JPH0651767B2 - Preparation of graft resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an adhesive, a coating agent, a modifier, a microdispersion aid or a polymer alloying agent, a functional molding material, a polymer compatibilizing agent, etc. The present invention relates to a method for producing a graft resin composition having high graft efficiency, which is useful as

[Conventional technology]

BACKGROUND ART Ethylene (co) polymers have hitherto been widely used because of their excellent properties, and have also been modified and applied to new uses.

As an ethylene-based (co) polymer, for example, a low-density ethylene polymer has been used as a molding material because of its good moldability and good physical and chemical properties of a molded product.

In order to improve the rigidity, dimensional stability, printability, etc. of the low density ethylene polymer as the molding material, a vinyl polymer such as polystyrene is blended with the low density ethylene polymer.

Further, it is well known that the epoxy group-containing ethylene copolymer exhibits a good adhesive force as an adhesive agent between a metal and a plastic material due to its polarity.

Furthermore, since it has its elastic properties and reactivity,
It is also used as an impact resistance improver by reacting with a condensation polymer, especially an engineering plastic.

Further, since ethylene- (meth) acrylic acid ester copolymers and α-olefin-vinyl ester copolymers have excellent flexibility, weather resistance and impact resistance, they are widely used as molding materials, and α-olefins Vinyl ester copolymers are also widely used in hot melt adhesives.

Further, both copolymers have recently been attempted to be used as impact modifiers for engineering plastics.

Furthermore, ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber has excellent rubber elasticity,
Since it has flexibility, cold resistance, and weather resistance, it is widely used mainly as a rubber material, and in recent years, its use has also been tried as an impact resistance improving agent for engineering plastics.

However, a blend of an ethylene (co) polymer and a vinyl polymer is generally poor in compatibility, and therefore, the vinyl polymer has not been blended in an amount of 10% by weight or more. Only% vinyl polymer was blended.

Even when such a small amount of vinyl polymer is blended, the blended product tends to have low impact resistance and poor appearance due to poor compatibility of both resins.

Further, when an ethylene copolymer is used as an impact resistance improver for engineering plastics, compatibility and dispersibility are low and sufficient effect of improving impact resistance cannot be obtained, which is a problem.

For example, in the case of an epoxy group-containing ethylene copolymer,
Its application range is limited to base materials that react with epoxy groups.For example, for base materials that do not react with epoxy groups such as vinyl-based polymers, sufficient adhesive force cannot be obtained or the dispersive power to the base material is low. Sufficient impact resistance was not obtained.

Therefore, attempts have been made to increase the compatibility with engineering plastics.

For example, in an attempt to increase compatibility with engineering plastics by increasing the ratio of (meth) acrylic acid ester or vinyl ester of ethylene- (meth) acrylic acid ester copolymer or α-olefin-vinyl ester copolymer. is there. Furthermore, functional groups such as epoxy groups, carboxyl groups, acid anhydride groups, etc. are introduced into the copolymer to react with the remaining functional groups of engineering plastics, especially condensation engineering plastics to improve compatibility and impact resistance. Attempts have also been made to improve the improvement effect.

On the other hand, in order to improve the compatibility with other resins, a graft copolymer obtained by chemically bonding a polymer having a high compatibility with another resin and a polymer having a function to be expressed in one molecule is used. It is known that coalescence is preferred.

Generally, a method of graft-bonding a vinyl polymer to an ethylene (co) polymer is to irradiate ionizing radiation to graft polymer a vinyl polymer, for example, a styrene-based polymer onto the ethylene (co) ethylene (co) Polymers have been proposed and this method has shown considerable effectiveness in uniformly dispersing vinyl polymers in ethylene (co) polymers.

Furthermore, as another known method, there is a solution graft polymerization method using a solvent such as xylene or toluene.
There is also an emulsion graft polymerization method.

It has also been proposed to impregnate ethylene (co) polymer particles with a vinyl monomer and polymerize it in an aqueous suspension system (JP-B-58-51010 and JP-B-58-53003).

According to this method, the resin composition that has completed the polymerization is uniformly blended with the vinyl polymer, which is preferable to the other methods.

[Problems to be Solved by the Invention] However, the conventional method of graft-bonding a vinyl polymer to an ethylene (co) polymer has the following problems.

That is, since the method of irradiating with ionizing radiation is a special method called a radiation graft polymerization method, there is a problem in economical efficiency and it is difficult to put it into practical use.

In addition, this method is not preferable because the amount of vinyl monomer to be introduced is limited.

Next, in the solution graft polymerization method, from the viewpoint of the solubility of the ethylene (co) polymer, since the polymerization is carried out in a state diluted with a large amount of solvent, the vinyl monomer, the polymerization initiator and the ethylene (co) polymer are used. It is economically disadvantageous because it has a few chances of contacting the polymers with each other and generally has a low reaction efficiency of vinyl monomers, and the post-treatment process such as solvent recovery is complicated.

Further, there is an emulsion graft polymerization method, but in this case, since the reaction is limited only to the surface reaction of the ethylene (co) polymer particles, there is a drawback that the homogeneity of the product is poor.

In addition, the polymerization method in an aqueous suspension system is a vinyl polymer which is uniformly dispersed at the time of completion of the polymerization by heating by secondary processing or contact with a solvent because the graft efficiency of the resin composition obtained by this method is low. Secondary agglomeration of particles is likely to occur, which has been a problem when the obtained resin composition is used as a microdispersion aid, a polymer alloying agent or a polymer compatibilizing agent.

[Means for Solving the Problems]

The present inventors have obtained a grafted resin composition having a high grafting efficiency of these conventional ethylene (co) polymers and vinyl polymers, and also to a polymer component forming a dispersed phase in these resin compositions. As a result of intensive research aimed at increasing the grafting efficiency and preventing the secondary aggregation of the dispersed phase due to the secondary processing, the grafting efficiency is dramatically improved by kneading a specific grafting precursor under melting at a specific temperature. It has been found that a resin composition having a high viscosity can be obtained, and the present invention has been completed.

That is, the present invention, a grafting precursor obtained by the following method or a mixture of 1 to 99% by weight of the grafting precursor and 99 to 1% by weight of the following polymer under melting at 100 to 300 ° C., The present invention relates to a method for producing a graft resin composition, which comprises carrying out a grafting reaction by kneading.

The grafting precursor is an ethylene-based (co) polymer 10
0 parts by weight was suspended in water, and separately selected from the group consisting of vinyl aromatic monomer, (meth) acrylic acid ester monomer, (meth) acrylonitrile and vinyl ester monomer. 5 kinds or two or more kinds of vinyl monomers
To 400 parts by weight, one or a mixture of two or more radical (co) polymerizable organic peroxides represented by the following general formula (I) or (II) is added in an amount of 0.1 to 100 parts by weight of the vinyl monomer. ~
10 parts by weight and a decomposition temperature of 40 to obtain a half-life of 10 hours
A solution of a radical polymerization initiator having a temperature of ~ 90 ° C dissolved in 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of the vinyl monomer and the radical (co) polymerizable organic peroxide is added,
It is heated under the condition that decomposition of the radical polymerization initiator does not substantially occur, and the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator are impregnated in the ethylene (co) polymer, and further, When the content of free vinyl monomer, radical (co) polymerizable organic peroxide and radical polymerization initiator was less than the initial 50% by weight, the temperature of this aqueous suspension was raised to increase the vinyl monomer content. Quantum and Radical (Co)
A resin composition obtained by copolymerizing a polymerizable organic oxide in an ethylene (co) polymer.

The radical (co) polymerizable organic peroxide represented by the general formula (I) is a compound represented by the formula: Indicated by.

(In the formula, R ₁ hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, R _{5 is} an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or an alkyl group having 3 to 12 carbon atoms. Indicates a cycloalkyl group. m is 1 or 2. ) Further, the radical (co) polymerizable organic peroxide represented by the general formula (II) is represented by the formula: Indicated by.

(In the formula, R ₆ hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₇ a hydrogen atom or a methyl group, _{R 8} and _{R 9} are each an alkyl group having 1 to 4 carbon _{atoms, R 1 0} is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a 3 to 12 carbon atoms Represents a cycloalkyl group. n is 0, 1 or 2. ) The polymer forming a mixture with the grafted precursor is
One selected from the group consisting of (i) ethylene-based (co) polymer, (ii) vinyl aromatic monomer, (meth) acrylic acid ester monomer, (meth) acrylonitrile and vinyl ester monomer Alternatively, it is a polymer composed of one or both of vinyl polymers obtained by polymerizing two or more vinyl monomers.

