composed of an alkyl (meth) acrylate monomer (B _a ), an alkyl (meth) acrylate monomer (C _a ), a crosslinking agent and / or a graft cross-link. Agent (C
consists _g), and the B _a (co) polymer and C _a (co) when in the polymer were respectively manufactured for measuring the glass transition temperature of each (co) polymer, the B _a (co) C than polymer
_The alkyl (meth) acrylate monomer (C _a ) is selected and used so that the (co) polymer of a has a higher glass transition temperature. If the alkyl (meth) acrylate monomer (B _a ) is not contained in the monomers constituting the polyalkyl (meth) acrylate rubber component [C], the polyalkyl (meth) acrylate rubber component [ B] and the compatibility of the polyalkyl (meth) acrylate rubber component [C] is reduced and the interface is easily peeled off. Therefore, the weather resistance of the resin composition using the obtained impact modifier,
In particular, discoloration due to aging is apt to proceed, which is not preferable. Also, when measuring (co) (co) with polymer produced respectively the glass transition temperature of each (co) polymer of the polymer and C _a of B _a, glass (co) polymer of C _a When (co) polymer a glass transition temperature higher than become as alkyl (meth) acrylate monomer of the transition temperature B _a (C _a) is selected, the impact resistance is preferable to further improved. Such a graft copolymer containing a liquid compound containing the polyalkyl (meth) acrylate rubber components [B] and [C] has a glass transition temperature derived from the component [B] and a glass transition temperature derived from the component [C]. And the glass transition temperature derived from the component [C] is higher than the glass transition temperature derived from the component [B].

As long as these conditions are satisfied, examples of the alkyl (meth) acrylate monomer (C _a ) include methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Alkyl acrylates and hexyl methacrylates such as 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate,
Alkyl methacrylates such as 2-ethylhexyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate and stearyl methacrylate can be used. These may be used alone or as a mixture of two or more, but it is preferable to use n-butyl acrylate because it is particularly excellent in impact resistance.

Polyalkyl (meth) acrylate rubber
Alkyl (meth) acrylate monomer in component [C]
Body (B_a) And an alkyl (meth) acrylate monomer (C
_a)) Is not particularly limited._aAnd C_aThe sum of 1
Alkyl (meth) acrylate
G monomer (B_a) Is preferably 1 to 50% by weight, more preferably
Preferably, the content is 1 to 40% by weight, and the alkyl (meth)
Relate monomer (C_aIs preferably 50 to 99% by weight
And more preferably 60 to 99% by weight. Alkyl
(Meth) acrylate monomer (B_aIs less than 1% by weight
May reduce impact resistance, especially at low temperatures.
Kill (meth) acrylate monomer (C _a) Is 50% by weight
If it is less than 10, the impact resistance may be reduced.

The polyalkyl (meth) acrylate rubber component [C] in the crosslinking agent and / or graft-linking agent as a (C _g) is, [B] used in the component cross-linking agent and / or graft-linking agent (B _g And the like, for example, as a crosslinking agent, ethylene glycol dimethacrylate, propylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4
Silicones such as butylene glycol dimethacrylate, divinylbenzene, and polyfunctional methacrylic group-modified silicones, and the like; graft-crossing agents include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and / or graft crossing agents (C _g ) may be used alone or
More than one species can be used in combination. These crosslinking agents and / or graft-linking agent (C _g), the weight ratio of in the polyalkyl (meth) acrylate rubber component [C], the crosslinking agent and / or graft-linking agent (B _g), polyalkyl It is preferable that the weight ratio is larger than the weight ratio in the (meth) acrylate rubber component [B]. When the amount of the cross-linking agent and / or the graft-linking agent (C _g ) satisfies such a condition, the impact resistance of the obtained impact strength modifier and the resin composition using the same, especially the low-temperature impact resistance Can be improved.

In the acrylic rubber component containing a liquid compound, the content of the liquid compound [A] is preferably 0.001 to 20% by weight, more preferably 0.005 to 15% by weight. If the amount is less than 0.001% by weight, the resulting impact strength modifier and the resin composition using the same may have low impact resistance at low temperatures. If the content exceeds 20% by weight, the resulting impact strength modifier and the resin composition using the same may have reduced impact resistance, or may have a poor appearance when the resin composition is molded. In the liquid compound-containing acrylic rubber component, the ratio of the polyalkyl (meth) acrylate rubber component [B] to the polyalkyl (meth) acrylate rubber component [C] is the sum of the components [B] and [C]. 10
When it is 0% by weight, the component [B] is preferably 1 to 8%.
0% by weight, more preferably 3 to 65% by weight,
Component (C) is preferably 99 to 20% by weight, more preferably 97% to 35% by weight. [B] component is 1% by weight
Below, the impact resistance at a low temperature of the resulting impact strength modifier and a resin composition using the same may be insufficient,
If the component [C] is less than 20% by weight, the weather resistance may deteriorate.

