JPH06145432A - Olefinic polymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of providing films, sheets, etc., excellent in adhesion, coating adhesion and printability without carrying out the primer coating or plasma treatment by blending an olefinic polymer with a specific copolymer composition. CONSTITUTION:The objective composition is obtained by reacting (A) a polyhydroxy hydrocarbon-based polymer having 500-20000 number-average molecular weight (preferably a hydrogenated polyhydroxy diene-based polymer) with (B) a compound having both a polymerizable unsaturated group and NCO group (e.g. methacryloyloxyethyl isocyanate) under conditions so as to provide >=1.5 ratio of the hydroxyl group equiv. of the component (A)/NCO group equiv. of the component (B), copolymerizing the resultant polymerizable composition with a vinylic monomer (preferably methacryloyloxyethyltrimethylammonium chloride, etc.), affording a copolymer composition and then blending the obtained copolymer composition with an olefinic polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an olefin polymer having improved adhesion and coating adhesion. Specifically, an olefin-based polymer composed of an olefin-based polymer and a copolymer obtained by copolymerizing a polymerizable reactant having a polymerizable unsaturated group at the end of a hydrocarbon-based polymer skeleton and a vinyl-based monomer. It relates to a combined composition.

[0002]

2. Description of the Related Art Conventionally, it is known that a polyolefin resin does not have a polar group in its structure, so that the adhesive force of the paint is weak when it is applied and the adhesive force of the adhesive is weak when it is adhered. . Therefore, in order to improve the poor adhesion and adhesiveness, a primer is applied to the surface of the polyolefin resin, or the surface is modified by plasma treatment or the like.

[0003]

However, such a method has the following problems. That is,
In the primer method, there is a drawback that the cost is high due to the need to use an expensive primer and the number of steps, and the solvent for the primer needs to be volatilized. However, there was a risk of fire and there was a problem with safety.

On the other hand, the plasma processing method has the drawbacks that the cost is high due to the need for expensive equipment and poor productivity, and the plasma-treated surface is in an unstable state. The process control was very difficult.

[0005]

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the gist of the present invention is an olefin polymer,
The hydroxyl group equivalent of the polyhydroxy hydrocarbon polymer (A) having a number average molecular weight of 500 to 20,000 is A, and the isocyanate group equivalent of the compound (B) having both a polymerizable unsaturated group and an isocyanate group in one molecule is B. Where C is the equivalent weight of the carboxyl group or the functional group derived from the carboxyl group of the compound (C) having both a polymerizable unsaturated group and a carboxyl group or a functional group derived from the carboxyl group in one molecule, A / A polymerizable composition obtained by reacting (A) and (B) under the condition that B is 1.5 or more, or (A) and (C) are reacted under the condition that A / C is 1.5 or more. An olefin-based polymer composition is characterized in that it comprises a copolymer composition obtained by copolymerizing the polymerizable composition obtained by the above-mentioned method and a vinyl-based monomer.

The present invention will be described in more detail below. The polyhydroxy hydrocarbon polymer of the component (A) used in the present invention has at least one hydroxyl group per molecule and has a number average molecular weight of 500 to 2000.
0, main chain structure is hydrocarbon, preferably iodine value is 1
Examples of the wax having a value of 00 or less and being in the form of a liquid or brittle wax at room temperature can be given.

Examples of such polyhydroxy hydrocarbon polymers include hydrogenated products of polyhydroxydiene-based polymers, hydrogenated products of oxidative decomposition reduction products of isobutylene-diene-based monomer copolymers, and α-olefins. (For example, ethylene, propylene, etc.)-A non-conjugated diene (or conjugated diene) copolymer oxidative decomposition reduction product hydrogenated product and the like can be mentioned. Of these, hydrogenated products of polyhydroxydiene-based polymers are particularly preferable.

Thus, the polyhydroxydiene polymer is produced by a known method such as a conjugated diene or a conjugated diene and a vinyl monomer as a raw material, for example, a radical polymerization method or an anionic polymerization method. In the case of radical polymerization, a conjugated diene-based polymer or copolymer having a hydroxyl group directly at the terminal can be obtained by polymerizing with hydrogen peroxide as a polymerization initiator, but in the case of anionic polymerization, an alkali metal is first added to the terminal by using an anionic polymerization catalyst. A living polymer having a bonded structure is produced and then reacted with a monoepoxy compound, formaldehyde and the like. As the raw material conjugated diene, 1,3-butadiene, isoprene, chloroprene and the like can be used. As the copolymerization component, styrene,
Vinyl monomers such as acrylonitrile, methyl (meth) acrylate, vinyl acetate, etc. may be mentioned. The amount of the copolymerization component used is preferably 30% by weight or less of the total amount of monomers.

