JPH01138214A - Preparation of graft resin composition - Google Patents

Abstract

PURPOSE:To obtain a graft resin compsn. useful for adhesives, coatings, modifiers, etc., with a high grafting efficiency, by melting and kneading a specified graft precursor at a specified temp. CONSTITUTION:A grafting precursor (P) or a mixture of 1-99wt.% precursor P with 99-1wt.% ethylne (co)polymer is melted and kneaded at 100-300 deg.C. The precursor P is a resin compsn. obtd. by suspending 100 pts.wt. ethylene (co)polymer (A) in water, adding a soln. wherein 0.1-10 pts.wt. radical-(co) polymerizable org. peroxide (C) of formula I or II based on 100 pts.wt. vinyl monomer (B) such as vinyl arom. monomer or (meth)acrylonitrile and 0.01-5 pts.wt. radical polymn. initiator (D) having a decomposition temp. of 40-90 deg.C for obtaining a half life period of 10hr based on 100 pts.wt. sum of B and C are dissolved in 5-400 pts.wt. vinyl monomer (B), heating the mixture under a condition where decomposition of D does not occur to impregnate A with B, C and D, elevating the temp. of this aq. suspension when the sum of free B, C and D becomes less than 50wt.% of the initial amt. to copolymerize B and C in A.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to adhesives, coating agents, modifiers, microdispersion aids or polymer alloying agents, saturable molded body materials, and polymer compatibilizers. The present invention relates to a method for producing a grafted resin composition with high grafting efficiency, which is useful as such.

[Conventional technology]

Ethylene-based (co)polymers have been widely used since they have excellent properties, and they are also being modified and applied to new uses.

As an ethylene-based (co)polymer, for example, low-density ethylene polymer has poor moldability and physical properties of molded products.

It has also been used as a molding material because of its good chemical properties.

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

Furthermore, it is well known that epoxy group-containing ethylene copolymers exhibit good adhesive strength as adhesives between metals and plastic materials due to their polarity.

Furthermore, due to its elastic properties and reactivity,
It is also used as an impact modifier by reacting with condensation polymers, especially engineering plastics.

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

Further, in recent years, attempts have been made to use double-valve polymers as impact modifiers for engineering plastics.

Furthermore, ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber has excellent rubber elasticity,
Because it has flexibility, cold resistance, and weather resistance, it is widely used mainly as a rubber material, and recently it has also been attempted to be used as an impact modifier for engineering plastics.

However, blends of ethylene (co)polymers and vinyl polymers generally have poor compatibility, so blending more than 10% by weight of vinyl polymers is not done, and usually 0.2 to 10% by weight. Only 5% by weight of vinyl polymer was blended.

Even when such a small amount of vinyl polymer was blended, the blended product tended to have lower impact resistance and poor appearance due to poor compatibility between the two resins. When used as an impact modifier for engineering plastics, it has also been problematic because it has low compatibility and dispersibility, and a sufficient effect of improving impact resistance cannot be obtained.

For example, in the case of an epoxy group-containing ethylene copolymer,
The scope of its application is limited to substrates that react with epoxy groups. For example, for substrates that do not react with epoxy groups, such as vinyl polymers, sufficient adhesive strength may not be obtained or the dispersion force against the substrate may be low. Sufficient impact resistance could not be obtained.

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

For example, attempts have been made to increase the compatibility with engineering plastics by increasing the ratio of (meth)acrylic ester and vinyl ester in ethylene-(meth)acrylic ester copolymers and α-olefin-vinyl ester copolymers. be. Furthermore, functional groups such as epoxy groups, carboxyl groups, and acid anhydride groups are introduced into the copolymer and reacted with the remaining functional groups of engineering plastics, especially condensed engineering plastics, to increase compatibility and improve impact resistance. Attempts are also being made to improve the improvement effect.

On the other hand, in order to improve compatibility with other resins, a graft copolymer in which a polymer with high compatibility with other resins and a polymer with the desired function are chemically bonded in one molecule is used. It is known that coalescence is preferred.

In general, as a method for grafting a vinyl polymer onto an ethylene (co)polymer, a vinyl polymer, such as a styrene polymer, is graft-polymerized onto an ethylene (co)polymer by irradiation with ionizing radiation. 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 (Japanese Patent Publication No. 58-51010, Japanese Patent Publication No. 58-530).
Publication No. 03).

According to this method, the vinyl polymer is uniformly blended in the resin composition after polymerization, and this method provides preferable results compared to 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 ionizing radiation is a special method called radiation graft polymerization, there are economical problems and it is difficult to put it into practical use.

Furthermore, this method is not preferred because there is a limit to the amount of vinyl monomer that can be introduced.

Next, in the solution graft polymerization method, from the viewpoint of solubility of the ethylene (co)polymer, polymerization is performed while diluted in a large amount of solvent. It has the disadvantage that there are few opportunities for mutual contact between the polymers, - the reaction efficiency of the vinyl monomer in the membrane is low, and the post-processing steps such as solvent recovery are complicated, so it is economically disadvantageous. .

Furthermore, there is also an emulsion graft polymerization method, but in this case, the reaction is limited to only the surface reaction of the ethylene (co)polymer particles, so it has the disadvantage that the homogeneity of the product is poor.

Furthermore, in the polymerization method using an aqueous suspension system, the grafting efficiency of the resin composition obtained by this method is low. Secondary aggregation of particles is likely to occur, which poses a problem when the resulting resin composition is used as a microdispersion aid, a polymer alloying agent, or a polymer compatibilizer.

[Means to solve the problem]

The present inventors aimed to obtain grafted resin compositions with high grafting efficiency of these conventional ethylene (co)polymers and vinyl polymers, and to As a result of extensive research aimed at increasing grafting efficiency and preventing secondary agglomeration of the dispersed phase during secondary processing, we found that by kneading a specific grafting precursor under melting conditions at a specific temperature, we were able to dramatically improve grafting efficiency. The inventors have discovered that a resin composition with a high viscosity can be obtained, and have completed the present invention.

That is, in the present invention, a grafted precursor obtained by the following method or a mixture consisting of 1 to 99% by weight of the grafted precursor and 99 to 1% by weight of the following polymer is
The present invention relates to a method for producing a grafted resin composition, characterized in that a grafting reaction is carried out by kneading in a melted state at .degree.