Examples of the ethylene-based (co) polymer used in the present invention include:
For example, a low-density ethylene polymer, an epoxy group-containing ethylene copolymer obtained by copolymerizing ethylene and glycidyl (meth) acrylate, an ethylene copolymer comprising ethylene and a (meth) acrylate ester, ethylene And an ethylene-based copolymer comprising ethylene and a vinyl ester, an ethylene-propylene copolymer rubber, an ethylene-propylene-diene-copolymer rubber, and the like.

The low density ethylene polymer used in the present invention has a density of 0.
It is preferably 910 to 0.935 g / cm ₃ , specifically, ethylene homopolymer obtained by a high pressure polymerization method, ethylene and α-olefin for density adjustment such as propylene, butene-1, pentene-1 and the like. The copolymer of

The low density ethylene polymer may be in the form of pellets having a particle size of 1 to 5 mm, or may be in the form of powder. These are preferably used properly according to the blending ratio of the low density ethylene polymer in the grafting precursor. For example, when the low-density ethylene polymer in the grafting precursor is 50% by weight or more, it is preferable to use the pelletized one, and when it is less than 50% by weight, the powdered one is preferable.

The epoxy group-containing ethylene copolymer used in the present invention is a copolymer of ethylene and glycidyl (meth) acrylate.

At this time, ethylene is preferably 60 to 99.5% by weight.

The copolymerization ratio of glycidyl (meth) acrylate is 0.5 to 4
It is 0% by weight, preferably 2 to 20% by weight. Copolymerization amount
If it is less than 0.5% by weight, the effect is not sufficient when used as an impact resistance improver. On the other hand, if it exceeds 40% by weight, the fluidity at the time of melting is lowered, which is not preferable.

In addition, the copolymerization ratio of glycidyl (meth) acrylate is 40
When it is less than wt%, (meth) acrylic acid ester monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, vinyl ester monomers such as vinyl acetate and vinyl propionate, vinyl ether monomers, It is also possible to copolymerize one or more kinds of (meth) acrylonitrile, vinyl aromatic monomer, carbon monoxide and the like, and these are included in the present invention.

Specific examples of the epoxy group-containing ethylene copolymer include ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene. / Carbon monoxide / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer and the like. Especially preferred is ethylene /
It is a glycidyl methacrylate copolymer.

These epoxy group-containing ethylene copolymers can be mixed and used.

The shape of the epoxy group-containing ethylene copolymer has a particle size of 0.
It is preferably in the form of powder or pellets of about 1 to 5 mm. These are preferably used properly according to the blending ratio of the epoxy group-containing ethylene copolymer in the grafting precursor.

If the particle size is transiently large, not only is it difficult to disperse during polymerization, but it also takes a long time to impregnate a vinyl monomer or the like.

The ethylene- (meth) acrylic acid ester copolymer used in the present invention includes, specifically, ethylene- (meth) acrylic acid methyl copolymer, ethylene- (meth) acrylic acid ethyl copolymer, ethylene- A butyl (meth) acrylate copolymer is mentioned. It is preferably an ethylene-ethyl acrylate copolymer.

At this time, ethylene is preferably 50 to 99% by weight.

In ethylene- (meth) acrylic acid ester copolymer,
The copolymerization ratio of the (meth) acrylic acid ester is 1 to 50% by weight, preferably 2 to 40% by weight. When the copolymerization ratio is less than 1% by weight, when used as an impact resistance improver,
The effect is not enough.

On the other hand, when it exceeds 50% by weight, moldability is deteriorated, which is not preferable.

The shape and blending ratio of the ethylene- (meth) acrylic acid ester copolymer are the same as those of the epoxy group-containing ethylene copolymer.

The ethylene-vinyl ester copolymer used in the present invention includes ethylene and vinyl propionate; vinyl acetate; vinyl caproate; vinyl caprylate; vinyl laurate; vinyl stearate; vinyl trifluoroacetate and the like. It is a copolymer of one or more kinds of monomers in the presence of a radical polymerization initiator, and is preferably an ethylene-vinyl acetate copolymer.

The copolymerization ratio of the vinyl ester monomer in the ethylene-vinyl ester copolymer is the same as the copolymerization ratio of the (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer.

The shape and blending ratio of the ethylene-vinyl ester copolymer are also the same as those of the ethylene- (meth) acrylic acid ester copolymer.

The ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber used in the present invention has an ethylene content of 40 to 80% by weight and propylene of 60 to 20% by weight,
An ethylene-propylene copolymer rubber having a Mooney viscosity of 15 to 90 and an ethylene content of 40 to 80% by weight, propylene of 60 to 20% by weight, ethylidene norbornene;
4-hexadiene; a rubber obtained by terpolymerizing dicyclopentadiene and the like as a non-conjugated diene component, wherein the content of the diene is 4 to 30 by iodination and the Mooney viscosity is 15 to 120. Appropriate.

The Mooney viscosity is a value determined by JIS K6300 (100 ° C).

These ethylene-propylene copolymer rubbers or ethylene-propylene-diene copolymer rubbers can also be mixed and used.

In order to facilitate impregnation of the vinyl monomer and prevent aggregation during suspension polymerization, the ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber particles have a narrow particle size distribution and an average particle size of 2 to It is preferable that the pellet is about 8 mm.

If the particle size is excessively large, not only dispersion during polymerization is difficult but also the impregnation speed of the vinyl monomer becomes slow and the reaction time becomes long.

The vinyl monomer used in the present invention is specifically a vinyl aromatic monomer such as styrene; a nucleus-substituted styrene such as methylstyrene; dimethylstyrene; ethylstyrene; isopropylstyrene; chlorostyrene;
α-Substituted styrene, for example, α-methyl styrene; α-ethyl styrene; (meth) acrylic acid ester monomer, for example, an alkyl ester of (meth) acrylic acid having 1 to 7 carbon atoms; (meth) acrylonitrile; Examples thereof include vinyl propionate; vinyl acetate; vinyl caproate; vinyl caprylate; vinyl laurate; vinyl stearate; vinyl trifluoroacetate and the like.

Further, vinyl halide or vinylidene (particularly, vinyl chloride, vinylidene chloride), vinylnaphthalene, vinylcarbazole, acrylamide, methacrylamide, maleic anhydride, and the like can be used, either alone or in combination of two or more. Used.

Of these, vinyl aromatic monomers and (meth) acrylic acid ester monomers are preferable.

Particularly when these are used as impact modifiers for engineering plastics, those obtained by (co) polymerizing a mixture containing 50% by weight or more of a vinyl aromatic monomer or a (meth) acrylic acid ester monomer are preferable. The reason is that the compatibility with engineering plastics is good. Further, it is particularly preferable that the hydrophilic or solid vinyl monomer is used by dissolving it in an oil-soluble monomer.

The amount of the vinyl monomer is 5 to 400 with respect to 100 parts by weight of the ethylene (co) polymer in the production of the grafting precursor.
Parts by weight, preferably 10 to 200 parts by weight. This amount is 5
If the amount is less than parts by weight, the grafting precursor after the grafting reaction is not preferable because the performance as a grafting precursor is difficult to be expressed although the grafting efficiency is high.

Also, if this amount exceeds 400 parts by weight, vinyl monomer,
Of the radical (co) polymerizable organic peroxides and radical polymerization initiators represented by the general formula (I) or (II), those which are not impregnated in the ethylene (co) form are liable to be 50% by weight or more, and are free. This is not preferable because the amount of the vinyl homopolymer is increased. Japanese Patent Publication 58-51010 or Japanese Patent Publication 5
According to 8-53003, in the aqueous suspension polymerization method,
It is said that the content of the free vinyl-based monomer is less than 20% by weight. However, in the present invention, the resulting grafting precursor has a peroxy group in the vinyl polymer molecule and has a grafting ability, so that the free vinyl monomer, the general formula (I ) Or (I
Even if the total amount of the radical (co) polymerizable organic peroxide represented by I) and the radical polymerization initiator is 20% by weight or more
If it is less than 50% by weight, a sufficiently excellent grafting ability can be exhibited.

The radical (co) polymerizable organic peroxide used in the present invention is a compound represented by the above general formula (I) or (II).