In the acrylic rubber containing a liquid compound comprising the liquid compound [A], the polyalkyl (meth) acrylate rubber component [B], and the polyalkyl (meth) acrylate rubber component [C], The compound [A] may or may not have a chemical bond with the polyalkyl (meth) acrylate rubber components [B] and [C]. It must be at least physically captured. Here, the physically incorporated state includes, for example, a state in which the substance is dispersed in the graft polymer particles, or a state in which a unique domain is formed, and the like. On the other hand, a liquid compound [A] component, a polyalkyl (meth) acrylate rubber component [B], and a polyalkyl (meth)
In the method of simply mixing the acrylate rubber components [C] after they are produced, the liquid compound [A] does not chemically bond to the polyalkyl (meth) acrylate rubber components [B] and [C]. And since it is not physically taken into the acrylic rubber component containing a liquid compound, the resulting impact strength modifier cannot provide impact resistance.

The method for producing the liquid compound-containing acrylic rubber component is, as described above, a method in which the liquid compound [A] is at least physically incorporated into the liquid compound-containing acrylic rubber. Although not particularly limited, usually, an alkyl (meth) acrylate monomer (B _a ) and a crosslinking agent and / or a graft cross-linking agent (B _g ) are emulsion-polymerized in the presence of the liquid compound [A]. A rubber component comprising a liquid compound [A] and a polyacryl (meth) acrylate rubber component [B] is obtained, and then, in the presence of the rubber component, an alkyl constituting a polyacryl (meth) acrylate rubber component [C] is obtained. (meth) acrylate monomer (B _a) and alkyl (meth) acrylate monomer (C _a) and the crosslinking agent and / or graft-linking agent (C _g) and polymerized to a Produced by the method of obtaining a Jo compound-containing acrylic rubber component. Specifically, the liquid compound [A], the alkyl (meth) acrylate monomer (B _a ), and a crosslinking agent and / or a graft cross-linking agent (B _g ) are mixed and then emulsion-polymerized to obtain [A] components and to obtain a rubber component latex consisting of [B] component, the rubber component latex, polyalkyl (meth) acrylate rubber component [C] monomers constituting the component (B _a and C _a) and the crosslinking agent And / or a graft cross-linking agent (C _g ) is added, and the rubber component latex particles of the component (A) and the component (B) are impregnated, and then polymerized by a method in which a usual radical polymerization initiator is allowed to act. .
As the polymerization proceeds, an acrylic rubber latex containing a liquid compound containing a rubber component composed of the components [A] and [B] and a polyalkyl (meth) acrylate rubber component [C] is obtained.

Further, the method of emulsion-polymerizing an alkyl (meth) acrylate monomer (B _a ) and a cross-linking agent and / or a graft cross-linking agent (B _g ) in the presence of the liquid compound [A] is carried out by forced emulsification. Preferably, it is a polymerization method. According to the forced emulsion polymerization method, the liquid compound [A] is likely to be physically taken into the alkyl (meth) acrylate monomer (B _a ) and the crosslinking agent and / or the graft crosslinking agent (B _g ). It is preferred. Further, a liquid compound [A] and a polyacryl (meth) acrylate rubber component [B]
Alkyl (meth) constituting the polyacryl (meth) acrylate rubber component [C] in the presence of a rubber component consisting of
In the method of polymerizing the acrylate monomer (B _a ), the alkyl (meth) acrylate monomer (C _a ), and the crosslinking agent and / or the graft-crosslinking agent (C _g ), the polymerization reaction is carried out after all of them are mixed. It is preferable to use a batch polymerization method. The batch polymerization method is preferred in that a rubber component having more excellent impact resistance can be obtained. The alkyl (meth) acrylate monomers _Ba and C constituting the polyalkyl (meth) acrylate rubber components [B] and [C]
_When at least one of 2-ethyl acrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate is used as a constituent component and is manufactured by emulsion polymerization, these monomers are poor in water solubility, so forced emulsification. The use of a polymerization method is particularly preferred in production.

The impact strength modifier of the present invention comprises a liquid compound-containing graft obtained by graft-polymerizing one or more vinyl monomers [D] to the liquid compound-containing acrylic rubber component obtained as described above. A copolymer is used as a main component. Examples of the vinyl monomer [D] to be graft-polymerized to the liquid compound-containing acrylic rubber component include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methacrylic esters such as methyl methacrylate and 2-ethylhexyl methacrylate; Acrylic esters such as methyl acrylate, ethyl acrylate, and n-butyl acrylate; and various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more. Can be Liquid compound [A] and polyalkyl (meth)
With respect to 100 parts by weight of a liquid compound-containing acrylic rubber component composed of an acrylate rubber component [B] and a polyalkyl (meth) acrylate rubber component [C],
The ratio of graft polymerization of the vinyl monomer [D] is not particularly limited, but is preferably 1 to 60 parts by weight, more preferably 5 to 50 parts by weight. If the amount of the vinyl monomer [D] to be graft-polymerized is less than 1 part by weight, the dispersibility of the graft copolymer in the resin composition may be deteriorated and the processability may be reduced. The strength developability may be significantly reduced.