In addition, hydrogenation in producing a hydrogenated product of a polyhydroxydiene polymer is carried out by using a catalyst such as nickel, cobalt, platinum, palladium, ruthenium or rhodium alone or by supporting it on a carrier. By the usual method,
It may be carried out under hydrogen. A polymer obtained by partially hydrogenating a polyhydroxydiene polymer can also be used.

As another method for producing a hydrocarbon polymer having a hydroxyl group, there may be mentioned a method of subjecting a copolymer of an α-olefin and another monomer to oxidative decomposition treatment and then reducing it. For example, isobutylene and butadiene or 1,
A butyl rubber-based polymer obtained by cationically polymerizing 3-pentadiene is subjected to ozonolysis treatment and then reduced with lithium aluminum hydride to obtain polyhydroxyisobutylene.

It is also possible to react these polyhydroxy hydrocarbons with diisocyanates, diesters, etc. and use them as high molecular weight polyhydroxy hydrocarbons. In the present invention, a part of the polyhydroxy hydrocarbon polymer may be replaced with another polyol. Examples of other polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and other polyalkylene glycols, polycaprolactone polyols, castor oil, ethylene glycol, lower polyols such as trimethylolpropane, and trimethylolpropane and other ethylene. Examples thereof include those to which oxide or the like has been added. The substitutable amount is 0 to 49% by weight of the polyhydroxy hydrocarbon polymer. If it exceeds this range, the hydrolysis resistance, weather resistance and heat resistance, which are the characteristics of the polyhydroxy hydrocarbon polymer, are deteriorated, which is not preferable.

Next, the other component (B) used in the present invention is a compound having both a polymerizable unsaturated group and an isocyanate group in one molecule. Here, the polymerizable unsaturated group means an ethylenically unsaturated group capable of radical polymerization, anionic polymerization, cationic polymerization and the like, and specifically, a styryl group, an α-methylstyryl group, a vinyl ether group, a vinyl ester group. , (Meth) acrylic group, substituted acrylic group,
Examples thereof include an allyl group. Specific examples of such a compound having both a polymerizable unsaturated group and an isocyanate group in one molecule include:

[0013]

[Chemical 1]

[0014] Another example of the compound having both a polymerizable unsaturated group and an isocyanate group in one molecule is a reaction product of a compound having a polymerizable unsaturated group and a hydroxyl group in one molecule and a diisocyanate compound. . Typical compounds having a polymerizable unsaturated group and a hydroxyl group in one molecule are 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth).
Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate, and the diisocyanate compound includes tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate,
Examples thereof include isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and the like. Here, the reaction product of a compound having a polymerizable unsaturated group and a hydroxyl group in one molecule and a diisocyanate compound was given as an example, but a compound having both a polymerizable unsaturated group and an isocyanate group in one molecule by the reaction. However, it is not limited to these.

Next, the other component (C) used in the present invention is derived from a polymerizable unsaturated group in one molecule and a carboxyl group or a carboxyl group which reacts with a hydroxyl group to form an ester bond. It is a compound having both functional groups. Here, the polymerizable unsaturated group means an ethylenically unsaturated group capable of radical polymerization, anionic polymerization, cationic polymerization and the like, and specifically, a styryl group, an α-methylstyryl group, a vinyl ether group, a vinyl ester group. , (Meta)
Examples thereof include an acrylic group, a substituted acrylic group, an allyl group and the like. Specific examples of such a compound having a polymerizable unsaturated group and a functional group derived from a carboxyl group which reacts with a carboxyl group or a hydroxyl group to form an ester bond in one molecule include vinyl benzoic acid and Unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid chloride, (meth) acrylic acid bromide, etc. Examples thereof include unsaturated acid anhydrides such as (meth) acrylic acid halides and maleic anhydride.

Of these, methyl (meth) acrylate and (meth) acrylic acid chloride are preferable. Therefore, in the present invention, the component (A) and the component (B) are represented by A and B, where the hydroxyl group equivalent of (A) is A and the isocyanate group equivalent of (B) is B. React. If this equivalent ratio is less than 1.5, the proportion of the polyfunctional component in the component (A) to react with the component (B) increases, and the polyfunctional component in the resulting polymerizable composition also increases. If it is attempted to copolymerize this with other monomers using this as a raw material, it becomes very easy to gel.

The reaction between the component (A) and the component (B) is a urethane-forming reaction, which is performed at room temperature to 120 ° C. for 10 minutes to
It can be suitably performed in about 24 hours. If necessary, a solvent such as toluene may be used in the reaction, or a catalyst such as dibutyltin dilaurate may be used. Therefore, in the present invention, the component (A) and the component (C) are derived from a hydroxyl group equivalent of (A) from the carboxyl group of A or (C) or a carboxyl group which forms an ester bond by reacting with the hydroxyl group. A / C =, where C is the equivalent of the functional group
The reaction is carried out at an equivalent ratio of 1.5 or more. This equivalence ratio is 1.5
If it is less than the above, the proportion of the polyfunctional component in the component (A) and the component (C) reacts with each other, and the polyfunctional component in the resulting polymerizable composition also increases. When it is attempted to copolymerize with the polymer, it becomes very easy to gel.