Specifically, as the compound represented by the general formula (I), t
-Butylperoxyacryloyloxyethyl carbonate; t-Amylperoxyacryloyloxyethyl carbonate; t-Hexylperoxyacryloyloxyethyl carbonate; 1,1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate; Cumylperoxy Acryloyloxyethyl carbonate; p-isopropyl cumyl peroxyacryloyloxy ethyl carbonate; t-butyl peroxymethacryloyloxyethyl carbonate; t-amyl peroxymethacryloyloxyethyl carbonate; t-hexyl peroxymethacryloyloxyethyl carbonate; 1, 1,3,3-Tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumylperoxymethacryloyloxyethyl carbonate; p-isop Pilcumyl peroxymethacryloyloxyethyl carbonate; t-butyl peroxyacryloyloxyethoxyethyl carbonate; t-amyl peroxyacryloyloxyethoxyethyl carbonate; t-hexyl peroxyacryloyloxyethoxyethyl carbonate; 1, 1, 3, 3 -Tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl carbonate; p-isopropyl cumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethyl carbonate; t-amylperoxy Methacryloyloxyethoxyethyl carbonate; t-hexyl peroxymethacryloyloxyethoxyethyl carbonate; 1, 1, 3, -Tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethyl carbonate; p-isopropyl cumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t-amylperoxyacrylic acid Loyloxy isopropyl carbonate; t-hexyl peroxyacryloyloxy isopropyl carbonate; 1, 1,
3,3-Tetramethylbutylperoxyacryloyloxy isopropyl carbonate; Cumyl peroxyacryloyloxy isopropyl carbonate; p-Isopropyl cumyl peroxyacryloyloxy isopropyl carbonate; t-Butyl peroxymethacryloyloxy isopropyl carbonate; t-Amyl peroxymethacryl Loyloxyisopropyl carbonate; t-hexyl peroxymethacryloyloxyisopropyl carbonate; 1,
Examples include 1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate; cumylperoxymethacryloyloxyisopropyl carbonate; p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate.

Further, as the compound represented by the general formula (II), t-
Butyl peroxyallyl carbonate; t-amyl peroxyallyl carbonate; t-hexyl peroxyallyl carbonate; 1,1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate: t-butyl Peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate; 1,1,3,3-tetramethylbutyl peroxy methallyl carbonate; p-menthane peroxy methallyl carbonate; cumyl peroxy methallyl carbonate Carbonate; t-butyl peroxyallyloxyethyl carbonate; t-amyl peroxyallyloxyethyl carbonate; t-hexyl peroxyallyloxyethyl carbonate; t-butylpe Oxymetalryloxyethyl carbonate; t-amyl peroxymetalloyloxyethyl carbonate; t-hexyl peroxy metalryloxyethyl carbonate; t-butyl peroxyallyloxy isopropyl carbonate; t-amyl peroxyallyloxy isopropyl carbonate; t-hexyl peroxyallyloxy isopropyl carbonate Examples thereof include: t-butyl peroxy metalryloxy isopropyl carbonate; t-amyl peroxy metal ryloxy isopropyl carbonate; t-hexyl peroxy metal ryloxy isopropyl carbonate.

Among them, t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallyl carbonate; t-butylperoxymethallyl carbonate are preferable.

The amount of the radical (co) polymerizable organic peroxide used is 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl monomer.

If the amount used is less than 0.1 parts by weight, the amount of active oxygen contained in the resulting grafting precursor used in the present invention is small and it is difficult to exhibit sufficient grafting ability, which is not preferable.

On the other hand, if the amount exceeds 10 parts by weight, the radical (co) polymerizable organic peroxide undergoes induced decomposition during the polymerization, and a large amount of gel is generated in the grafting precursor at the completion of the polymerization, and further the grafting precursor is generated. Although the grafting ability of the body is increased, the gel forming ability is also increased at the same time, which is not preferable.

The radical polymerization initiator used for producing the grafted precursor in the present invention has a decomposition temperature for obtaining a half-life of 10 hours (hereinafter referred to as 10-hour half-life temperature) of 40 to 90 ° C., preferably 50. ~ 75 ℃. This is because the polymerization at the time of producing the grafting precursor in the present invention must be carried out under the condition that the radical (co) polymerizable organic peroxide used is not decomposed at all, while the radical (co) polymerizable organic peroxide is used. The 10-hour half-life temperature of peroxide itself is 90-110 ° C.
Therefore, the polymerization temperature must be 110 ° C. or lower.

When the 10-hour half-life temperature of the radical polymerization initiator exceeds 90 ° C., the polymerization temperature becomes high and the radical (co) polymerizable organic peroxide may be decomposed during the polymerization, which is not preferable.
Further, if the temperature is lower than 40 ° C., the polymerization is started in the process of impregnating the ethylene-based (co) polymer with the vinyl monomer, and the resulting grafting precursor becomes non-uniform, which is not preferable. Here, the 10-hour half-life temperature means benzene 1
Add 0.1 mol of polymerization initiator to liter and
This is the temperature at which the decomposition rate of the polymerization initiator becomes 50% over time.

As such a radical polymerization initiator, specifically,
For example, diisopropyl peroxydicarbonate (4
0.5 ° C); di-n-propylperoxydicarbonate (40.5 ° C); dimyristyl peroxydicarbonate (40.9 ° C); di (2-ethoxyethyl) peroxydicarbonate (43.4 ° C); di (methoxyisopropyl) peroxydicarbonate (43.5 ° C.); di (2-ethylhexyl) peroxydicarbonate (43.5 ° C.); t-hexyl peroxy neodecanoate (44.7 ° C.); di (3-
Methyl-3-methoxybutyl) peroxydicarbonate (46.5 ° C.); t-butyl peroxy neodecanoate (46.5 ° C.); t-hexyl peroxy neohexanoate (51.3 ° C.); t-butyl peroxy neohexanoate ( 53 ° C); 2,4-dichlorobenzoyl peroxide (53
° C); t-hexyl peroxypivalate (53.2 ° C); t-
Butyl peroxypivalate (55 ° C); 3,5,5-trimethylhexanoyl peroxide (59.5 ° C); octanoyl peroxide (62 ° C); lauroyl peroxide (62 ° C); cumyl peroxyoctoate (65.1 ° C):
Acetyl peroxide (68 ° C); t-butylperoxy-
2-Ethylhexanoate (72.5 ° C); m-toluoyl peroxide (73 ° C); benzoyl peroxide (74
C); t-butyl peroxyisobutyrate (78 C); 1,
1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane (90 ° C.) and the like can be mentioned (10 hours half-life temperature is shown in parentheses).

The amount of the radical polymerization initiator used is 0.01 to 5 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the total of the vinyl monomer and the radical (co) polymerizable organic peroxide.

If the amount used is less than 0.01 parts by weight, the vinyl monomer and the radical (co) polymerizable organic peroxide are not completely polymerized, which is not preferable. Further, if it exceeds 5 parts by weight, intermolecular cross-linking of the ethylene (co) polymer is likely to occur during the polymerization, and further the radical (co) polymerizable organic peroxide is apt to undergo induced decomposition, which is not preferable. .

The polymerization for producing the grafted precursor in the present invention is carried out by a commonly used aqueous suspension polymerization method.

Therefore, an ethylene-based (co) polymer, a solution prepared by dissolving a radical polymerization initiator and a radical (co) polymerizable organic peroxide, which are separately prepared, in a vinyl monomer in advance are suspended in an aqueous solution. A suspending agent that can be used for the polymerization, for example, a water-soluble polymer, that is, polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose or the like, or a poorly water-soluble inorganic substance, such as calcium phosphate, magnesium oxide or the like, is stirred and dispersed in water.

The concentration of the aqueous suspension in this case is arbitrary, but generally 10
It is carried out at a ratio of 5 to 150 parts by weight with respect to 0 parts by weight.

In the present invention, the impregnation of the ethylene-based (co) polymer with the solution is preferably performed at a temperature as high as possible.
However, when the radical polymerization initiator decomposes and starts polymerization during impregnation, the composition of the resulting grafting precursor becomes very inhomogeneous, so it is generally higher than the 10-hour half-life temperature of the radical polymerization initiator used. It is preferable to carry out at a temperature lower than 5 ° C.

The total amount of the free vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator after impregnation is
It should be less than 50% by weight, preferably less than 20% by weight, based on the total initial amount used. When this amount is 50% by weight or more, the grafting ability of the grafting precursor in the present invention is extremely reduced, which is not preferable.

For the amount of free vinyl monomer, radical (co) polymerizable organic peroxide and radical polymerization initiator, sample an arbitrary amount of the aqueous suspension, and quickly filter this using a wire mesh of about 300 mesh. Then, the ethylene (co) polymer and the liquid phase are separated, and the amounts of the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator in the liquid phase are measured and calculated.