The grafting precursor is an ethylene (co)polymer 1
00 parts by weight were suspended in water, and separately, vinyl aromatic monomer, (meth)acrylic acid ester monomer, (
one or more vinyl monomers selected from the group consisting of meth)acrylonitrile and vinyl ester monomers 5
~400 parts by weight of one or a mixture of two or more radical (co)polymerizable organic peroxides represented by the following general formula (1) or (II) based on 100 parts by weight of the above vinyl monomer. 0.1 to 10 parts by weight of a radical polymerization initiator whose decomposition temperature is 40 to 90°C to obtain a half-life of 10 hours is added to the vinyl monomer and the radical (co)polymerizable organic peroxide. A solution containing 0.01 to 5 parts by weight per 100 parts by weight of the total is added and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, resulting in vinyl monomer and radical (co)polymerization. The content of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is When the amount is less than 50% by weight, the temperature of the aqueous suspension is raised to copolymerize the vinyl monomer and the radical (co)polymerizable organic peroxide in the ethylene (co)polymer. 6. The radical (co)polymerizable organic peroxide represented by the general formula (I) is a resin composition obtained by formula % (where R1 is a hydrogen atom or a carbon number of 1 to 2). Alkyl group, R2 is a hydrogen atom or a methyl group, Ro and R4 are each an alkyl group having 1 to 4 carbon atoms, Rs 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. represents a cycloalkyl group. m is 1 or 2.) In addition, the radical (co)polymerizable organic peroxide represented by the general formula (n) is the formula % formula % (wherein R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R7 is a hydrogen atom or a methyl group, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R□.

represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0.1 or 2. ) The polymer forming the mixture with the grafting precursor is (i) ethylene-based (co)polymer, (ii) vinyl aromatic monomer, (meth)acrylic acid ester monomer, (meth) It is a polymer consisting of one or both of vinyl polymers obtained by polymerizing one or more vinyl monomers selected from the group consisting of acrylonitrile and vinyl ester monomers.

The ethylene (co)polymer used in the present invention is 1
For example, low-density ethylene polymer, epoxy group-containing ethylene copolymer obtained by copolymerizing ethylene and (glycidyl methacrylate), ethylene copolymer consisting of ethylene and (meth)acrylic ester, ethylene and vinyl These include ethylene copolymers consisting of esters, ethylene-propylene copolymer rubbers, ethylene-propylene-diene copolymer rubbers, and the like.

The low density ethylene polymer used in the present invention has a density of 0.
．． 910 to 0.935 g/cm, specifically, ethylene homopolymer obtained by high-pressure polymerization, ethylene and α-olefin for density adjustment, such as propylene, butene-1°pentene- Examples include copolymers with No. 1 and the like.

The shape of this low-density ethylene polymer may be pellets with a particle size of 1 to 5 mm, or powder. It is preferable to use these appropriately depending on the blending ratio of the low density ethylene polymer in the grafting precursor. For example, if the low density ethylene polymer in the grafting precursor is
When it is 0% by weight or more, it is preferable to use pellets, and when it is less than 50% by weight, it is preferable to use powder.

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

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

The copolymerization ratio of glycidyl (meth)acrylate is 0.5
-40% by weight, preferably 2-20% by weight. If the amount of copolymerization is less than 0.5% by weight, the effect will not be sufficient when used as an impact resistance improver. Also 40% by weight
If it exceeds this, the fluidity during melting will decrease, which is not preferable.

In addition, the copolymerization ratio of glycidyl (meth)acrylate is 4
If the weight is less than 0 weight, methyl (meth)acrylate, (
(meth)acrylic acid ester monomers such as ethyl acrylate, vinyl ester monomers such as vinyl acetate and vinyl propionate, vinyl ether monomers, (meth)
It is also possible to copolymerize one or more of acrylonitrile, a vinyl aromatic monomer, -carbon oxide, etc., and these are included in the present invention.

Specifically, epoxy group-containing ethylene copolymers include, for example, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, and ethylene/glycidyl methacrylate copolymer. /-carbon oxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, and the like. Among them, ethylene/glycidyl methacrylate copolymer is preferred.

These epoxy group-containing ethylene copolymers can also be used in combination.

In addition, 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. It is preferable to use these appropriately depending on the blending ratio of the epoxy group-containing ethylene copolymer in the grafting precursor.

If the particle size is too large, not only will it be difficult to disperse during polymerization, but there will also be a drawback that it will take a long time to impregnate vinyl monomer and the like.

Specifically, the ethylene-(meth)acrylate copolymer used in the present invention includes ethylene-methyl(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, and ethylene-(meth)acrylate copolymer. (Meth)butyl acrylate copolymer may be mentioned. Preferred is ethylene-ethyl acrylate co-7 mineral combination.

At this time, it is preferable that ethylene is 50 to 99% by weight.

In the ethylene-(meth)acrylic acid ester copolymer, (
The copolymerization ratio of the meth)acrylic acid ester is 1 to 50% by weight, or 2 to 40% by weight. Copolymerization ratio is 1
If the content is less than %, the effect will not be sufficient when used as an impact resistance improver.

Moreover, when it exceeds 50 heavy electron microscopy, moldability deteriorates, which is not preferable.

Further, 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 refers to ethylene and vinyl esters such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. It is copolymerized with one or more 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 ester in the ethylene-(meth)acrylic ester copolymer.

Further, 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 a propylene content of 60 to 20% by weight.
Weight%, Mooney viscosity, 5-9o ethylene-
Propylene copolymer rubber and ethylene content 40-80
In terms of weight%, propylene is 60 to 20% by weight, and the rubber is ternary copolymerized with ethylidene norbornene: 1,4-hexadiene: dicyclopentadiene, etc. as a non-conjugated diene component, and the content of the diene is is 4~ with iodination
30, and a Mooney viscosity of 15 to 120 is suitable.

In addition, Mooney viscosity is JISK6300 (100℃
).

These ethylene-propylene copolymer rubbers or ethylene-propylene-diene copolymer rubbers can also be used in combination.

In order to facilitate impregnation with vinyl monomer and prevent agglomeration during suspension polymerization, 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 2. Preferably, the pellets are about 8 mm in size.

If the particle size is too large, not only will it be difficult to disperse during polymerization, but the impregnation rate of the vinyl monomer will be slow, resulting in a prolonged reaction time.

The vinyl monomer used in the present invention is specifically a vinyl aromatic monomer, such as styrene; nuclear substituted styrene, such as methylstyrene; dimethylstyrene; ethylstyrene; isopropylstyrene; chlorostyrene; α
-Substituted styrenes such as α-methylstyrene; α-ethylstyrene; (meth)acrylic acid ester monomers, such as C1-7 alkyl esters of (meth)acrylic acid; (meth)acrylonitrile; vinyl ester monomers , for example, vinyl propionate; vinyl acetate; vinyl caproate; vinyl caprylate; vinyl laurate; vinyl stearate; (In particular, vinyl chloride, vinylidene chloride), vinyl naphthalene, vinyl carbazole, acrylamide, methacrylamide, maleic anhydride, and others may also be used, and may be used alone or in combination of two or more.

Among these, vinyl aromatic monomers and (meth)acrylic acid ester monomers are preferred.

These are especially Nm'B of engineering plastics.
When used as a property improver, it is preferable to (co)polymerize a mixture containing 50% by weight or more of a vinyl aromatic monomer or a (meth)acrylic acid ester monomer. The reason is that it has good compatibility with engineering plastics. In particular, hydrophilic or solid vinyl monomers are preferably used dissolved in oil-soluble monomers.

The amount of vinyl ll1t is 5 parts by weight per 100 parts by weight of the ethylene (co)polymer in the production of the grafting precursor.
-400 parts by weight, preferably 10-200 parts by weight. If this amount is less than 5 parts by weight, the grafted precursor after the grafting reaction becomes difficult to exhibit its performance as a grafted precursor, although the grafting efficiency is high, which is not preferable.