The reaction between the component (A) and the component (C) is an ester-forming reaction, and when (C) is an unsaturated carboxylic acid, a (meth) acrylic acid ester or an unsaturated acid anhydride, a mineral acid, Using an acid catalyst such as paratoluene sulfonic acid or a metal catalyst such as titanium alkoxide, zinc acetate, antimony oxide, etc., while removing the elimination component as necessary,
It can be suitably carried out at a temperature of room temperature to 200 ° C. for about 30 minutes to 24 hours. When (C) is a (meth) acrylic acid halide, a base such as triethylamine or pyridine is used, or an acid halide generated by flowing an inert gas stream is removed, and the temperature is from room temperature to 150 ° C.
It can be suitably performed in a time of about minutes to 24 hours. For these reactions, a solvent such as toluene may be used if necessary.

The vinyl monomer used in the present invention is a conventionally known radically polymerizable monomer. Preferred vinyl monomers include ionic residues containing quaternary ammonium salt, metal salt, etc., pyrrolidone or polymerization degree of 1 to 20.
A nonionic hydrophilic group consisting of 0 polyethylene oxide,
Perfluoroalkyl group having 4 to 20 carbon atoms, polymerization degree 1 to
200 polysiloxanes, hydrolyzable silyl groups, benzotriazoles, hindered amines, benzophenones, hindered phenols, phosphoric acid esters, aromatic sulfonyls, aromatic imines, vinyl monomers having characteristic groups such as aromatic nitrogen, aromatic halogen, etc. To be

Specific examples of the monomer having an ionic group include dimethylaminoethyl (meth) acrylate having a cationic group, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, Diisopropylamino (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminovinyl sulfide, diethylaminoethyl vinyl ether, vinylbenzyl-N, N'-dimethylamine, vinylpyridine, vinylquinoline, etc. There are quaternized products of nitrogen monomers. This quaternization is carried out by publicly known methods to give a tertiary amino group hydrogen chloride, hydrogen bromide,
It can be carried out by acting an inorganic acid such as sulfuric acid or a quaternizing agent such as benzyl chloride, benzyl bromide, methyl chloride or methyl bromide. The quaternization step may be carried out at the stage of the monomer before the copolymerization or at any stage after the copolymerization. Further, as the monomer having an anionic group, (meth) acrylic acid, α
-Chloro (meth) acrylic acid, vinyl sulfonic acid, sulfonated styrene, 2-acrylamido-2-methylpropane sulfonic acid, sulfomethyl (meth) acrylate,
2-sulfoethyl (meth) acrylate, 3-sulfoethyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, allylsulfonic acid, 1-phenylvinylsulfonic acid, acid phosphooxyethyl (meth)
A vinyl-based monomer having a carboxyl group, a sulfonic acid group, a phosphoric acid group such as acrylate, 3-chloro-2-amidophosphooxypropyl (meth) acrylate, and acidphosphooxypropyl (meth) acrylate, or
These alkali metal salts, ammonium salts, or,
Organic amines such as dimethylamine, triethylamine and triethanolamine, and tetrabutylphosphonium salts. When a metal salt or an organic salt is used among these, the corresponding monomer may be directly used for the polymerization, or may be neutralized after the polymerization at the stage of the organic acid monomer.

Any of the copolymers of the present invention synthesized using these monomers can be expected to have antistatic properties by coating or mixing with a resin, but preferably 4
It is a copolymer synthesized from a monomer containing a primary ammonium salt. Further, as the monomer having a nonionic hydrophilic group, N-vinylpyrrolidone, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol (meth) represented by the following general formula [VII] is used. An acrylate is mentioned.

[0022]

Embedded image R ¹ —O— (CH ₂ CH ₂ —O—) _n CO—CH (R ⁴ ) ═CH ₂ [VII]

R ¹ is an alkyl group having 1 to 20 carbon atoms, R ^1
4 represents hydrogen or a methyl group, and n represents an integer of 1 to 200. The copolymer of the present invention synthesized from these monomers is expected to impart hydrophilicity by coating or kneading with a resin.

Further, examples of the monomer having a perfluoroalkyl group include the following structures.