The polymerization for producing the grafted precursor in the present invention is usually carried out at a temperature of 30 to 110 ° C. because,
This is to prevent decomposition of the radical (co) polymerizable organic peroxide during polymerization as much as possible.

If the temperature exceeds 110 ° C. and the polymerization time is 5 hours or more, the amount of decomposition of the radical (co) polymerizable organic peroxide increases, which is not preferable. The polymerization time is generally 2
~ 20 hours is appropriate.

Further, the grafting precursor in the present invention is a vinyl polymer blended therein, as an active oxygen amount of 0.
Must contain from 01 to 0.73% by weight.

When the amount of active oxygen is less than 0.01% by weight, the grafting ability of the grafting precursor is extremely reduced, which is not preferable. Also,
When it exceeds 0.73% by weight, the gel-forming ability at the time of grafting is increased, which is also not preferable. The amount of active oxygen in this case can be calculated by extracting the vinyl polymer from the grafted precursor by solvent extraction and determining the amount of active oxygen of this vinyl polymer by the iodometry method.

The grafting resin composition of the present invention is a grafting reaction by melting the above-mentioned grafting precursor alone or by kneading a mixture of this grafting precursor and the following polymer at a specific temperature. Then, a graft resin composition is obtained.

In the present invention, the polymer that forms a mixture with the grafting precursor is preferably the same as that used in the production of the grafting precursor, and either one of an ethylene (co) polymer or a vinyl polymer or It is a polymer composed of both.

For example, when the ethylene polymer in the grafting precursor is a low density ethylene polymer, those having the same monomer composition or density are preferable.

If the monomer composition or the density is different, kneading tends to be insufficient, and the mechanical strength and appearance of the obtained graft resin composition may be deteriorated, which is not preferable.

Also in the case of other ethylene (co) polymers, those having the same monomer composition are preferable for the same reason.

In the present invention, the vinyl polymer that forms a mixture with the grafting precursor is a vinyl monomer used in the production of the grafting precursor, specifically, a vinyl aromatic monomer; Substituted styrenes such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrenes such as α-methylstyrene, α-ethylstyrene; (meth) acrylic acid ester monomers such as (meth) acrylic An alkyl ester of an acid having 1 to 7 carbon atoms; (meth) acrylonitrile; a vinyl ester monomer, for example, a polymer obtained by polymerizing one or more of vinyl acetate and vinyl propionate. And, it is preferable that the monomer composition is the same as that of the vinyl polymer in the grafting precursor, and if the monomer composition is different, kneading tends to be insufficient similarly to the above, and the obtained graft resin composition is obtained. The mechanical strength and appearance of the product may deteriorate, which is not preferable.

When used as a mixture, the graft resin composition of the present invention comprises 1 to 99% by weight of a grafting precursor and 99 to 1% by weight of a polymer kneaded with the precursor.

If the amount of the grafting precursor is less than 1% by weight, that is, if the polymer to be kneaded exceeds 99% by weight, the amount of the grafted product in the graft resin composition will be small and delamination will occur.

In the production of the graft resin composition of the present invention, the grafting reaction is carried out by kneading under melting at 100 to 300 ° C.

If this temperature is lower than 100 ° C., melting is insufficient and kneading is difficult, and it takes a long time to decompose the radical (co) polymerizable organic peroxide in the grafting precursor, which is not preferable.

On the other hand, if the temperature exceeds 300 ° C., molecular cleavage (decomposition) of the grafted precursor occurs, which is not preferable.

In the present invention, kneading is necessary for maintaining the uniformity of the graft resin composition and controlling the particle size of the dispersed phase.

In particular, when the temperature of the grafting reaction during the production of the graft resin composition exceeds 200 ° C., aggregation of the dispersed phase easily occurs, but this aggregation can be prevented by kneading.

The time of the grafting reaction during the production of the graft resin composition is
Although it depends on the temperature of the grafting reaction, it is generally within 1 hour.

The heating, melting and kneading for the grafting reaction are performed using, for example, an extruder, an injection molding machine, a mixer and the like.

[Effect of the Invention] According to the present invention, a graft resin composition can be obtained easily in a short time and by using an existing kneader, and the composition ratio can be changed simply by changing the mixing ratio. .

Further, since the graft resin composition obtained by the present invention has a higher content of the graft product than the conventional product, less aggregation of the vinyl polymer due to secondary processing, an adhesive, a coating agent,
A graft resin composition useful as a modifier, a microdispersion aid, a polymer alloying agent, a functional molded material, a polymer compatibilizer, etc. can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Pure water 2500 was placed in a stainless steel autoclave with an internal volume of 5.
g and add polyvinyl alcohol 2.5 as a suspending agent
g was dissolved. Into this, 700 g of a low-density ethylene polymer having a density of 0.925 g / cm ³ (trade name "Sumikasen G-401", manufactured by Sumitomo Chemical Co., Ltd., particle size: 3 to 4 mm) is added, stirred and dispersed. Let Separately, 1.5 g of benzoyl peroxide (trade name “Nyper B”, manufactured by NOF CORPORATION, 10-hour half-life temperature 74 ° C.) as a radical polymerization initiator, and t-butylperoxy as a radical (co) polymerizable organic peroxide. 6 g of methacryloyloxyethyl carbonate was dissolved in 300 g of styrene as a vinyl monomer, and this solution was stirred into the autoclave.

Next, the autoclave was heated to 60 to 65 ° C and stirred for 1 hour while radical polymerization initiator and radical (co)
A vinyl monomer containing a polymerizable organic peroxide was impregnated into a low density ethylene polymer. Then, after confirming that the content of free vinyl monomer, radical (co) polymerizable organic peroxide and radical polymerization initiator is less than 50% by weight at the beginning, the temperature is set to 80 to 85 ° C. Up to 7 at that temperature
Polymerization was completed by maintaining for a period of time, washed with water and dried to obtain a grafted precursor.

The active oxygen content of the styrenic polymer in this grafted precursor was measured by the iodometry method and found to be 0.13% by weight.
Met. Furthermore, when this grafted precursor was extracted with xylene using a Soxhlet extractor, xylene insoluble matter was not present.

Then, this grafted precursor was treated with Laboplast Mill B.
-75 type mixer (manufactured by Toyo Seiki Co., Ltd.)
Kneading was performed at 180 rpm at a rotation speed of 50 RPM for 10 minutes to carry out a grafting reaction. With respect to the product subjected to this grafting reaction, the styrene-based polymer not grafted with ethyl acetate was extracted with a Soxhlet extractor, and the result was 3.3% by weight based on the total amount. Therefore, the graft efficiency of the styrene-based polymer was calculated to be 89% by weight.

Moreover, xylene insoluble matter was 17.5% by weight in the extraction with xylene, and as a result of further analyzing this xylene insoluble matter by pyrolysis gas chromatography, low-density ethylene polymer: styrene-based polymer was 79.0% by weight: 21.0% by weight. %
Met.

Examples 2 to 4 In Example 1, the kneading temperature of the grafted precursor is shown in Table 1.
The grafting reaction was carried out in the same manner as in Example 1 except that the above was changed, and the grafting efficiency and the xylene-insoluble content of the styrene-based polymer were measured. The results are shown in Table 1.

Example 5 In Example 1, the kneading machine was changed from a Labo Plastomill B-75 type mixer to a Banbury type mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the grafting reaction was carried out in the same manner as in Example 1.

As a result, the graft efficiency of the styrene-based polymer was 86% by weight,
The xylene insoluble content was 15.6% by weight.

Example 6 In Example 1, the kneading machine was replaced with a single-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the grafting reaction was carried out in the same manner as in Example 1.

As a result, the graft efficiency of the styrene-based polymer is 80% by weight,
The xylene insoluble content was 20% by weight.

Example 7 In Example 1, 500 g of low-density ethylene polymer, 2.5 g of benzoyl peroxide and t-
Butyl peroxymethacryloyloxyethyl carbonate was replaced by 10 g, styrene was replaced by 500 g, and a grafting precursor was produced in the same manner as in Example 1 except that the grafting reaction was carried out. As a result, the graft efficiency of the styrene polymer was 85% by weight, and the xylene insoluble content was 23% by weight.

Example 8 In Example 1, 300 g of styrene was added to methyl methacrylate.
Instead of 300 g, a grafting precursor was produced in the same manner as in Example 1 and the grafting reaction was carried out.