In addition, when this amount exceeds 400 parts by weight, vinyl monomers, radicals (co) represented by general formula (1) or (II)
Among the polymerizable organic peroxides and radical polymerization initiators, those that are not impregnated with the ethylene-based (co)mer tend to be 50% by weight or more, which is not preferable because the amount of free vinyl-based homopolymer increases. According to Japanese Patent Publication No. 58-51010 or Japanese Patent Publication No. 58-53003, in the aqueous suspension polymerization method, this free vinyl monomer is
It is said that it is necessary that the content be less than 0% by weight.
However, in the present invention, the generated grafting precursor has a peroxy group in its vinyl polymer molecule and has grafting ability, so free vinyl monomers and general formula (I ) or (■) as long as the total amount of the radical (co)polymerizable organic peroxide and the radical polymerization initiator is 20% by weight or more but less than 50% by weight, the graft is sufficiently excellent. can show the ability to

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 a compound represented by general formula (I), t
-f-thyl peroxyacryloyloxyethyl carbonate; t-amyl peroxyacryloyloxyethyl carbonate; hat-hexyl peroxyacryloyloxyethyl carbonate; 1.1.3.3-tetramethylbutyl peroxyacryloyloxyethyl carbonate; cumyl Peroxyacryloyloxyethyl carbonate;
p-isopropylcumylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1.1
．． 3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethyl carbonate; t-butylperoxyacryloyloxyethoxyethyl carbonate; t-amylperoxy Acryloyloxyethoxyethoxyethyl carbonate; Cyhexylperoxyacryloyloxyethoxyethyl carbonate; 1.1.3.
3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethoxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethoxyethyl carbonate; t-amyl Peroxyacryloyloxyethoxyethyl carbonate; t-hexylperoxyacryloyloxyethoxyethyl carbonate; 1.1.3.3-tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl carbonate; p -isopropylcumylperoxyacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t-
amylperoxyacryloyloxyisopropyl carbonate; t-hexylperoxyacryloyloxyisopropyl carbonate; 1.1.3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacryloyloxyisopropyl carbonate; p-isopropyl cumylperoxyacryloyloxyisopropyl carbonate; t-butylperoxymethacryloyloxyisopropyl carbonate; t-amylperoxyacryloyloxyisopropyl carbonate; t-hexylperoxyacryloyloxyisopropyl carbonate; 1.1.3.3- Examples include tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacryloyloxyisopropyl carbonate; p-isopropylcumylperoxyacryloyloxyisopropyl carbonate.

Furthermore, as a compound represented by general formula (II), t
-butylperoxyallyl carbonate; t-amylperoxyallyl carbonate; t-hexylperoxyallyl carbonate; 1.1.3.3-tetramethylbutylperoxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate; t -butylperoxymethallyl carbonate; t-amylperoxymethallyl carbonate; t-
Hexylperoxymethallyl carbonate; 1.1.3
．． 3-tetramethylbutylperoxymethallyl carbonate; p-menthane peroxymethallyl carbonate;
cumylperoxymethallyl carbonate; t-butylperoxyallyloxyethyl carbonate; t-amylperoxyallyloxyethyl carbonate; t-hexylperoxyallyloxyethyl carbonate; t-butylperoxymethallyloxyethyl carbonate; t-amylperoxymethallyloxy Ethyl carbonate; t-hexylperoxyallyloxyethyl carbonate; t-
Butylperoxyallyloxyisopropyl carbonate; t-amylperoxyallyloxyisopropyl carbonate-hexylperoxyallyloxyisopropyl carbonate; t-butylperoxyallyloxyisopropyl carbonate; t-amylperoxyallyloxyisopropyl carbonate; 1=hexylperoxyallyloxyisopropyl Examples include carbonate and the like.

Among them, preferred are t-butylperoxyacryloyloxyethyl carbonate; t-butylberoxymethacryloyloxyethyl carbonate at-butylperoxyallyl carbonate; and t-butylperoxymethallyl carbonate.

The amount of the radical (co)polymerizable organic peroxide used is 0.00 parts by weight per 100 parts by weight of the vinyl monomer. It is 1 to 10 parts by weight.

When the amount used is less than 0.1 part by weight, the amount of active oxygen contained in the grafted precursor used in the present invention to be produced is small;
This is not preferable because it becomes difficult to exhibit sufficient grafting ability.

Moreover, if it exceeds 10 parts by weight, radicals (co-) may be generated during polymerization.
The polymerizable organic peroxide undergoes induced decomposition, and a large amount of gel is generated in the grafting precursor upon completion of polymerization, and although the grafting ability of the grafting precursor increases, the gel-forming ability also increases at the same time. This is not desirable because it can cause

The radical polymerization initiator used to produce the grafted precursor in the present invention has a decomposition temperature (hereinafter referred to as 10-hour half-life temperature) of 40 to 90% to obtain a 10-hour half-life.
0°C, preferably 50 to 75°C. This is because the polymerization during production of the grafting precursor in the present invention must be carried out under conditions in which the radical (co)polymerizable organic peroxide used does not decompose at all; Since the 10-hour half-life temperature of peroxide itself is 90 to 110°C, the polymerization temperature is 1
This is because the temperature has to be kept at 10°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 decompose during polymerization, which is not preferable. Further, if the temperature is lower than 40°C, polymerization will be initiated during the process of impregnating the ethylene (co)polymer with the vinyl monomer, resulting in non-uniformity of the resulting grafted precursor, which is not preferable. Here, the 10-hour half-life temperature refers to the temperature at which the decomposition rate of the polymerization initiator becomes 50% when 0.1 mol of the polymerization initiator is added to 1 liter of benzene and 10 hours elapse at a certain temperature.

Specifically, such radical polymerization initiators include:
For example, diisopropyl peroxydicarbonate (4
di-n-propyl peroxydicarbonate (40.5°C); cimilistyl peroxydicarbonate (40.9°C); di(2-nitoxyethyl) peroxydicarbonate (43.4°C) °C); di(methoxyisopropyl) peroxydicarbonate (43.5 °C);
Di(2-ethylhexyl) peroxydicarbonate (
43.5°C); t-hexyl peroxyneodecanoate (44.7°C); di(3-methyl-3-methoxybutyl) peroxydicarbonate (46.5°C); t-butyl peroxyneodecanoate (46.5℃):t-
Hexylperoxyneohexanoate (51.3℃)
;t-butylperoxyneohexanoate (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
octanoyl peroxide (62°C); lauroyl peroxide (62°C); cumyl peroxyoctoate (65°C);

Acetyl peroxide (68°C); t-Butylperoxy-2-ethylhexanoate (72.5°C)
m-toluoyl peroxide (73°C); benzoyl peroxide (74°C); -butylberoxyisobutyrate (78°C); 1,1-bis(t-butylperoxy)-3,5,5-trimethyl Cyclohexane (9
(0°C) (the value in parentheses represents the 10-hour half-life temperature).

The amount of the radical polymerization initiator used is 0.01-5 parts by weight, preferably 0.1-2. 5
Parts by weight.

If the amount used is less than 0.01 part by weight, the vinyl monomer and the radical (co)polymerizable organic peroxide will not be completely polymerized, which is not preferable. Furthermore, if the amount exceeds 5 parts by weight, intermolecular crosslinking of the ethylene (co)polymer becomes more likely to occur during one polymerization, and the radical (co)polymerizable organic peroxide becomes more susceptible to induced decomposition, which is not preferable. .

The polymerization for producing the grafted precursor in the present invention is generally carried out in an aqueous manner! @Performed by turbidity polymerization method.