The impact strength modifier of the present invention comprises the above-mentioned liquid compound-containing graft copolymer as a main component, and the liquid compound-containing graft copolymer has an average particle size of 0.01 to 0.01.
5 μm. When the liquid compound-containing graft copolymer having such an average particle size is used as an impact strength modifier, impact resistance can be imparted even when a small amount of the graft copolymer is mixed with the resin, and the average particle size is preferably 0. If it is less than 01 μm, the impact resistance may decrease, and if it exceeds 5 μm, the weather resistance may deteriorate. Further, the number distribution of the particle diameter of the liquid compound-containing graft copolymer has at least one peak at 0.01 to 0.1 μm, and at least one peak at 0.1 to 0.5 μm. It is preferable to have a bidisperse distribution. Here, the number distribution means a certain particle diameter d _p and d _p + Δ
5 is a distribution showing the number ratio of particles within a minute interval with d _p to all particles in percentage. An impact strength modifier using a graft copolymer containing a liquid compound having such a particle size distribution is preferable because higher impact resistance can be imparted.

The method for producing the liquid compound-containing graft copolymer is as follows: a liquid compound [A], a polyalkyl (meth) acrylate rubber component [B], and a polyalkyl (meth) acrylate rubber component [C]. A method in which a vinyl monomer [D] is graft-polymerized in the presence of the constituted liquid compound-containing acrylic rubber component is preferred. Specifically, a method in which a vinyl monomer [D] is added to the liquid compound-containing acrylic rubber component latex and radical polymerization is performed is preferable. If necessary during polymerization, a known chain transfer agent,
A graft crosslinking agent, a crosslinking agent, and the like may be mixed and used. The liquid compound-containing graft copolymer is poured into a hot water in which a latex containing the same is dissolved in an acid such as sulfuric acid or hydrochloric acid, or a metal salt such as calcium chloride, calcium acetate, or magnesium sulfate, salted out, coagulated and separated. , Which are obtained as particles. Further, it can be obtained by a direct drying method such as a spray drying method.

In the obtained liquid compound-containing graft copolymer, the liquid compound [A] is a polyalkyl (meth)
It is not necessary to have a chemical bond with the acrylate rubber components [B] and [C], but it is necessary to have a chemical bond with the vinyl monomer [D]. It is necessary that the liquid compound [A] be in a state of being physically incorporated at least in the liquid compound-containing gract copolymer. As described above, when the liquid compound [A] is in a state of being incorporated into the graft copolymer containing the liquid compound, the obtained impact modifier can provide high impact resistance. The graft copolymer containing a liquid compound obtained by the above method is used by being blended with a thermoplastic resin such as a hard vinyl chloride resin (PVC resin) as an impact strength modifier.

The thermoplastic resin to which the impact strength modifier is blended is not limited to hard vinyl chloride resin (PVC resin). For example, semi-rigid, soft vinyl chloride resin (PVC resin), polypropylene (PP) , Polyethylene (P
E) and other olefin resins (olefin resins), polystyrene (PS), high impact polystyrene (H
IPS), (meth) acrylate / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SM)
A), styrene resin (St resin) such as ABS, ASA, AES, etc., polymethyl methacrylate (PMMA)
Acrylic resin (Ac resin), polycarbonate resin (PC resin), polyamide resin (PA resin), polyester resin (PEs resin) such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) ), (Modified) polyphenylene ether resin (PPE resin), polyoxymethylene resin (POM resin), polysulfone resin (PSO resin), polyarylate resin (PAr resin), polyphenylene resin ( Engineering plastics such as PPS resin), thermoplastic polyurethane resin (PU resin), styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, Thermoplastic elastomers (TPE) such as elementary elastomers, 1,2-polybutadiene, trans 1,4-polyisoprene, and PC resins such as PC / ABS / St resin alloys and PVC resins such as PVC / ABS / St resin alloy, PA resin such as PA / ABS / St resin alloy, PA resin / TP
E alloy, PA resin such as PA / PP / Polyolefin resin alloy, PBT resin / TPE, PC / PBT
PC-based resin / PEs-based resin alloy, polyolefin-based resin / TPE, alloy of olefin-based resins such as PP / PE, PPE / HIPS, PPE / PBT,
PPE resin alloys such as PPE / PA, PVC / PM
It can be used for polymer alloys such as PVC-based resin / Ac-based resin alloy such as MA, and can also be suitably used for hard PVC-based resin, but the present invention is not limited only to such specific examples. .