As a result, the grafting efficiency of methyl methacrylate polymer
The content was 64% by weight and 22% by weight insoluble matter in xylene.

Example 9 In Example 1, 300 g of styrene was replaced with a mixed monomer of 210 g of styrene and 90 g of acrylonitrile, and the other examples were used.
A grafting precursor was produced according to the above, and a grafting reaction was carried out.

As a result, the graft efficiency of the styrene-acrylonitrile copolymer was 58% by weight, and the xylene-insoluble content was 28% by weight.

Example 10 In Example 1, except that 300 g of styrene was replaced with a mixed monomer of 210 g of styrene and 90 g of n-butyl acrylate, a grafting precursor was produced in the same manner as in Example 1, and the grafting reaction was carried out. I did.

As a result, the graft efficiency of the styrene-acrylic acid-n-butyl copolymer was 62% by weight and the xylene insoluble content was 23% by weight.

Example 11 In Example 1, 300 g of styrene was added to 300 g of vinyl acetate,
6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butylperoxyallyl carbonate, and a grafting precursor was produced in the same manner as in Example 1 except that the grafting reaction was carried out. As a result, the graft efficiency of the vinyl acetate-based polymer was 69% by weight, and the xylene-insoluble content was
It was 29% by weight.

Example 12 In Example 1, the low-density ethylene polymer was replaced with a powdered low-density ethylene polymer (trade name “FLOWCEN G-401”, manufactured by Iron and Chemicals Co., Ltd., density 0.925 g / cm ³ ), and the others were used. A grafting precursor was produced according to Example 1, and a grafting reaction was performed. As a result, the graft efficiency of the styrene polymer was 85% by weight, and the xylene-insoluble content was 13% by weight.

Comparative Example 1 The grafting precursor prepared according to Example 1 was tested for grafting reaction at 90 ° C. for 1 hour using a Labo Plastomill B-75 type mixer at a rotation speed of 50 RPM, but the system did not melt. I couldn't knead.

At that time, the graft efficiency of the styrene-based polymer was measured according to Example 1, and as a result, the graft efficiency was 8% by weight and the reaction was insufficient.

Comparative Example 2 The grafting reaction was carried out in the same manner as in Example 1 except that the grafting temperature was 320 ° C.

As a result, the grafted precursor was decomposed and the resin was colored.

Comparative Example 3 In Example 1, a grafting precursor was produced according to Example 1 except that t-butylperoxymethacryloyloxyethyl carbonate was not used, and a grafting reaction was performed.

As a result, the graft efficiency of the styrene-based polymer was 7% by weight,
The content of xylene insoluble was 3% by weight, and the effect of t-butylperoxymethacryloyloxyethyl carbonate was clearly confirmed.

Example 13 Grains of the grafted precursor prepared in Example 1 50 g
Further, 50 g of granular low-density ethylene polymer having a density of 0.925 g / cm ³ was further added and well mixed at room temperature, and the kneading and grafting reaction was carried out in the same manner as in Example 1 except that this mixture was used to carry out the grafting reaction. A composition was obtained. With respect to this graft resin composition, the graft efficiency of the styrene polymer was determined in accordance with Example 1 and it was found to be 72% by weight.

The xylene insoluble content was 9.7% by weight.

Then, this graft resin composition was press-molded at 200 ° C. to prepare a plate having a thickness of 2 mm. The appearance was uniform white and no phase separation was observed. Further, when the plate was broken, delamination was not observed.

Examples 14 to 17 A graft resin composition was produced in the same manner as in Example 13 except that the blending ratio of the grafting precursor and the low density ethylene polymer was changed as shown in Table 2.

Table 2 shows the graft efficiency of the styrene polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200 ° C.

Examples 18 to 20 In Example 13, the kneading temperature was changed as shown in Table 3, and the graft resin composition was produced in the same manner as in Example 13. Table 3 shows the graft efficiency of the styrene-based polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200 ° C.

Example 21 In Example 13, the kneading machine was replaced with the Banbury type mixer used in Example 5 from the Labo Plastomill B-75 type mixer, and the graft resin composition was produced in the same manner as in Example 13. Grafting efficiency of the styrene polymer of the graft resin composition is 78% by weight, xylene insoluble content is 9.2% by weight, and
No phase separation or delamination was observed on the plate press-molded at ℃.

Example 22 A graft resin composition was produced in the same manner as in Example 13 except that the kneading machine was replaced with the single-screw extruder used in Example 6. Grafting efficiency of the styrene-based polymer of the graft resin composition is 68% by weight, xylene insoluble content is 13.1% by weight,
No phase separation or delamination was observed on the plate press-molded at 200 ° C.

Example 23 In Example 13, except that low-density ethylene was used as the kneaded product, styrene polymer (trade name "Dialex HF-55", manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was used as the vinyl polymer, except that 50 g was used. A graft resin composition was produced according to Example 13.

In this graft resin composition, the styrene polymer is considered to be matrix, so it is considered that it is originally preferable to determine the graft efficiency of the low density ethylene polymer, but unfortunately, there is no suitable measuring means. Therefore, the graft efficiency of the styrene-based polymer to the low-density ethylene polymer was determined according to Example 1. As a result, the graft efficiency of the styrene polymer was 20% by weight, and the xylene insoluble content was 2.8% by weight. Furthermore, no phase separation or delamination was observed in the plate molded from this graft resin composition according to Example 13.

Examples 24 to 27 In Example 23, a graft resin composition was produced in the same manner as in Example 13, except that the mixing amount of the grafting precursor and the styrene polymer was changed as shown in Table 4. Graft efficiency of styrene-based polymer of graft resin composition, xylene-insoluble matter and
Table 4 shows the appearance of the plate press-molded at 200 ° C.

As seen in Examples 26 and 27, when the styrene-based polymer was used as a matrix, the grafting efficiency of the styrene-based polymer to the low-density ethylene polymer was low in calculation, but was low in the dispersed phase. The density ethylene polymer is
It seems that it is grafted to the styrenic polymer with extremely high efficiency.

Examples 28 to 31 In Example 13, 700 g of the low-density ethylene polymer used in the production of the grafted precursor was added to 500 g, and 300 g of styrene was added.
500 g, benzoyl peroxide 1.5 g to 2.5 g, t-butyl peroxymethacryloyloxyethyl carbonate 6 g
Was replaced with 1 g, and a grafted precursor was produced in the same manner as in Example 13. Then, a graft resin composition was produced in the same manner as in Example 13 except that the mixing amount of the grafted precursor with the low density ethylene polymer and the styrene polymer was changed as shown in Table 5. Table 5 shows the graft efficiency of the styrene polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200 ° C.

Examples 32-36 In Example 13, 300 g of styrene was added to methyl methacrylate.
A grafted precursor was produced according to Example 13 except that 0.6 g of n-dodecyl mercaptan was additionally used as a molecular weight modifier instead of 300 g. The amount of the grafted precursor and the low-density ethylene polymer and the methyl methacrylate polymer (trade name "Derpett 50N", manufactured by Asahi Kasei Kogyo Co., Ltd.) was changed as shown in Table 6, and the others were changed to Example 13. A graft resin composition was produced in the same manner. The test results are shown in Table 6.

Examples 37-41 In Example 13, instead of 300 g of styrene, styrene
210 g, acrylonitrile 90 g, n- as a molecular weight regulator
A grafted precursor was produced according to Example 13, except that 0.6 g of a mixed monomer of dodecyl mercaptan was used. Separately, 500 g of a 1% aqueous solution of polyvinyl alcohol contained 70 g of styrene, 30 g of acrylonitrile, and n-dodecyl mercaptan.
A mixed solution of 0.2 g and benzoyl peroxide 0.5 g was added, and the temperature was maintained at 80 to 85 ° C. for 7 hours to complete the polymerization to obtain an acrylonitrile-styrene copolymer. A graft resin composition was produced in the same manner as in Example 13, except that the mixing amount of the copolymer, the grafting precursor and the low density ethylene polymer was changed as shown in Table 7. The test results are shown in Table 7.

Example 42 In Example 13, 300 g of styrene was added to methyl methacrylate.
A grafted precursor was produced in the same manner as in Example 13 except that the mixed monomer of 210 g and 90 g of n-butyl acrylate was used. Then, a graft resin composition was produced according to Example 13 using 50 g of the grafted precursor and 50 g of the low density ethylene polymer. As a result, the graft efficiency of the methyl methacrylate-acrylic acid-n-butyl copolymer was 62% by weight and the xylene insoluble content was 8.9% by weight. In addition, no phase separation or delamination was observed in the plate press-molded according to Example 13.