Therefore, an aqueous suspension of an ethylene-based (co)polymer, a separately prepared radical polymerization initiator, and a radical (co)polymerizable organic peroxide dissolved in vinyl monomer in advance. It is stirred and dispersed in water in the presence of a suspending agent that can be used for polymerization, such as a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, etc., or a poorly water-soluble inorganic substance such as calcium phosphate, magnesium oxide, etc.

The concentration of the aqueous suspension in this case is arbitrary, but generally water 1
The reaction component is used in an amount of 5 to 150 parts by weight per 00 parts by weight.

In the present invention, it is preferable that the ethylene-based (co)polymer be impregnated with the solution at as high a temperature as possible.

However, when the radical polymerization initiator decomposes during impregnation and starts polymerization, the composition of the resulting grafted precursor becomes very heterogeneous. , it is preferable to carry out at a temperature lower than 5°C.

In addition, the total amount of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator after impregnation is:
Less than 50% by weight, preferably 2% based on the total amount initially used
It should be less than 0% by weight. If this amount is 50 weight or more, it is not preferable because the grafting ability of the grafting precursor in the present invention is extremely reduced.

The amounts of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator can be determined by sampling an arbitrary amount of the aqueous suspension and quickly filtering it using a wire mesh of about 300 mesh. The ethylene-based (co)polymer is separated into a liquid phase, and the amounts of vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator in the liquid phase are measured and calculated.

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

When this temperature exceeds 110'C and the polymerization time exceeds 5 hours, the amount of decomposition of the radical (co)polymerizable organic peroxide increases, which is not preferable. Generally, a suitable polymerization time is 2 to 20 hours.

In addition, the grafted precursor in the present invention has a vinyl polymer blended therein with an amount of active oxygen of 0.
．． 01 to 0.73% by weight.

If the amount of active oxygen is less than 0.01% by weight, the grafting ability of the grafting precursor will be extremely reduced, which is not preferable. Moreover, if it exceeds 0.73% by weight, the ability to form a gel during grafting increases, 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 in the vinyl polymer by iodometry.

The grafting resin composition of the present invention can be prepared by melting and kneading the above-mentioned grafting precursor alone or a mixture of the grafting precursor and the following polymer at a specific temperature, so that the grafting reaction can be carried out. As a result, a grafted resin composition is obtained.

In the present invention, the polymer forming the mixture with the grafting precursor is preferably the same as that used for producing the grafting precursor, and is either an ethylene (co)polymer or a vinyl polymer, or It is a polymer consisting of both.

For example, when the ethylene polymer in the grafting precursor is a low-density ethylene polymer, it is preferable that the monomer composition or density is the same.

If the monomer composition or density is different, crosstalk tends to be insufficient, and the mechanical strength and appearance of the resulting grafted resin composition may deteriorate, which is not preferable.

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

In the present invention, the vinyl polymer forming the mixture with the grafting precursor is a vinyl monomer used for producing the grafting precursor, specifically a vinyl aromatic monomer; for example, styrene, 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 Alkyl ester of acid having 1 to 7 carbon atoms; (meth)acrylonitrile; a polymer obtained by polymerizing one or more vinyl ester monomers, such as vinyl acetate and vinyl propionate. Preferably, the monomer composition is the same as that of the vinyl polymer in the grafting precursor; if the monomer composition is different, crosstalk is likely to be insufficient as described above, and the obtained graft resin composition This is undesirable as it may deteriorate the mechanical strength and appearance of the product.

When used as a mixture, the grafted resin composition of the present invention is comprised of 1 to 99% by weight of the grafting precursor and 99 to 1% by weight of the polymer kneaded therein.

If the amount of the grafting precursor is less than 1% by weight, that is, if the amount of the polymer to be kneaded exceeds 99% by weight, the amount of the grafted body in the grafted resin composition will decrease, causing delamination, etc., which is not preferable.

In producing 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 less than 100'C, the melting will be insufficient and crosstalk will be difficult, and it will take a long time to decompose the radical (co)polymerizable organic peroxide in the grafting precursor, which is not preferable.

Furthermore, if the temperature exceeds 300°C, molecular cleavage (decomposition) of the grafting precursor occurs, which is not preferable.

In the present invention, crosstalk is necessary to maintain the uniformity of the graft resin composition and to control the particle size of the dispersed phase.

In particular, if the temperature of the grafting reaction during production of the graft resin composition exceeds 200° C., agglomeration of the dispersed phase tends to occur, but this aggregation can be prevented by crosstalk.

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

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

[Effects 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 kneading machine, and the composition ratio can be changed by simply changing the blending ratio. .

In addition, since the graft resin composition obtained by the present invention has a higher content of graft bodies than conventional products, there is less aggregation of vinyl polymers during secondary processing, and adhesives, coatings, etc.
Modifier, microdispersion aid.

A graft resin composition useful as a polymer alloying agent, a functional molded body material, a polymer compatibilizer, etc. is obtained.

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

Example 1 A stainless steel autoclave with an internal volume of 5 breaths was filled with 25 liters of pure water.
00g of polyvinyl alcohol was added thereto, and 2.5g of polyvinyl alcohol was further dissolved therein as a suspending agent. In this, density 0.925
g / cm
mm) and stirred to disperse. Separately, 1.5 g of benzoyl peroxide (trade name: Niper BJ, manufactured by NOF Corporation, 10 hour half-life temperature: 74°C) was used as a radical polymerization initiator, and t-butyl peroxide was used 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 poured into the autoclave and stirred.

Next, the temperature of the autoclave was raised to 60 to 65°C, and while stirring for 1 hour, the radical polymerization initiator and the radical (
Co) A vinyl monomer containing a polymerizable organic peroxide was impregnated into a low density ethylene polymer. Next, after confirming that the content of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator was less than 50% by weight, the temperature was lowered to 80 to 85°C. The polymerization was completed by raising the temperature to 7 hours and washing with water and drying to obtain a grafted precursor.

The amount of active oxygen in the styrene polymer in this grafted precursor was measured by iodometry, and was found to be 0.13.
% by weight. Furthermore, when this grafted precursor was extracted with xylene using a Soxhlet extractor, no xylene-insoluble matter was present.

This grafted precursor was then transferred to Laboplastomil B
The grafting reaction was carried out by kneading at 180°C for 10 minutes at a rotational speed of 50 RPM using a -75 type mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The non-grafted styrenic polymer was extracted with ethyl acetate using a Soxhlet extractor from the grafted polymer, and the amount was found to be 3.3% by weight based on the total amount. Therefore,
The grafting efficiency of the styrenic polymer was calculated to be 89% by weight.

In addition, when extracted with xylene, the amount of xylene insoluble matter is 17.
Furthermore, as a result of analyzing this xylene insoluble content by pyrolysis gas chromatography, the low density ethylene polymer: styrenic polymer was 79.0% by weight:
It was 21.0% by weight.

Examples 2 to 4 In Example 1, the crosstalk temperature of the grafting precursor is shown in Table 1.
The grafting reaction was carried out in the same manner as in Example 1, except for the following changes, and the grafting efficiency and xylene insoluble content of the styrenic polymer were measured.

The results are shown in Table 1.