When the impact strength modifier of the present invention is incorporated into a thermoplastic resin, as long as the physical properties are not impaired, a conventional stabilizer may be used at the time of compounding, kneading and molding the resin according to the purpose. Fillers and the like can be added. Examples of the stabilizer include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; and metals such as potassium, magnesium, barium, zinc, cadmium, and lead. And 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid,
Metallic soap-based stabilizers derived from fatty acids such as ricinoleic acid, linoleic acid, and behenic acid, organic tin-based stabilizers derived from alkyl groups, ester groups and fatty acid salts, maleates, and sulfide-containing compounds, Ba-Zn System, Ca-Zn system, Ba-
Ca-Sn system, Ca-Mg-Sn system, Ca-Zn-Sn
, Pb-Sn-based, Pb-Ba-Ca-based composite metal soap-based stabilizers, metal groups such as barium and zinc and branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid and trialkylacetic acid, oleic acid and ricinoleic acid Metal salts based on usually two or more organic acids, such as unsaturated fatty acids such as linoleic acid, aliphatic acids such as naphthenic acid, and aromatic acids such as phenolic acid, benzoic acid, salicylic acid and their substituted derivatives Dissolving these stabilizers in petroleum hydrocarbons, alcohols, organic solvents such as glycerin derivatives, and further phosphites, epoxy compounds, anti-coloring agents,
In addition to metal-based stabilizers such as metal salt liquid stabilizers that are formulated with stabilizing aids such as transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, and lubricants, epoxy resins,
Epoxy compounds such as epoxidized soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl ester, and the like, in which phosphorus is substituted with an alkyl group, aryl group, cycloalkyl group, alkoxyl group, etc.
Organic phosphite having an aromatic compound such as polyhydric alcohol, hydroquinone, bisphenol A, BHT
UV absorbers such as hindered phenols such as bisphenols dimerized with sulfur or methylene groups, salicylic acid esters, benzophenone, benzotriazole, light stabilizers of hindered amines or nickel complex salts,
UV shielding agents such as carbon black and rutile titanium oxide; polyhydric alcohols such as trimerol propane, pentaerythritol, sorbitol and mannitol; β-
Aminocrotonate, 2-phenylindole,
Nitrogen-containing compounds such as diphenylthiourea and dicyandiamide, sulfur-containing compounds such as dialkylthiodipropionate, acetoacetate, dehydroacetic acid, β-
Non-metallic stabilizers such as keto compounds such as diketones, organic silicon compounds, and borate esters are used, and these are used alone or in combination of two or more.

Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate and colloidal calcium carbonate, titanium oxide, clay, talc, mica, silica, carbon black, graphite, glass beads, and the like.
Examples include inorganic fibers such as glass fibers, carbon fibers, and metal fibers, organic fibers such as polyamide, organic materials such as silicone, and natural organic materials such as wood flour.

Others, MBS, ABS, AES, NB
R, EVA, impact strength modifiers such as chlorinated polyethylene, acrylic rubber, polyalkyl (meth) acrylate rubber-based graft copolymers, thermoplastic elastomers, and processing aids for (meth) acrylate-based copolymers Agents, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, alkyl esters of aromatic polybasic acids such as pyromet, dibutyl adipate, dioctyl adipate, disiononyl adiate Alkyl esters of fatty acid polybasic acids such as peat, dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphate esters such as tricresyl phosphate, adipic acid, azelaic acid, Molecular weight of polyhydric carboxylic acids such as basic acid and phthalic acid and polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol Polyester plasticizers such as polycondensates of about 600 to 8,000 whose ends are sealed with monohydric alcohol or monocarboxylic acid, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2 -Epoxy plasticizers such as ethylhexyl, plasticizers such as chlorinated paraffin, liquid paraffin, pure hydrocarbons such as low molecular weight polyethylene, halogenated hydrocarbons, higher fatty acids, fatty acids such as oxy fatty acids, fatty acid amides such as fatty acid amides, Polyhydric alcohol esters of fatty acids such as glycerides, fatty alcohols of fatty acids Ester (ester wax), metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, ester such as fatty acid and polyglycol, partial ester of polyglycerol, (meth) acrylic acid Ester copolymers and other such lubricants, chlorinated paraffins, aluminum hydroxide, antimony trioxide, flame retardants such as halogen compounds, (meth)
Heat-resistant improvers such as acrylate-based copolymers, imide-based copolymers, styrene-acrylonitrile-based copolymers, release agents, crystal nucleating agents, fluidity improvers, coloring agents, antistatic agents, and conductivity imparting Agents, surfactants, antifogging agents, foaming agents, antibacterial agents and the like can be added.

The impact strength modifier of the present invention is blended with a resin,
The method for producing the resin composition is not particularly limited, and an ordinary method can be used, but it is usually preferable to produce the resin composition by a melt mixing method. Moreover, you may use a small amount of solvent as needed. Examples of an apparatus to be used include an extruder, a Banbury mixer, a roller, a kneader, and the like, which are operated batchwise or continuously. The order of mixing the components is not particularly limited. In addition, the obtained resin composition is not limited in its use, for example, building materials, automobiles, toys, stationery and other miscellaneous goods, as well as OA equipment, home appliances and other molded products that require impact resistance, etc. Used.

[0032]

The present invention will be described in more detail with reference to the following examples and comparative examples. "Parts" in the description is "parts by weight"
Is shown. Reference Example 1 Production of Liquid Compound-Containing Graft Copolymer (1) Ethylene-α-olefin Cooligomer: Lucant H
C-100 (manufactured by Mitsui Chemicals, viscosity at 25 ° C. is 10
0.15 parts), allyl methacrylate 0.
15 parts of 2-ethylhexyl acrylate monomer containing 5% by weight and 0.075 part of tertiary butyl hydroperoxide were mixed to obtain a (meth) acrylate monomer mixture. 0.18 dipotassium alkenyl succinate
The above (meth) acrylate monomer mixture was added to 30 parts of distilled water in which
m, and then 300 kg with a homogenizer.
The emulsion was emulsified and dispersed at a pressure of / cm ² to obtain a liquid compound-containing (meth) acrylate emulsion. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and heated to 70 ° C. while replacing with nitrogen and mixing and stirring. When the temperature reached 70 ° C., 0.0003 parts of ferrous sulfate and disodium ethylenediaminetetraacetate 0.1% were added. After adding a mixture of 0009 parts, 0.039 parts of Rongalite and 0.75 parts of distilled water, the mixture was allowed to stand at 70 ° C. for 5 hours to complete the polymerization, and then cooled, and the components [A] and [B] A latex of a liquid compound-containing acrylic rubber (1-ABLx) was obtained.
The resulting liquid compound-containing acrylic rubber latex (1
-ABLx) was 99.7%, and the average particle size was 0.19 μm. The latex was coagulated and dried with ethanol to obtain a solid, which was then heated at 90 ° C.
Extraction was performed for 2 hours, and the gel content was measured to be 90.4% by weight.