Example 43 In Example 13, 300 g of styrene to 300 g of vinyl acetate,
A grafted precursor was produced according to Example 13 except that 6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butylperoxyallyl carbonate. Then, a graft resin composition was produced according to Example 13 using 50 g of the grafted precursor and 50 g of the low density ethylene polymer.

Further, the grafting efficiency was measured in Example 13 by changing the extraction solvent from ethyl acetate to methanol. As a result, the graft efficiency of the vinyl acetate polymer was 73% by weight, and the xylene-insoluble content was 16.3% by weight. In addition, no phase separation or delamination was observed in the plate press-molded according to Example 13.

Example 44 A grafted precursor was produced according to the procedure of Example 13. Then, as a low density ethylene polymer to be kneaded with the grafting precursor, trade name "Sumikasen G-201" (density 0.919 g / c
Using 50 g of m ³ and Sumitomo Chemical Co., Ltd., mixed with 50 g of the grafting precursor, a graft resin composition was produced according to Example 13. At this time, the graft efficiency of the styrene-based polymer was 74% by weight, and the xylene-insoluble content was 9.8% by weight. No phase separation was observed in the plate press-molded according to Example 13. However, a slight delamination phenomenon was observed on the fracture surface.

Comparative Example 4 A grafted precursor was produced in the same manner as in Example 13. Then 0.5 g of this grafted precursor, low density ethylene polymer
50 g, "Dialex HF-55" used in Example 23 49.5 g
Were mixed, and a graft resin composition was produced according to Example 13. At this time, the graft efficiency of the styrene polymer is 0.
3% by weight and xylene insolubles were 0.1% by weight. Also,
A phase separation phenomenon was observed in the plate press-molded according to Example 13, and a large delamination phenomenon also occurred in the fracture surface.

Comparative Example 5 The grafting reaction was tried according to Example 13 except that the kneading temperature of the grafting precursor and the polymer in Example 13 was changed to 90 ° C. However, melt-kneading was impossible because the kneading temperature was low.

Comparative Example 6 The grafting reaction was carried out in the same manner as in Example 13 except that the kneading temperature of the grafting precursor and the polymer was 320 ° C. As a result, the resin was decomposed during the grafting reaction, and the obtained graft resin composition was colored brown.

Comparative Example 7 The grafting reaction was carried out in the same manner as in Example 13 except that the grafting precursor was produced without using t-butylperoxymethacryloyloxyethyl carbonate. As a result, the graft efficiency of the styrene polymer was 7% by weight, and the xylene insoluble content was 2.8% by weight. However, a slight phase separation phenomenon was observed in the plate press-molded according to Example 13, and a large delamination phenomenon appeared on the fracture surface. That is, the effect of t-butylperoxymethacryloyloxyethyl carbonate, which is a radical (co) polymerizable organic peroxide, was clearly confirmed.

Examples 45 to 49 In place of the ethylene-based (co) polymer for the grafting precursor in Example 1, various ethylene-based (co) polymers shown in Table 8 were used, and the time for impregnation was 1 Each grafting precursor was obtained in the same manner as in Example 1 except that the time was changed from 2 hours to 2 hours, and the polymerization temperature during the production of the grafting precursor was also changed to the temperatures shown in Table 8.

These grafted precursors were extracted with ethyl acetate at room temperature for 7 days to obtain a styrene polymer solution, which was put into methanol to obtain a white powdery styrene polymer.

The amount of active oxygen of this styrene polymer was measured according to Example 1, and the results are shown in Table 8.

Then, xylene-insoluble matter was measured and the results are shown in Table 8.

Furthermore, using these grafted precursors, Example 1
The grafting reaction was carried out according to.

For each of the obtained graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene polymer were measured according to Example 1 and the results are shown in Table 8.

The graft efficiency represents the ratio of grafted polystyrene to the total polymerized polystyrene.

Examples 50 to 53 The grafting reaction was performed in the same manner as in Example 1 except that the grafting precursors obtained in the intermediates of Examples 45 to 48 were used and the kneading temperature was changed from 180 ° C. as shown in Table 9. Then, the graft efficiency and xylene insoluble content of each styrene polymer were measured. The results are shown in Table 9.

Examples 54 to 57 Using the grafted precursors obtained in the intermediates of Examples 45 to 48, the kneading machine was a Labo Plastomill B-75 type mixer.
The grafting reaction was carried out in the same manner as in Example 1 except that the kneading machine shown in 10 was used to obtain each graft resin composition.

For each, the graft efficiency of the styrenic polymer and
The xylene-insoluble matter was measured and the results are shown in Table 10.

Examples 58 to 61 In Example 1, the blending amounts of benzoyl peroxide, t-butylperoxymethacryloyloxyethyl carbonate, and each ethylene-based (co) polymer of styrene used for producing the grafted precursor are shown in Table 11. Instead of the above, the grafted precursor was manufactured in the same manner as in Example 1 except for the above.

A graft resin composition was obtained in the same manner as in Example 1 except that the grafted precursors were used.

With respect to each of the graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene polymer were measured according to Example 1, and the results are shown in Table 11.

Examples 62 to 73 A grafted precursor was prepared according to Example 1 except that styrene was changed as shown in Table 12 as the ethylene-based (co) polymer used in the preparation of the grafted precursor,
Then, a graft resin composition was obtained in the same manner as in Example 1 using each of the grafted precursors.

For each of the obtained graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene-based polymer were measured according to Example 1, and the results are shown in Table 12.

Examples 74 to 77 Example 1 was repeated except that the ethylene-based (co) polymer of styrene and t-butylperoxymethacryloyloxyethyl carbonate used in the preparation of the grafting precursor was changed as shown in Table 13. A grafted precursor was produced according to

A graft resin composition was obtained according to Example 1 using each of the grafted precursors.

The graft efficiency and the xylene-insoluble content of the vinyl acetate polymer were measured for each of the graft resin compositions by the method according to Example 1 and the results are shown in Table 13.

Examples 78 to 80 In Example 1, the low-density ethylene polymer as the ethylene-based (co) polymer used for producing the grafted precursor was
Epoxy group-containing ethylene copolymer in Example 78, ethylene-acrylic acid ester copolymer in Example 79, and in Example 80 ethylene-vinyl acetate copolymer instead of powdered by freeze pulverization The grafting reaction was carried out in the same manner as in Example 1 except that the graft resin compositions were obtained. As a result, the graft efficiency and the xylene-insoluble matter of the styrene polymer are shown in Table 14.

Example 81 The epoxy group-containing ethylene copolymer of Example 45 was treated with ethylene.
A grafting precursor was produced and a grafting reaction was carried out in the same manner as in Example 45 except that the composition was changed to 82% by weight, 12% by weight of glycidyl methacrylate and 6% by weight of vinyl acetate.

As a result, the graft efficiency of the styrene-based polymer was 79.5 and the xylene-insoluble content was 19.8% by weight.

Example 82 In Example 46, a copolymer of ethylene-acrylic acid ester copolymer consisting of 95% by weight of ethylene and 5% by weight of ethyl acrylate (trade name “Nisseki Lexuron EEA A-3
050 ", manufactured by Nippon Petrochemical Co., Ltd., except that the grafting precursor was manufactured according to Example 46 and the grafting reaction was carried out.

As a result, the graft efficiency of the styrene polymer was 76.7% by weight, and the xylene insoluble content was 18.8% by weight.

Example 83 In Example 47, the ethylene-vinyl acetate copolymer was replaced with a copolymer consisting of 72% by weight of ethylene and 28% by weight of vinyl acetate (trade name "Evaflex 260", manufactured by Mitsui Polychemical Co., Ltd.). A grafting precursor was produced and a grafting reaction was carried out in the same manner as in Example 47 except for the above.

As a result, the graft efficiency of the styrene polymer was 84.8% by weight, and the xylene insoluble content was 27.4% by weight.

Comparative Examples 8-11 Grafted precursors prepared according to Examples 45-49
When the grafting reaction was attempted at a rotation speed of 50 RPM using a Labo Plastomill B-75 type mixer at 1 ° C for 1 hour,
The system did not melt and could not be kneaded.

Further, at that time, the graft efficiency of the styrene-based polymer was measured according to Example 1, and the graft efficiency was found to be Comparative Example 8.
6.2 wt%, Comparative Example 9 3.1 wt% and Comparative Example 10 2.7
The reaction was inadequate because the content was wt%.