Table 1 Example 5 In Example 1, the kneader was Labo Plast Mill B-75.
The grafting reaction was carried out in accordance with Example 1 except that the type mixer was replaced with a Banbury type mixer (Toyo Seiki Seisakusho Co., Ltd.).

As a result, the grafting efficiency of styrenic polymer was 86% by weight.
The xylene insoluble content was 15.6% by weight.

Example 6 The grafting reaction was carried out in the same manner as in Example 1 except that the mixer was replaced with a single screw extruder (Toyo Seiki Seisakusho Layer).

As a result, the grafting efficiency of styrenic polymer was 80% by weight.
The xylene insoluble content was 20% by weight.

Example 7 In Example 1, the respective blending amounts were 500 g of low density ethylene polymer and 2 g of benzoyl peroxide.
．． 5g, t-butylperoxymethacryloyloxyethyl carbonate was replaced with Log, styrene was replaced with 500g,
Otherwise, a grafting precursor was produced in accordance with Example 1, and a grafting reaction was performed. As a result, the graft efficiency of the styrenic polymer was 82% by weight, and the xylene insoluble content was 23% by weight. A grafting precursor was prepared and a grafting reaction was performed.

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

Example 9 In Example 1, 300 g of styrene was replaced with 210 g of styrene.
A grafting precursor was prepared in the same manner as in Example 1 except for using a mixed monomer of 90 g of acrylonitrile and 90 g of acrylonitrile, and a grafting reaction was carried out.

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

Example 1゜In Example 1, 300g of styrene was replaced with 210g of styrene.
A grafting precursor was produced according to Example 1 except for the mixed monomer of g and n-butyl acrylate 90 g,
A grafting reaction was performed.

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

Example 11 In Example 1, 300 g of styrene was mixed with 30 g of vinyl acetate.
A grafting precursor was prepared according to Example 1 except that 6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butylperoxyallyl carbonate, and a grafting reaction was performed.

As a result, the grafting efficiency of the vinyl acetate polymer was 69% by weight, and the xylene insoluble content was 29% by weight.

Example 12 In Example 1, the low-density ethylene polymer was powdered low-density ethylene polymer (trade name "Frocene G-401J,
Manufactured by Seitetsu Kagaku Kogyo Co., Ltd., density 0゜925g/cm3)
Instead, 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 the styrene polymer was 85% by weight, and the xylene insoluble content was 13% by weight.

Comparative Example 1 A grafting precursor produced according to Example 1 was heated at 90°C.
When a grafting reaction was attempted for 1 hour using a Laboplasto Mill B-75 mixer at a rotational speed of 5 ORPM, the system did not melt and no crosstalk occurred.

Further, at that time, the grafting efficiency of the styrenic polymer was measured according to Example 1, and as a result, the grafting efficiency was 8% by weight, indicating that the reaction was insufficient.

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

As a result, decomposition of the grafted precursor occurred and coloration of the resin occurred.

Comparative Example 3 A grafting precursor was produced in the same manner as in Example 1 except that t-butylperoxymethacryloyloxyethyl carbonate was not used, and a grafting reaction was performed.

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

Example 13 50 g of granules of the grafted precursor prepared in Example 1
Further, 50 g of a granular low-density ethylene polymer with a density of 0.925 g/cm3 was added and mixed well at room temperature, and the same procedure as in Example 1 was followed except that this mixture was used, followed by kneading and grafting reaction to obtain a grafted resin. A composition was obtained. Regarding this graft resin composition, the grafting efficiency of the styrenic polymer was determined according to Example 1, and the result was 72% by weight.

Moreover, the xylene insoluble content was 9.7% by weight.

Next, this graft resin composition was press-molded at 200"C to produce a plate with a thickness of 2 m111. The appearance was uniform white, and no phase separation was observed. No peeling was observed.

Examples 14 to 17 Graft resin compositions were produced in accordance with 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 grafting efficiency of the styrene polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate molded at 200°C.

Examples 18-20 In Example 1.3, the crosstalk temperature was changed as shown in Table 3,
A graft resin composition was produced in accordance with Example 13 except for the above. Table 3 shows the graft efficiency of the styrenic polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200°C.

Table 3 Example 21 In Example 13, the crosstalk machine was Labo Plast Mill B-7.
A graft resin composition was produced according to Example j-3 except that the Banbury type mixer used in Example 5 was used instead of the Type 5 mixer. The grafting efficiency of the styrenic polymer of the graft resin composition was 78% by weight, the xylene insoluble content was 9.2% by weight, and no phase separation or single layer peeling was observed in the plate press-molded at 200°C.

Example 22 A graft resin composition was produced in accordance with Example 13, except that the mixer was replaced with the single screw extruder used in Example 6. Grafting efficiency of styrenic polymer of graft resin composition: 68% by weight, xylene insoluble content: 13.1
% by weight, and phase separation on a plate press-formed at 200°C.
No delamination was observed.

Example 23 In Example 13, instead of low-density ethylene as the crosstalk material, styrene polymer (trade name:
A plant resin composition was produced in accordance with Example 13, except that 50 g of "Dialex HF-55" (manufactured by Mitsubishi Monsando Kasei Co., Ltd.) was used.

Since this graft resin composition seems to have a styrene polymer as a matrix, it would originally be preferable to measure the grafting efficiency of a low-density ethylene polymer, but unfortunately there is no suitable measuring method. Therefore, it was decided to determine the grafting efficiency of the styrene polymer to the low density ethylene polymer according to Example 1. As a result, the grafting efficiency of the styrene polymer was 20% by weight, and the xylene insoluble content was 2.8% by weight. Further, in the plate formed from this graft resin composition according to Example 13, no phase separation or delamination was observed.

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

As seen in Examples 26 and 27, when a styrene polymer is used as a matrix, the grafting efficiency of the styrene polymer to a low density ethylene polymer is calculated to be low; It appears that the density ethylene polymer is grafted onto the styrenic polymer with a fairly high efficiency.

Examples 28 to 31 In Example 13, 700 g of low density ethylene polymer used in the production of the grafting precursor was changed to 500 g, 300 g of styrene was changed to 500 g, and benzoyl peroxide 1
．． A grafted precursor was produced in accordance with Example 13 except that 5 g was replaced with 2.5 g and 6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 1 g. Next, a graft resin composition was produced according to Example 13 except that the mixing amounts of this grafting precursor and the low-density ethylene polymer and styrene polymer were changed as shown in Table 5. Table 5 shows the graft efficiency of the styrenic polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200''C.

Examples 32 to 36 In Example 13, 300 g of styrene was replaced with 300 g of methyl methacrylate, and 0.6 g of n-dodecyl mercaptan was additionally used as a molecular weight regulator.
A grafted precursor was produced according to Example 13. The mixing amounts of this grafting precursor, low-density ethylene polymer, and methyl methacrylate polymer (trade name: Delpet 5ONJ, manufactured by Asahi Kasei Industries, Ltd.) were changed as shown in Table 6, and the other conditions were as in Example 13. A graft resin composition was produced in the same manner.The test results are shown in Table 6.

Examples 37 to 41 The same procedure as in Example 13 was used, except that instead of 300 g of styrene, a mixed monomer of 210 g of styrene, 90 g of acrylonitrile, and 0.6 g of n-dodecylmercaptan as a molecular weight regulator was used. A grafted precursor was produced. Separately, 70 g of styrene and 30 g of acrylonitrile were added to 500 g of a 1% polyvinyl alcohol aqueous solution.