The total amount of distilled water was 29% with respect to the liquid compound-containing acrylic rubber latex (1-ABLx).
5 parts, the mixture was purged with nitrogen, and then heated to 50 ° C., containing 2% by weight of allyl methacrylate as a component of the polyacryl (meth) acrylate rubber component, which is the component C of the present invention. -74 parts of an acrylate monomer mixture prepared such that the ratio of ethylhexyl acrylate to n-butyl acrylate is 10:64,
0.345 part of tertiary butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed solution was permeated into latex (I-ABLx) particles of a liquid compound-containing acrylic rubber. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization. The polymerization was completed by holding for a time, and a latex of a liquid compound-containing acrylic rubber (I-component) comprising the components [A], [B] and [C] was used.
ABCLx). A part of this latex was collected and the average particle diameter of the polyalkyl (meth) acrylate rubber was measured to be 0.22 μm. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 97.3% by weight.

To this liquid compound-containing acrylic rubber latex (1-ABCLx) was added 0.04 part of tertiary butyl hydroperoxide and methyl methacrylate 11
The mixture was added dropwise at 70 ° C. for 15 minutes and then kept at 70 ° C. for 4 hours to complete the graft polymerization onto the polyalkyl (meth) acrylate rubber. The polymerization rate of methyl methacrylate was 97.6%. The obtained graft copolymer latex was treated with calcium chloride 1.5
The solution was dropped into 200 parts by weight of hot water of 200% by weight, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain 98.9 parts of a powdery liquid compound-containing graft copolymer (1). This liquid compound-containing graft copolymer (1) has an average particle size of 0.1.
8 μm, and the number distribution of particle diameters was 0.08 μm and 0.1 μm.
It was a bidisperse distribution having a peak at 24 μm. Table 1 shows the compositions of the components [A] to [D] constituting the liquid compound-containing graft copolymer (1) in parts by weight. In addition, physical property evaluation was performed as follows. -Measurement of particle size distribution of the liquid compound-containing graft copolymer (1) The particle size distribution was measured using a particle size distribution measuring device CHDF-2000 manufactured by MATEC APPLIED SCIENCE. The measurement was performed under standard conditions recommended by MATEC.
Using a dedicated capillary cartridge for particle separation and a carrier liquid, the liquidity is almost neutral, and the flow rate is 1.4 ml /
0.1 ml of a diluted latex sample having a concentration of about 3% while maintaining the pressure at about 4000 psi and the temperature of 35 ° C. min.
Was used for the measurement. In addition, US DU as a standard particle size substance
0.02 monodisperse polystyrene manufactured by KE with a known particle size
A total of 12 points were used within the range of μm to 0.8 μm.

(Reference Examples 2 to 6, 13 to 18) Production of graft copolymers containing liquid compounds (2 to 6, 13 to 18) [A] component, [B] component, [C] component, [D] Components shown in Tables 1 and 2 are shown in Tables 1 and 2 respectively.
The liquid compound-containing graft copolymers (2-6, 13-
18). The particle diameter of the liquid compound-containing graft copolymer (2 to 6, 13 to 18) was measured in the same manner as in Reference Example 1. The results are shown in Tables 3 to 5 together with the results of the examples using these. The viscosity at 25 ° C. of the substance used as the liquid compound [A] is as follows. Lucant HC-20: 100cs Epoxidized soybean oil: 800cs Dioctyl phthalate: 100cs

Reference Example 7 Production of Graft Copolymer (7) 10 parts of n-butyl acrylate containing 1% by weight of allyl methacrylate and 0.12 part of tert-butyl hydroperoxide were mixed, and (meth) acrylate A monomer mixture was obtained. In a separable flask equipped with a condenser and a stirring blade, sodium dodecylbenzenesulfonate, which was purged with nitrogen while mixing and stirring, was added in an amount of 0.01%.
To 245 parts of partially dissolved distilled water was added 0.002 ferrous sulfate.
Parts, disodium ethylenediaminetetraacetate 0.006
, A mixture of 0.26 parts of Rongalite and 5 parts of distilled water, and then the temperature was raised to 60 ° C., and the above (meth) acrylate monomer mixture was added dropwise over 3 hours. Was completed to obtain a latex of poly (meth) acrylate. The polymerization rate of the resulting poly (meth) acrylate latex was 99.5%, and the average particle size was 0.20 μm. A solution consisting of 0.99 parts of sodium dodecylbenzenesulfonate and 55 parts of distilled water, 70 parts of n-butyl acrylate containing 1% by weight of allyl methacrylate, and tert-butyl hydroperoxide are added to the poly (meth) acrylate latex. 0.22
And a (meth) acrylate mixed solution, which is a component of poly (meth) acrylate, was simultaneously dropped for 3 hours, and then kept for 2 hours to complete polymerization to obtain an acrylic rubber latex. A part of this latex was collected, and the average particle size of the composite rubber was measured.
m. To this composite rubber latex, a mixed solution of 0.06 part of tert-butyl hydroperoxide and 20 parts of methyl methacrylate was dropped at 60 ° C. for 15 minutes, and then kept at 70 ° C. for 4 hours to carry out graft polymerization to acrylic rubber. Completed. The polymerization rate of methyl methacrylate was 98.4%. The obtained graft copolymer latex was treated with 200% hot water of 1.5% by weight of calcium chloride.
The mixture was coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain 97.8 parts of a powdery graft copolymer (7). The particle size of the graft copolymer (7) was measured in the same manner as in the case of the liquid compound-containing graft copolymer (1) of Reference Example 1. The results are shown in Tables 3, 4 and 6 together with the results of Comparative Examples using the same.