Comparative Examples 12 to 15 The grafting reaction was performed according to Comparative Examples 8 to 11 except that the temperature of the grafting reaction was 320 ° C. in Example 1.

As a result, decomposition of the grafted precursor occurs in both cases,
Coloring of the resin occurred.

Comparative Examples 16 to 19 In Examples 45 to 48, t-butylperoxymethacryloyloxyethyl carbonate was not used, and the other Example 45 was used.
Each of the grafting precursors was produced in accordance with ˜48 and the grafting reaction was performed.

As a result, in the epoxy group-containing ethylene copolymer system of Comparative Example 16, the graft efficiency of the styrene-based polymer was 3.2% by weight,
The xylene insoluble content was 0% by weight, and in Comparative Example 17 using the ethylene-ethyl acrylate copolymerization system, the graft efficiency of the styrene polymer was 1.2% by weight, and the xylene insoluble content was 0% by weight.
In Comparative Example 18 of the ethylene-vinyl acetate copolymer system, the graft efficiency of the styrene polymer was 1.9% by weight, the xylene insoluble content was 0% by weight, and the comparison using the ethylene-propylene-diene copolymer rubber system was made. In Example 19, the graft efficiency of the styrene-based polymer was 1.9% by weight, and the xylene-insoluble content was 0.
%, And the effect of t-butylperoxymethacryloyloxyethyl carbonate was clearly confirmed.

Examples 84-88 50 g of granules of various grafting precursors obtained in Examples 45-49
Further, a grafting reaction was carried out in the same manner as in Example 13 except that 50 g of the ethylene copolymer shown in Table 15 was further added to obtain each graft resin composition.

The grafting efficiency and the xylene-insoluble content of each of the graft resin compositions were measured by the method according to Example 1 and the results are shown in Table 15.

Then, these graft resin compositions were used in Example 13
A plate having a thickness of 2 mm similar to that was prepared. As a result, the appearance was uniform white and no phase separation was observed.

Further, when the plate was broken, no delamination was observed in any of them.

Examples 89 to 92 In Examples 84 to 87, except that the mixing amounts of the grafting precursor and the ethylene-based (co) polymer for producing the graft resin composition were changed as shown in Tables 16 to 19, respectively. Examples 84-87
Each graft resin composition was manufactured according to the above.

The graft efficiency and the xylene insoluble content of the styrene polymer were measured for each of the obtained graft resin compositions according to Example 1, and the appearance of the press-molded plates at 200 ° C. is shown in Tables 16 to 19, respectively.

Examples 93 to 96 In Examples 84 to 87, graft resin compositions were produced according to Examples 84 to 87 except that the kneading temperature was changed from 180 ° C as shown in Table 20. The grafting efficiency and xylene insoluble content of each styrenic polymer were measured.
Table 20 shows the appearance of the press-formed plate at 0 ° C.

Examples 97 to 100 In Examples 84 to 87, the kneading machine was Labo Plastomill B-
The grafting reaction was carried out in the same manner as in Examples 84 to 87 except that the kneading machine shown in Table 21 was used instead of the 75-type mixer to obtain each graft resin composition.

Table 21 shows the characteristics of each graft resin composition and the appearance of the press-molded plate.

Examples 101 to 104 In Examples 84 to 87, a styrene polymer (trade name "Dialex HF-55" manufactured by Mitsubishi Monsanto Chemical Co., Ltd. as a vinyl polymer instead of an ethylene-based (co) polymer mixed with a grafting precursor is used. Graft resin compositions were obtained in the same manner as in Examples 84 to 87 except that those manufactured by Co., Ltd. were used.

Table 22 shows the characteristics of each of the graft resin compositions and the appearance of the press-molded plate.

Examples 105-108 In Examples 101-104, each graft was prepared according to Examples 101-104 except that the mixing amounts of the grafting precursor and the styrene polymer were changed as shown in Tables 23-26, respectively. A resin composition was produced.

With respect to each of the obtained graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene polymer were measured according to Example 1, and the appearance of the press-molded plate at 200 ° C. is shown in Tables 23 to 26, respectively.

In addition, the grafting precursor / styrene polymer in Tables 23 to 26 =
As seen in 25/75 and 5/95, when the styrene-based polymer is used as a matrix, the graft efficiency of the styrene-based polymer to the ethylene-based copolymer becomes low in calculation, but the ethylene in the dispersion layer is used. The system-based copolymer is considered to be grafted to the styrene-based polymer at a considerably high rate.

Examples 109 to 112 In Examples 84 to 87, 500 g of ethylene-based copolymer 700 g used for producing the grafted precursor and 500 g of styrene 300 g are used.
To 1.5 g of benzoyl peroxide, and t-butyl peroxymethacryloyloxyethyl carbonate.
Each grafted precursor was produced according to Examples 84 to 87 except that 6 g was replaced with 9 g.

Then, the mixing amounts of the grafting precursor, the ethylene-based copolymer and styrene were changed as shown in Tables 27 to 30, and other conditions were followed to obtain a graft resin composition according to Polymerization 84 to 87.

The graft ratio and the xylene-insoluble content of each of the graft resin compositions were measured by the same method as in Example 1, and the appearance of the plates formed by press molding at 200 ° C. is shown in Tables 27-30.

Examples 113 to 116 Examples 84 to 87 are the same as Examples 84 to 87, except that styrene used for preparing the grafted precursor is replaced with methyl methacrylate and 0.6 g of n-dodecyl mercaptan is additionally used as a molecular weight modifier. The grafted precursors were produced in the same manner.

Except that the mixing amount of each grafted precursor and ethylene-based polymer and methyl methacrylate polymer (trade name "Delpet 50N", manufactured by Asahi Kasei Co., Ltd.) was changed as shown in Tables 31 to 34. Graft resin compositions were produced according to Examples 84-87.

The results are shown in Tables 31-34.

Examples 117 to 120 In Examples 84 to 87, except that 300 g of styrene was replaced with a mixed monomer of 210 g of styrene and 90 g of acrylonitrile, and 0.6 g of n-dodecyl mercaptan was additionally used as a molecular weight modifier. The grafted precursors were produced in the same manner.

Separately, in 500 g of a 1% polyvinyl alcohol aqueous solution, a mixed solution of 70 g of styrene, 30 g of acrylonitrile, 0.2 g of n-dodecyl mercaptan and 0.5 g of benzoyl peroxide was added, and the mixture was maintained at a temperature of 80 to 85 for 7 hours to complete the polymerization,
Acrylonitrile-styrene copolymers were obtained respectively.

Graft resin compositions were obtained in the same manner as in Examples 84 to 87 except that the blending amounts of the copolymer, the grafting precursor and the ethylene copolymer were changed as shown in Tables 35 to 38.

The results of the obtained graft resin composition are shown in Tables 35 to 38, respectively.

Examples 121 to 124 According to Examples 84 to 87, the grafted precursors were respectively prepared according to Examples 84 to 87, except that 300 g of styrene was replaced by a mixed monomer of 210 g of ethyl methacrylate and 90 g of n-butyl acrylate. Manufactured.

Then, using these grafting precursor 50g and the ethylene-based copolymer 50g shown in the following table, respectively, Examples 84-87.
A graft resin composition was obtained according to the above.

The results of each of the obtained graft resin compositions are shown in Table 39.

Examples 125-128 In Examples 84-87, 300 g of styrene was added to 300 g of vinyl acetate.
And the grafted precursors were respectively prepared according to Examples 84 to 87 except that 6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butylperoxyallyl carbonate.

Then, 50 g of these grafting precursors and 50 g of each of the same ethylene copolymers as those used for the grafting precursors were used to obtain graft resin compositions according to Examples 84 to 87.

Further, the grafting efficiency was measured by changing the extraction solvent from ethyl acetate to methanol, and the results are shown in Table 40.

Example 129 A grafted precursor was prepared according to Example 84.

Next, as the epoxy group-containing ethylene copolymer to be kneaded with this grafting precursor, 50 g of a copolymer composed of 82% by weight of ethylene, 12% by weight of glycidyl methacrylate and 6% by weight of vinyl acetate was used. 50 g were mixed and a graft resin composition was produced according to Example 84.

At this time, the graft efficiency of the styrene-based polymer was 55.5% by weight, and the xyle insoluble content was 14.5% by weight.

Further, no phase separation was observed in the plate press-formed according to Example 841, but slight delamination was observed on the fault plane.