A mixed solution of 0.2 g of n-dodecyl mercaptan and 0.5 g of benzoyl peroxide was added, and the temperature was maintained at 80 to 85° C. for 7 hours to complete polymerization to obtain an acrylonitrile-styrene copolymer. A graft resin composition was produced in accordance with Example 13, except that the mixing amounts of this copolymer, the grafting precursor, and the low-density ethylene polymer were changed as shown in Table 7.

The test results are shown in Table 7.

Example 42 A grafted precursor was produced in accordance with Example 13, except that 300 g of styrene was replaced with a monomer mixture of 210 g of methyl methacrylate and 90 g of n-butyl acrylate. Then, this grafted precursor 5
Example 1 using 0g and 50g of low density ethylene polymer.
A graft resin composition was produced according to 3. the result,
The grafting efficiency of methyl methacrylate-n-butyl acrylate copolymer is 62% by weight, and the xylene insoluble content is 8.9%.
% by weight. In addition, no phase separation or delamination was observed in the plate press-formed according to Example 13.

Example 43 In Example 13, 300 g of styrene was mixed with 3 vinyl acetate.
00g, t-butylperoxymethacryloyloxyethyl carbonate 6gf! : Example 1 except that each was replaced with 6 g of t-butylperoxyallyl carbonate.
A grafted precursor was produced according to 3. Next, 50 g of this grafting precursor and 50 g of low density ethylene polymer
using.

A graft resin composition was produced according to Example 13.

Furthermore, the grafting efficiency was measured in Example 13 by changing the extraction solvent from ethyl acetate to methanol. As a result, the grafting efficiency of vinyl acetate polymer was 73
The weight and xylene insoluble content was 16.3% by weight. In addition, no phase-separated one-layer peeling was observed in the plate press-formed according to Example 13.

Example 44 A grafting precursor was produced according to Example 13. Next, as a low-density ethylene polymer to be kneaded with the grafting precursor, a product named "Sumiriksen G-201J (density 0.919 g/ cm”, manufactured by Sumiya Kagaku Kogyo Co., Ltd.)
A graft resin composition was produced according to Example 13 by using 50 g of the grafted resin and mixing it with 50 g of the grafting precursor. At this time, the grafting efficiency of the styrene polymer was 74% by weight, and the xylene insoluble content was 9.8% by weight. In addition, Example 1
No phase separation was observed in the plate press-formed according to Example 3, but a slight delamination phenomenon was observed on the fracture surface.

Comparative Example 4 A grafted precursor was produced according to Example 13. Next, 0.5 g of this grafting precursor, 50 g of low density ethylene polymer, and "Dialex HF" used in Example 23 were added.
-55J 49.5g were mixed to produce a graft resin composition according to Example 13. At this time, the grafting efficiency of the styrene polymer was 0.3% by weight, and the xy-1-non insoluble content was 0.1% by weight. In addition, a phase separation phenomenon was observed in the plate press-formed according to Example 13, and a large delamination phenomenon also occurred on the fracture surface.

Comparative Example 5 A grafting reaction was attempted in the same manner as in Example 13, except that the crosstalk temperature between the grafting precursor and the polymer was 90°C. However, since the crosstalk temperature was low, melt crosstalk was impossible.

Comparative Example 6 A grafting reaction was carried out in the same manner as in Example 13, except that the crosstalk temperature between the grafting precursor and the polymer was 320°C. As a result, decomposition of the resin occurred during the grafting reaction, and the resulting grafted resin composition was colored brown.

Comparative Example 7 A 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 grafting efficiency of the styrene polymer was 7% by weight, and the xylene insoluble content was 2.8% by weight. However, in the plate press-formed according to Example 13, a slight phase separation phenomenon was observed, and furthermore, 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 Example 1, instead of the ethylene-based (co)polymer for the grafting precursor, various ethylene-based (co)polymers shown in Table 8 were used.
Example 1 was carried out, except that each co)polymer was used, the impregnation time was changed from 1 hour to 2 hours, and the polymerization temperature during the preparation of the grafted precursor was changed to the temperature shown in Table 8. The grafted precursors were obtained through various operations.

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

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

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

Furthermore, using these grafted precursors.

A grafting reaction was carried out according to Example 1.

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

Note that the grafting efficiency represents the ratio of grafted polystyrene to total polymerized polystyrene.

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

Examples 54 to 57 Same as Example 1 except that the grafted precursors obtained in the intermediate steps in Examples 45 to 48 were used, and the kneader was changed from the Laboplast Mill B-75 type mixer to the mixer shown in Table 10. A grafting reaction was carried out in the same manner to obtain each grafted resin composition.

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

Examples 58 to 61 Benzoyl peroxide, t-butylperoxymethacryloyloxyethyl carbonate, and t-butylperoxymethacryloyloxyethyl carbonate used in the preparation of the grafting precursor in Example 1.

Grafting precursors were produced in accordance with Example 1, except that the blending amounts of each ethylene-based (co)polymer of styrene were changed as shown in Table 11.

A grafted resin composition was obtained according to Example 1 using each grafting precursor.

For each of these graft resin compositions, the grafting efficiency of the styrenic polymer and the xylene insoluble content were measured according to Example 1, and the results are shown in Table 11.

Examples 62 to 73 Grafted precursors were produced according to Example 1, except that styrene was replaced as the ethylene-based (co)polymer used for producing the grafted precursor as shown in Table 12, Then, a graft resin composition was obtained according to Example 1 using each grafting precursor.

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

Examples 74 to 77 Example 1 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 the method described in .

A graft resin composition was obtained according to Example 1 using each grafting precursor.

For each of these graft resin compositions, the grafting efficiency of the vinyl acetate polymer and the xylene-insoluble content were measured in the same manner as in 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
In Example 78, the epoxy group-containing ethylene copolymer was used, in Example 79, the ethylene-acrylic acid ester copolymer was used, and in Example 8o, the ethylene-vinyl acetate copolymer was replaced with a powder obtained by freezing and pulverization. The grafting reaction was carried out in the same manner as in Example 1 except that each graft resin composition was obtained. As a result, the grafting efficiency and xylene insoluble content of the styrene polymer were as shown in Table 14.

Table 14 Example 81 Example 4 except that the epoxy group-containing ethylene copolymer of Example 45 was replaced with one consisting of 82% by weight of ethylene, 12% by weight of glycidyl methacrylate, and 6% by weight of vinyl acetate.
A grafting precursor was prepared according to 5, and a grafting reaction was performed.

As a result, the grafting efficiency of the styrenic polymer was 79.5,
The xylene insoluble content was 19.8% by weight.

Example 82 In Example 46, the ethylene-acrylic acid ester copolymer was converted into a copolymer consisting of 95% by weight of ethylene and 5% by weight of ethyl acrylate (trade name:
A grafting precursor was produced according to Example 46, except that A-3050J (manufactured by Nippon Petrochemicals, Ltd.) was used, and a grafting reaction was performed.

As a result, the grafting 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 260J, manufactured by Mitsui Polychemical Co., Ltd.). Except for this, a grafting precursor was produced in accordance with Example 47, and the grafting reaction was performed.