(Reference Examples 8 to 9) Graft copolymer (8,
Production of 9) Graft copolymers (8, 9) were produced in the same manner as in Reference Example 7, except that the components shown in Table 1 were used as components [D] other than the charged compositions shown in Table 1. The particle diameters of these graft copolymers (8, 9) were measured in the same manner as in the case of the liquid compound-containing graft copolymer (1) of Reference Example 1. The results are shown in Tables 3 and 4 together with the results of Comparative Examples using the same.

(Reference Examples 10 to 12, 19 to 20) Production of Graft Copolymer Compositions (10 to 12, 19 to 20) The powdery liquid compound-containing graft copolymers obtained in Reference Examples 7 to 9 ( 7 to 9), as shown in Tables 1 and 2, 0.15 parts of ethylene-α-olefin-based co-oligomer: Lucant HC-100 (manufactured by Mitsui Chemicals, Inc.) was mixed using a Henschel mixer, Graft copolymer compositions (10 to 12, 19 to 20) were produced. Also,
These graft copolymer compositions (10 to 12, 19 to
The particle size of 20) was measured in the same manner as in the case of the liquid compound-containing graft copolymer (1) of Reference Example 1. The results are shown in Tables 3, 4 and 6 together with the results of Comparative Examples using the same.
Shown in

(Examples 1 to 8, Comparative Examples 1 to 12) The liquid compound-containing graft copolymer, graft copolymer, and graft copolymer composition obtained in Reference Examples 1 to 12 were modified to have an improved impact strength. Tables 3 and 4 used as fillers (1 to 12)
As shown in Table 2, 100 parts of each matrix resin were blended at the ratios shown in Tables 3 and 4, respectively, and physical properties were evaluated. The results are shown in Tables 3 and 4. In addition, as a matrix resin, methyl methacrylate (PMM
A) Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd. is used as the resin, Iupilon S2000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd. is used as the polycarbonate (PC) -based resin, and polystyrene (PSt) -based resin is used as the polystyrene (PSt) -based resin. Sumibright M140, a general-purpose polystyrene manufactured by Sumitomo Chemical Co., Ltd., was used. The acrylonitrile-styrene copolymer (AS) resin is composed of 30% by weight of an acrylonitrile component and 70% by weight of a styrene component, and has a reduced viscosity (ηsp / c) measured in dimethylformamide at 25 ° C. of 0.71 dl /. g of AS resin was manufactured and used for measurement.

The physical properties were evaluated as follows. -Measurement of glass transition temperature 70 parts of the impact strength modifiers (1 to 12) and 30 parts of the matrix resin corresponding to each of the examples shown in Tables 3 and 4 were pelletized together at 250 ° C using a 25φ single screw extruder. , 2
Using a press machine set at 00 ° C., a plate prepared to a thickness of 3 mm was cut out to a width of about 10 mm and a length of about 12 mm.
Instruments DMA 983,
Measured under the condition of a temperature rising rate of 2 ° C./min, the obtained Tan
The temperature corresponding to the transition point of the δ curve was determined as the glass transition temperature. In addition, the measured glass transition temperature is a value derived from each impact strength modifier. -Izod impact resistance 25 m of the composition of the following formulation A adjusted to 280 ° C
Extruded by an mφ twin screw extruder, the pelletized product was sufficiently dried, and then, by an injection molding machine adjusted to 280 ° C. and a mold set to 80 ° C., ”″ × 1 /
A 4 ″ test piece was prepared and evaluated according to the method of ASTM D256. The measurement was performed at 23 ° C. and described as Measurement A in Tables 3 and 4. Formulation A: 100 parts of vinyl chloride resin (polymerization degree 700) dibutyltin Malate 3.5 parts Stearyl alcohol 0.8 parts Processing aid Metablen P-700 0.4 parts Impact strength modifier 10 parts