Example 130 In Example 85, a copolymer of ethylene-ethyl acrylate copolymer consisting of 95% by weight of ethylene and 5% by weight of ethyl acrylate (trade name “Nisseki Lexulon EEA A-305
0 ", manufactured by Nippon Petrochemical Co., Ltd.)
A graft resin composition was produced according to 5. as a result,
The graft efficiency was 49.5% by weight, and the xylene insoluble content was 9.7% by weight.

Example 131 In Example 86, the ethylene-vinyl acetate copolymer was replaced with a copolymer composed of 72% by weight of ethylene and 28% by weight of vinyl acetate (trade name "Evaflex 260", manufactured by Mitsui Polychemical Co., Ltd.). A graft resin composition was produced in the same manner as in Example 86 except for the above. As a result, the graft efficiency was 53.3% by weight and the xylene insoluble content was 10.5% by weight.

Comparative Examples 20-23 Grafted precursors were produced according to Examples 84-87.

Next, 0.5 g of each of these grafted precursors and 50 g of an ethylene-based copolymer similar to that used in the production of each grafted precursor, and the same styrene polymer 4 used in Example 101.
9.5 g were mixed with each other to prepare a graft resin composition according to Examples 84 to 87. At this time, the graft efficiency of the styrene-based polymer was 0.3% by weight, 0.4% by weight, 0.9% by weight, 0.7% by weight in order from Comparative Example 20, and the xylene-insoluble content was 0.1% by weight, 0.4% by weight, respectively. 0.3% by weight, 0.2% by weight
Met. Phase-separation was observed in all of the press-formed plates, and a large delamination phenomenon occurred on the fracture surface.

Comparative Examples 24-27 In Examples 84-87, the grafting reaction was tried according to Examples 84-87, except that the kneading temperature of the grafting precursor and the ethylene copolymer were both 90 ° C. . However, melt-kneading was impossible because the kneading temperature was low.

Comparative Examples 28 to 31 In Examples 84 to 87, except that the kneading temperature of the grafting precursor and the ethylene-based copolymer was 320 ° C, Example 84
Grafting reaction was performed according to ~ 87. As a result, the resin was decomposed during the grafting reaction, and the obtained resin composition was colored brown.

Comparative Examples 32-35 In Examples 84-87, the grafting reaction was carried out according to Examples 84-87, respectively, except that the grafting precursor was produced without using t-butylperoxymethacryloyloxyethyl carbonate. I did. As a result, the graft efficiency of the styrene-based polymer was 0.1 in order from Comparative Example 32, respectively.
%, 0% by weight, 0.2% by weight, 0% by weight, and the xylene-insoluble content was 0% by weight. In addition, phase separation was observed in all of the press-molded plates, and large delamination phenomenon also appeared in the fracture surface. From this, it is apparent that the radical (co) polymerizable organic peroxide is t. The effect of -butylperoxymethacryloyloxyethyl carbonate was confirmed.

 ─────────────────────────────────────────────────── --Continued from the front page (31) Priority claim number Japanese patent application Sho 62-199613 (32) Priority date Sho 62 (1987) August 10 (33) Country of priority claim Japan (JP) (31) Priority Claim Number Japanese Patent Application Sho 62-199614 (32) Priority Date Sho 62 (1987) August 10 (33) Priority Claim Country Japan (JP) (31) Priority Claim Number Japanese Patent Application Sho 62-199616 (32) Priority Japan Sho 62 (1987) August 10 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese patent application Sho 62-199617 (32) Priority date Sho 62 (1987) August 10 (33) ) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. Sho 62-199619 (32) Priority date Sho 62 (1987) August 10 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. Sho 62-199620 (32) Priority date Sho 62 (1987) August 10 (33) Country of priority claim Japan (JP)

Claims (16)

[Claims] 1. A grafting precursor obtained by the following method or 1 to 99% by weight of the grafting precursor and the following polymer 99 to
A method for producing a graft resin composition, which comprises performing a grafting reaction by kneading a mixture consisting of 1% by weight at 100 to 300 ° C. while kneading. The grafting precursor is an ethylene-based (co) polymer 10
0 parts by weight was suspended in water, and separately selected from the group consisting of vinyl aromatic monomer, (meth) acrylic acid ester monomer, (meth) acrylonitrile and vinyl ester monomer. 5 kinds or two or more kinds of vinyl monomers
To 400 parts by weight, one or a mixture of two or more radical (co) polymerizable organic peroxides represented by the following general formula (I) or (II) is added to 100 parts by weight of the vinyl monomer. 0.1 ~ 10
40 parts by weight and decomposition temperature to obtain a half-life of 10 hours
Radical polymerization was performed by adding a solution in which 0.01 to 5 parts by weight of a radical polymerization initiator at 90 ° C. was dissolved with respect to 100 parts by weight of the total of the vinyl monomer and the radical (co) polymerizable organic peroxide. It is heated under conditions where the decomposition of the initiator does not substantially occur, and the ethylene monomer (co) polymer is impregnated with the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator. When the total amount of the vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator becomes less than 50% by weight at the beginning, the temperature of the aqueous suspension is raised to increase the vinyl monomer. And radicals
A resin composition obtained by copolymerizing a polymerizable organic peroxide in an ethylene (co) polymer. The radical (co) polymerizable organic peroxide represented by the general formula (I) is a compound represented by the formula: (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, and R ₅ is a carbon atom having 1 carbon atom. To 12 alkyl group, phenyl group, alkyl-substituted phenyl group, or cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2.). Further, the radical (co) polymerizable organic peroxide represented by the general formula (II) has the formula (Wherein, _{R 6} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, _{R 7} is a hydrogen atom or a methyl group, each _{R 8} and _{R 9} is an alkyl group having 1 to 4 carbon _{atoms, R 1 0} is the number of carbon atoms 1-12
Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1
Or 2. ) Is a compound represented by. The polymer forming a mixture with the grafted precursor,
Ethylene-based (co) polymers, vinyl aromatic monomers,
Any one of vinyl polymers obtained by polymerizing one or more vinyl monomers selected from the group consisting of (meth) acrylic acid ester monomers, (meth) acrylonitrile and vinyl ester monomers. It is a polymer composed of one or both. 2. The ethylene-based polymer has a density of 0.910 to 0.935 g / c.
The method for producing a graft resin composition according to claim 1, which is a low-density ethylene polymer having m ³ . 3. The ethylene-based copolymer is ethylene and (meth).
The method for producing a graft resin composition according to claim 1, which is an epoxy group-containing ethylene copolymer obtained by copolymerizing with glycidyl acrylate. 4. The epoxy group-containing ethylene copolymer obtained by copolymerizing 60 to 99.5% by weight of ethylene and 0.5 to 40% by weight of glycidyl (meth) acrylate. A method for producing the described graft resin composition. 5. The ethylene-based copolymer is ethylene and (meth).
The method for producing a graft resin composition according to claim 1, which comprises an acrylic ester. 6. The method for producing a graft resin composition according to claim 1, wherein the ethylene-based copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of a (meth) acrylic acid ester. 7. The method for producing a graft resin composition according to claim 1, wherein the ethylene-based copolymer comprises ethylene and a vinyl ester. 8. The method for producing a graft resin composition according to claim 7, wherein the vinyl ester is vinyl acetate. 9. The method for producing a graft resin composition according to claim 1, wherein the ethylene-based copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of a vinyl ester. 10. The method for producing a graft resin composition according to claim 1, wherein the ethylene-based copolymer is an ethylene-propylene copolymer rubber. 11. The method for producing a graft resin composition according to claim 1, wherein the ethylene-based copolymer is an ethylene-propylene-diene copolymer rubber. 12. The monomer composition of the ethylene (co) polymer kneaded with the grafting precursor is the same as the monomer composition of the ethylene (co) polymer in the grafting precursor. A method for producing the graft resin composition according to claim 1. 13. The graft resin composition according to claim 1, wherein the density of the low density ethylene polymer kneaded with the grafting precursor is the same as the density of the low density ethylene polymer in the grafting precursor. Manufacturing method. 14. The method for producing a graft resin composition according to claim 1, wherein 50% by weight or more of the vinyl monomer used for producing the grafting precursor comprises a vinyl aromatic monomer. 15. The graft resin composition according to claim 1, wherein 50% by weight or more of the vinyl monomer used for producing the grafting precursor is composed of a (meth) acrylic acid ester monomer. Production method. 16. The graft resin according to claim 1, wherein the monomer composition of the vinyl polymer kneaded with the grafting precursor is the same as the monomer composition of the vinyl polymer in the grafting precursor. A method for producing a composition.