As a result, the grafting efficiency of the styrenic polymer was 84.8% by weight, and the xylene insoluble content was 27.4% by weight. Comparative Examples 8 to 11 The grafting precursor produced according to Examples 45 to 49 was 'C for 1 hour, Labo Plastomil B-75
When a grafting reaction was attempted using a mold mixer at a rotational speed of 5 ORPM, the system did not melt and no crosstalk occurred.

At that time, as a result of measuring the grafting efficiency of the styrenic polymer according to Example 1, the grafting efficiency was found to be 8 in Comparative Example 8.
6.2% by weight in Comparative Example 9, 3.1% by weight in Comparative Example 1
The reaction was insufficient at 0 and 2.7% by weight.

Comparative Examples 12 to 15 In Example 1, the grafting reaction was carried out according to Comparative Examples 8 to 11, except that the temperature of the grafting reaction was 320°C.

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, the grafted precursors were produced in accordance with Examples 45 to 48, except that t-butylberoxymethacryloyloxyethyl carbonate was not used, and
A grafting reaction was performed.

As a result, in the epoxy group-containing ethylene copolymer system of Comparative Example 16, the grafting efficiency of the styrene polymer was 3.2% by weight, and the xylene insolubility was 90% by weight, and in the comparative example using the ethylene-ethyl acrylate copolymer system. In Comparative Example 17, the grafting efficiency of the styrene polymer was 1.2% by weight, and the xylene insoluble content was 0% by weight, and in Comparative Example 18, which was an ethylene-vinyl acetate copolymer, the grafting efficiency of the styrene polymer was 1.9% by weight. , xylene insoluble 90% by weight, and ethylene-
In Comparative Example 19 using a propylene-diene copolymer rubber system, the grafting efficiency of the styrene polymer was 1.9% by weight, and the xylene insoluble content was 0% by weight.

The effect of t-butylperoxymethacryloyloxyethyl carbonate was clearly confirmed.

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

The grafting efficiency and xylene insoluble content of each of these graft resin compositions were measured in the same manner as in Example 1, and the results are shown in Table 15.

Next, Example 1 was carried out using these graft resin compositions.
A plate with a thickness of 2 mm similar to No. 3 was prepared. As a result, all had a uniform white appearance, and no phase separation was observed.

Furthermore, when the plates were fractured, 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 for producing the graft resin composition and the ethylene (co)polymer were changed as shown in Tables 16 to 19, respectively. Each graft material composition was manufactured according to Examples 84 to 87.

For each of the obtained graft resin compositions, the plant efficiency and xylene insoluble content of the styrene polymer were measured according to Example 1, and the appearance of the press-formed plates at 200'C is shown in Tables 16 to 19. .

Examples 93 to 96 Graft resin compositions were produced according to Examples 84 to 87, except that the crosstalk temperature was changed from 180° C. as shown in Table 20. Measure the grafting efficiency and xylene insoluble content of each styrenic polymer,
Table 2 also shows the appearance of the press-formed plate at 200°C.
0.

Examples 97 to 100 In Examples 84 to 87, the grafting reaction was carried out in accordance with Examples 84 to 87, except that the mixer was changed from the Laboplast Mill B-75 type mixer to the mixer shown in Table 21. A graft resin composition was obtained.

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") was used as a vinyl polymer instead of the ethylene (co)polymer mixed with the grafting precursor.
Graft resin compositions were obtained according to Examples 84 to 87, except that J Mitsubishi Monsanto Chemical Co., Ltd. product was used.

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

Examples 105 to 1o8 In Examples 101 to 104, each graft was prepared according to Examples 101 to 104, except that the mixing amounts of the grafting precursor and the styrene polymer were changed as shown in Tables 23 to 26, respectively. A resin composition was produced.

For each of the obtained graft resin compositions, the grafting efficiency of the styrene polymer and the xylene insoluble content were measured according to Example 1, and the appearance of the press-formed plates at 200'C is shown in Tables 23 to 26, respectively. .

In addition, as seen in Tables 23 to 26 where grafting precursor/styrene polymer = 25/75 and 5/95, when a styrene polymer is used as a matrix, the Although the grafting efficiency is calculated to be low, it seems that the ethylene copolymer that is the dispersed layer is grafted onto the styrene polymer at a fairly high rate.

Examples 109 to 112 In Examples 84 to 87, 700 g of the ethylene copolymer used for producing the grafted precursor was changed to 5° OgLC, 300 g of styrene was changed to 500 g, 1.5 g of benzoyl peroxide was changed to 2.5 g, and Each grafting precursor was produced according to Examples 84 to 87, except that 6 g of t-butylperoxymethacryloyloxyethyl carbonate f-6 was replaced with 9 g.

Next, graft resin compositions were obtained according to Polymerizations 84 to 87 except that the mixing amounts of this grafting precursor, ethylene copolymer, and styrene were changed as shown in Tables 27 to 30.

The grafting efficiency and xylene insoluble content of each of these graft resin compositions were measured in the same manner as in Example 1, and the appearance of the plates press-molded at 200°C is shown in Tables 27 to 30.

Examples 113 to 116 Examples 84 to 87, except that styrene used in the preparation of the grafted precursor was replaced with methyl methacrylate, and 0.6 g of n-dodecyl mercaptan was additionally used as a molecular weight regulator. The grafted precursors were each produced according to the method described in 87.

Except that the mixing amount of each grafting precursor, ethylene system, and methyl methacrylate polymer (trade name "Delpet 5ON", manufactured by Asahi Kasei Industries, 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 to 34.6 Examples 117 to 120 In Examples 84 to 87, 300 g of styrene was replaced with a mixed monomer of 210 g of styrene and 90 g of acrylonitrile, and n-dodecyl mercaptan was used as a molecular weight regulator.
．． Grafted precursors were each produced according to Examples 84 to 87, except that 6 g was additionally used.

Separately, in 500 g of 1% polyvinyl alcohol aqueous solution,
70 g of styrene, 30 g of acrylonitrile, 0.2 g of n-dodecyl mercaptan, 0.0 g of benzoyl peroxide.
5 g of the mixed solution was added and maintained at a temperature of 80-85 for 7 hours to complete the polymerization, thereby obtaining acrylonitrile-styrene copolymers.

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

Tables 35 to 38 are for the results of the obtained graft resin composition.
are shown respectively.

Examples 121 to 124 In Examples 84 to 87, 300 g of styrene was mixed with 210 g of ethyl methacrylate and 90 g of n-butyl acrylate.
Grafting precursors were produced in accordance with Examples 84 to 87, except that the mixed monomers were replaced with the following.

Next, using 50 g of these grafting precursors and 50 g of the ethylene copolymer shown in the following table, Example 8 was prepared.
A graft resin composition was obtained according to No. 4-87.

Table 39 shows the results of each graft resin composition obtained.
Shown below.

Examples 125 to 128 Examples 84 to 87, except that 300 g of styrene was replaced with 300 g of vinyl acetate, and 6 g of t-butylperoxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butylperoxyallyl carbonate. Each grafting precursor was produced according to the method described in the following.

Then, graft resin compositions were obtained according to Examples 84 to 87 using 50 g of each of these grafted precursors and 50 g each of the same ethylene copolymer used for the grafted precursor.