(Examples 9 to 16, Comparative Examples 13 to 17) The liquid compound-containing graft copolymers and graft copolymers obtained in the above Reference Examples (1, 2, 7, 10, 13 to 20) Graft copolymer composition (1, 2, 7, 10, 13
-20) and a commercially available MBS-based modifier “METABLEN C-223” as an impact strength modifier, blended with a vinyl chloride resin in the following composition A and composition B, respectively, An evaluation was performed. The results are shown in Tables 5 and 6. The measurement of the glass transition temperature was performed in the same manner as in Example 1. Formulation A: Vinyl chloride resin (polymerization degree 700) 100 parts Dibutyltin malate 3.5 parts Stearyl alcohol 0.8 parts Processing aid Metablen P-700 0.4 parts Impact strength modifier 10 parts Formulation B: Vinyl chloride resin (Degree of polymerization 1100) 100 parts Dibasic lead phosphite 2.5 parts Dibasic lead stearate 0.7 parts Lead stearate 0.5 parts Calcium stearate 0.9 parts Polyethylene wax (molecular weight 2200) 0.1 Part Calcium carbonate 5.0 part Processing aid (METABLEN P-501) 1.0 part Impact strength modifier 10 parts

Izod impact resistance Each of the compositions of Formula A and Formula B shown above was
With a 25mmφ single screw extruder adjusted to 90 ° C, 1 /
A 2 "x 1/4" square bar was extruded and evaluated according to the method of ASTM D256. The measurement was performed at 23 ° C. for Formula A and at 0 ° C. for Formula B, and are shown as Measurement A and Measurement B in Tables 5 and 6, respectively. -Weather resistance The composition obtained by adding 0.5 part of carbon black to the above-mentioned composition B was further kneaded at 200 ° C and 15 rpm for 5 minutes using a 6-inch test roll machine manufactured by Kansai Roll Co., Ltd. C for 6 minutes, then 50kg /
A sheet test piece obtained by cooling while applying a pressure of ² cm ² was applied to an I-Super UV tester manufactured by Dainippon Plastics Co., Ltd., which was adjusted to 60 ° C., for 8 hours.
The operation of placing in a thermo-hygrostat adjusted to 95% and humidity for 16 hours was repeated 5 times, and the appearance of the sheet test piece was visually evaluated. In Tables 5 and 6, ○ indicates good fading resistance and X indicates bad.

[0043]

[Table 1]

[0044]

[Table 2]

In Tables 1 and 2, abbreviations indicate the following. 2EHA: 2-ethylhexyl acrylate BA: butyl acrylate AMA: allyl methacrylate MMA: methyl methacrylate AN: acrylonitrile St: styrene LMA: lauryl methacrylate In addition, * marks in Reference Examples 10, 11, 12, 19, and 20 indicate post-addition. Note that both Lucant HC-100 and Lucant HC-20 are ethylene-α-olefin oligomers manufactured by Mitsui Chemicals, Inc.

[0046]

[Table 3]

In Table 3, abbreviations indicate the following. PMMA: methyl methacrylate resin PAS: acrylonitrile styrene copolymer

[0048]

[Table 4]

In Table 4, abbreviations indicate the following. PC: Polycarbonate resin PSt: Polystyrene resin

[0050]

[Table 5]

[0051]

[Table 6]

From Tables 3 and 4, all of the resin compositions of Examples 1 to 8 using the liquid compound-containing graft copolymers produced in Reference Examples 1 to 6 as impact modifiers have excellent impact resistance. I was On the other hand, Comparative Examples 1, 2, 7, and 8 in which no impact modifier was added, and Comparative Examples 3, 4, 9, and 10 in which the graft copolymers of Reference Examples 7 to 9 were used as impact strength modifiers.
And Comparative Examples 5, 6, 11, and 12 in which the graft copolymer compositions of Reference Examples 10 to 12 to which the component [A] was added later were used as impact strength modifiers, all of which had poor impact strength development. . Also, from Tables 5 and 6, Example 9 in which the liquid compound-containing graft copolymer obtained in Reference Example (1, 2, 13 to 18) was used as an impact strength modifier.
All of the resin compositions Nos. To 16 exhibited high impact resistance, good impact resistance at low temperatures, and excellent weather resistance. On the other hand, the graft copolymer of Reference Example 7, Reference Example 10,
In Comparative Examples 13 to 17 in which the graft copolymer compositions of Nos. 19 and 20 and the commercially available MBS-based modifier “METABLEN C-223” were used as the impact strength modifier, the impact strength development was poor. In Comparative Example 17, the test piece after the weather resistance test faded, and the weather resistance was insufficient.

[0053]

As described above, the impact strength modifier of the present invention can be added in a small amount to improve the impact resistance of a resin, especially the low-temperature impact resistance, and to improve the fading resistance of the obtained molded article. And good weather resistance such as impact resistance. Particularly, the compounding with a vinyl chloride resin is suitable. Further, the resin composition containing such an impact strength modifier is excellent in both impact resistance and weather resistance.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J002 AA01Y AC03Y AC06Y BB03Y BB12Y BB15X BC03Y BC06Y BC07Y BD03Y BD12Y BG04X BG05X BG05Y BG06Y BG07X BH01Y BN06Y BN12W BN12Y CF16Y CB12Y CB12Y BN14Y00 BN14Y00 EH036 EH056 EH096 EH146 EH156 EW046 FD010 FD020 FD030 FD130 FD170 4J011 PA23 PA30 PA64 PA69 PA86 PA99 PC02 PC06 4J026 AA17 AA18 AA45 AA46 AA48 AA49 AA61 AB44 AC18 AC34 BA05 GA04 BA03 GA03 DA03 GA04