Furthermore, 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 produced according to Example 84.

Next, as an epoxy group-containing ethylene copolymer to be kneaded with this grafted precursor, 82% polymerization of ethylene, 12% by weight of glycidyl methacrylate, and 6% by weight of vinyl acetate were used.
Using 50 g of a copolymer consisting of
A graft resin composition was prepared according to Example 84.

At this time, the grafting efficiency of the styrene polymer was 55.5
The xylem insoluble content was 14.5% by weight.

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

Example 130 In Example 85, the ethylene-ethyl acrylate copolymer was mixed with 95% by weight of ethylene and 5% by weight of ethyl acrylate.
A copolymer consisting of
A graft resin composition was produced in accordance with Example 85, except that A-3050J (manufactured by Nippon Petrochemicals Co., Ltd.) was used instead. As a result, the grafting 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 consisting of 72% by weight of ethylene and 28% by weight of vinyl acetate (trade name: "Evaflex 260J," manufactured by Mitsui Polychemical Co., Ltd.) A graft resin composition was produced in accordance with Example 86 except for the following.As a result, the grafting 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, 50 g of the same ethylene copolymer used in the production of each grafted precursor, and 49.5 g of the same styrene polymer used in Example 101 were added. Examples 84 to 87
A graft resin composition was produced according to the method. At this time, the grafting efficiency of the styrene polymer was 0.3% by weight, Or4% by weight, 0.9% by weight, and 0.7% by weight in order from Comparative Example 20, and the xylene-insoluble content was 0.3% by weight, Or4% by weight, 0.9% by weight, and 0.7% by weight, respectively. 1-wt%, 0.4 wt%, 0.3 wt%, and 0.2 wt%. Phase separation was observed in all of the press-formed plates, and large delamination phenomena also occurred on the fracture surfaces.

Comparative Examples 24 to 27 Grafting reactions were attempted in accordance with Examples 84 to 87, except that the crosstalk temperature of the grafting precursor and the ethylene copolymer was 90'C. Ta. However, since the crosstalk temperature was low, melt crosstalk was impossible.

Comparative Examples 28 to 31 Grafting reactions were carried out in the same manner as in Examples 84 to 87, except that the crosstalk temperature between the grafting precursor and the ethylene copolymer was 320°C. As a result, decomposition of the resin occurred during the grafting reaction, and the resulting resin composite acid was colored brown.

Comparative Examples 32 to 35 In Examples 84 to 87, the grafting reactions were carried out in the same manner as in Examples 84 to 87, except that the respective grafting precursors were produced without using t-butylperoxymethacryloyloxyethyl carbonate. I did it. As a result, the grafting efficiency of the styrene polymer was 0.1% by weight, 0% by weight, 0.2% by weight, and 0% by weight in the order from Comparative Example 32, and the xylene-insoluble content was 0% by weight. there were. In addition, phase separation was observed in all press-formed plates, and large delamination phenomena also appeared on the fractured surfaces.

From this result, the effect of t-butylperoxymethacryloyloxyethyl carbonate, which is a radical (co)polymerizable organic peroxide, was clearly confirmed.

Claims (1)

[Claims] 1. A grafted precursor obtained by the following method or a mixture consisting of 1 to 99% by weight of the grafted precursor and 99 to 1% by weight of the following polymer is melted at 100 to 300°C. 2. A method for producing a grafted resin composition, which comprises carrying out a grafting reaction by kneading. The grafting precursor is an ethylene (co)polymer 1
00 parts by weight were suspended in water, and separately, vinyl aromatic monomer, (meth)acrylic acid ester monomer, (
one or more vinyl monomers selected from the group consisting of meth)acrylonitrile and vinyl ester monomers 5
~400 parts by weight of one or two radical (co)polymerizable organic peroxides represented by the following general formula (I) or (II).
A radical polymerization initiator having a decomposition temperature of 40 to 90°C to obtain a half-life of 10 hours is added to the vinyl monomer in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer. A solution in which 0.01 to 5 parts by weight of the monomer and radical (co)polymerizable organic peroxide are dissolved in 100 parts by weight in total is added to ensure that the radical polymerization initiator is not substantially decomposed. The ethylene-based (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 polymerizable organic peroxide and the radical polymerization initiator is less than 50% by weight, the temperature of this aqueous suspension is increased to combine the vinyl monomer and the radical (co)polymerizable organic peroxide. This is a resin composition obtained by copolymerizing an oxide with an ethylene-based (co)polymer. The radical (co)polymerizable organic peroxide represented by the above general formula (I) has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (I) (wherein R_1 is a hydrogen atom or a carbon number of 1 to 1) 2 alkyl group, R_2 is a hydrogen atom or methyl group, R_3 and R_4
each represents an alkyl group having 1 to 4 carbon atoms, and R_5 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) is a compound represented by In addition, the radical (co)polymerizable organic peroxide represented by the above general formula (II) has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (II) (where R_6 is a hydrogen atom or a carbon number 1 to 4 alkyl groups, R_7 is a hydrogen atom or methyl group, R_8 and R_9
each represents an alkyl group having 1 to 4 carbon atoms, and R_1_0 represents an alkyl group having 1 to 12 carbon atoms, 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 the mixture with the grafting precursor is:
One type selected from the group consisting of (1) ethylene-based (co)polymers, (2) vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile, and vinyl ester monomers. Alternatively, it is a polymer consisting of one or both of vinyl polymers obtained by polymerizing two or more types of vinyl monomers. 2. Ethylene polymer has a density of 0.910 to 0.935 g
2. The method for producing a graft resin composition according to claim 1, wherein the graft resin composition is a low density ethylene polymer having a density of ethylene/cm^3. 3. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an epoxy group-containing ethylene copolymer obtained by copolymerizing ethylene and glycidyl (meth)acrylate. 4. The ethylene copolymer contains 60 to 99.5% by weight of ethylene and 0.5 to 40% by weight of glycidyl (meth)acrylate.
The method for producing a graft resin composition according to claim 1, which is an epoxy group-containing ethylene copolymer obtained by copolymerizing with. 5. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer consists of ethylene and (meth)acrylic acid ester. 6. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of (meth)acrylic acid ester. 7. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer consists of ethylene and 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 copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of vinyl ester. 10. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an ethylene-propylene copolymer rubber. 11. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an ethylene-propylene-diene copolymer rubber. 12. Ethylene system (co) kneaded into the grafting precursor
Claim 1: The monomer composition of the polymer is the same as the monomer composition of the ethylene (co)polymer in the grafting precursor.
A method for producing the graft resin composition described. 13. The method for producing a grafted resin composition according to claim 1, wherein the density of the low density ethylene polymer kneaded into the grafted precursor is the same as the density of the low density ethylene polymer in the grafted precursor. . 14. The method for producing a grafted resin composition according to claim 1, wherein 50% by weight or more of the vinyl monomers used in producing the grafted precursor are vinyl aromatic monomers. 15. The method for producing a grafted resin composition according to claim 1, wherein 50% by weight or more of the vinyl monomers used in producing the grafted precursor are (meth)acrylic acid ester monomers. 16. The grafted resin composition according to claim 1, wherein the monomer composition of the vinyl polymer kneaded into the grafting precursor is the same as the monomer composition of the vinyl polymer in the grafting precursor. Production method.