Claims (10)

[Claims] 1. Chemical formula C _n H _{(2n + 2)} (where n is an integer)
A hydrocarbon compound containing a compound represented by the formula:
[(CH ₂ —CH ₂ ) _x (CH ₂ —CHR _a ) _y ]-(wherein
x and y are integers, _Ra is a hydrocarbon compound including a compound having a repeating unit represented by H or an alkyl group, a chemical formula-(CH ₂ -CXCOOR _b )-(where X is H or CH ₃ , R _b is an alkyl group), a compound including a (meth) acrylate oligomer having a repeating unit represented by the following formula: aliphatic monobasic acid ester, aliphatic dibasic acid ester, dihydric alcohol ester, oxyacid ester,
One or more compounds selected from phthalic acid esters, phosphoric acid esters, trimetic acid esters, epoxy group fatty acid esters, epoxidized oil-based compounds, and polyorganosiloxane-based oil compounds.
A liquid compound [A] containing a compound having a viscosity at 5 ° C. of 4,000,000 cs or less, an alkyl (meth) acrylate monomer (B _a ), a crosslinking agent and / or a graft cross-linking agent (B _g ) Polyalkyl (meth) acrylate rubber component [B] composed of
And the same alkyl (meth) acrylate monomer (B _a ) as that constituting the polyalkyl (meth) acrylate rubber component [B]; and the above-mentioned alkyl (meth) acrylate monomer when polymerized alone. One or more alkyl (meth) acrylate monomers (C _a ) selected to be higher than the glass transition temperature of the (co) polymer of (B _a ), and a crosslinking agent and / or a graft cross-linking agent (C _g ) a polyalkyl (meth) acrylate rubber component [C] and a liquid compound-containing acrylic rubber component comprising at least one vinyl monomer [D] graft-polymerized to have an average particle diameter of An impact strength modifier comprising a liquid compound-containing graft copolymer having a particle size of 0.01 to 5 µm. 2. The number distribution of the particle diameter of the liquid compound-containing graft copolymer is at least 1 in 0.01 to 0.1 μm.
The impact strength modifier according to claim 1, wherein the impact strength modifier has a bidisperse distribution having at least one peak and at least one peak at 0.1 to 0.5 µm. 3. A polyacryl (meth) acrylate rubber component 99.99 comprising a liquid compound-containing graft copolymer comprising 0.001 to 20% by weight of a liquid compound [A] and components [B] and [C]. And the weight ratio of the component [B] and the component [C] is [B]: [C] =
1:60 to 100 parts by weight of a vinyl monomer [D] is graft-polymerized with respect to a total of 100 parts by weight of a liquid compound-containing rubber component in a range of 1:80 to 99:20. The impact strength modifier according to claim 1 or 2, wherein 4. The polyalkyl (meth) acrylate rubber component [B] has a glass transition temperature lower than that of a homopolymer of n-butyl acrylate. 3. The impact strength modifier according to item 1. 5. An alkyl (meth) acrylate monomer (B _a ) comprising 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate The impact strength modifier according to any one of claims 1 to 4, wherein the alkyl (meth) acrylate monomer (C _a ) is n-butyl acrylate. Quality agent. 6. An alkyl (meth) acrylate monomer (B _a ) and a crosslinking agent and / or _a crosslinking agent in the presence of a liquid compound [A].
Alternatively, a rubber component composed of the liquid compound [A] and the polyacryl (meth) acrylate rubber component [B] is obtained by emulsion polymerization of a graft crossing agent (B _g ) with the polymer. The alkyl (meth) acrylate monomer (B _a ) and the alkyl (meth) acrylate monomer (C _a ) constituting the acrylic (meth) acrylate rubber component [C] and a crosslinking agent and / or a graft crossing agent (C _g) ) To obtain a liquid compound-containing acrylic rubber component, and then, in the presence of the liquid compound-containing acrylic rubber component, graft-polymerize a vinyl monomer [D]. 6. The method for producing an impact strength modifier according to any one of claims 1 to 5. 7. An alkyl (meth) acrylate monomer (B _a ) in the presence of a liquid compound [A] and a crosslinking agent and / or
7. The method for producing an impact strength modifier according to claim 6, wherein the method of emulsion-polymerizing the graft crosslinking agent (B _g ) is a forced emulsion polymerization method. 8. An alkyl (meth) acrylate constituting a polyacryl (meth) acrylate rubber component [C] in the presence of a rubber component comprising a liquid compound [A] and a polyacryl (meth) acrylate rubber component [B]. Monomer (B _a ) and an alkyl (meth) acrylate monomer (C
_The method for producing an impact strength modifier according to claim 6 or 7, wherein the method for polymerizing _a ) and the crosslinking agent and / or the graft crosslinking agent ( _Cg ) is a batch polymerization method. 9. A thermoplastic resin composition comprising the impact strength modifier according to claim 1 and a thermoplastic resin. 10. A vinyl chloride resin composition comprising the impact strength modifier according to claim 1 and a hard vinyl chloride resin.