Embedded image CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ )
= CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC
(CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ )
₅ (CH ₂ ) ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ )
₇ (CH ₂ ) ₇ (CH ₂ ) ₄ OCOCH = CH ₂ , CF
₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCONHCH ₂ CH ₂ O
COC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO _{2
N (C 3 H 7) (} CH 2) 2 OCOCH = CH 2, CF
₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OC
OC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ CONH
(CH ₂ ) ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) _{7
CONH (CH 2) 2 OCOC (} CH 3) = CH 2, H
(CF ₂ ) ₁₀ CH ₂ OCOCH = CH ₂ , CF ₂ Cl
(CF ₂ ) ₁₀ CH ₂ OCOCH = CH ₂ or other polyfluoroalkyl group-containing (meth) acrylate, CF ₃ (CF
₂ ) ₈ CH ₂ CH ₂ OCH ₂ CH ₂ OCH = CH ₂ ,
_{(CF 3) 2 CF (CF} 7) CH 2 CH 2 OCH = CH
_{2, (CF 3) 2 CF} (CF 2) 7 CH 2 CH 2 OCH
₂ CH ₂ OCH = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ C
H ₂ OCH = CH ₂ , H (CF ₂ ) ₁₀ CH ₂ CH ₂ OC
H = CH ₂ or other polyfluoroalkyl group-containing vinyl ether

[0025]

[Chemical 4]

Perfluoroalkyl group substitution (α
-Methyl) styrene, CHF = CF ₂ , CHCl
= CFCl, CHF = CF ₂ , CF ₂ = C (C
F ₃ ) ₂ , CF ₃ CH = CH ₂ , C ₃ F ₇ CH = CH ₂
Fluorine-containing vinyl monomers such as

As the monomer having a siloxane bond,

[0028]

[Chemical 5]

[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

[Chemical 8]

And the like. The copolymer of the present invention synthesized from these fluorine-containing and siloxane-containing monomers is expected to impart water repellency to the substrate by kneading or coating with a resin, but is particularly preferable. Is perfluoro (meth) acrylate or siloxane (meth) acrylate described below.

[0033]

[Chemical 9]

As the monomer having a hydrolyzable silyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyltriacetoxysilane,
Examples thereof include vinylmethyldiacetoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. Any of the copolymers of the present invention synthesized from these monomers,
By kneading with a resin, it is expected that the dispersibility of the inorganic filler can be increased and the adhesion to a metal or the like can be improved, but preferably 3-methacryloxypropylmethyldimethoxysilane and 3-methacryl silane are used. Roxypropyltrimethoxysilane.

Benzotriazole, hindered amine,
Examples of the benzophenone-containing monomer include the following structures.

[0036]

[Chemical 10]

The copolymers of the present invention synthesized from these monomers all have an ultraviolet absorbing ability, and when added to a resin, unlike ordinary low molecular weight additives, bleed-out may occur. And maintain its performance for a long time. Further, examples of the monomer containing hindered phenol, phosphate ester, aromatic sulfonyl, and aromatic imine include the following structures.

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

The copolymers of the present invention synthesized from these monomers all have an antioxidant property, and when added to the resin, unlike the general low molecular weight additives, bleed-out There is no fear and the performance is maintained for a long time. Furthermore, examples of the aromatic nitrogen-containing or aromatic halogen-containing monomer include the following structures.

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

The copolymer of the present invention synthesized from these monomers has antibacterial properties, and when added or applied to a resin, it has the effect of suppressing the generation of mold on the substrate for a long period of time. Can be expected. The copolymerization of the polymerizable reaction product and the vinyl-based monomer can be easily performed by an ordinary radical polymerization method. That is, a radical polymerization initiator such as an azo compound or a peroxide is usually added to the polymerizable reactant and the vinyl monomer in an amount of 0.1 to 10% by weight, and the mixture is added at 0 ° C to 20 ° C.
It can be suitably carried out at a temperature of 0 ° C. for 1 hour to 24 hours.

Here, a chain transfer agent such as alkyl mercaptan may be added in order to adjust the degree of polymerization.
As the polymerization method, any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like, which are usually employed in radical polymerization, may be used. The weight ratio of the polymerizable reactant to the vinyl monomer is 1:99 to 99: 1, preferably 5:95 to 95: 5. When the ratio of the vinyl-based monomer is less than 1, it is difficult for the vinyl-based monomer to exhibit expected properties such as antistatic property. When the ratio of the polymerizable reaction product is less than 1, when mixed with another resin, the affinity is deteriorated and the resin cannot be uniformly dispersed, and in order to exhibit the expected performance, a larger amount is required. It is not preferable because the copolymer has to be added.

Further, in the copolymer of the present invention, a part of the above-mentioned polymerizable reaction product and vinyl-based monomer can be replaced with another monomer. Examples of other monomers include styrene, vinyl acetate, and (meth) acrylic acid esters derived from alcohols having 1 to 20 carbon atoms. The substitutable amount is 50% by weight or less, preferably 40% by weight or less based on the whole amount. This ratio is 50
When the content exceeds the weight%, various functions and compatibility with other resins, which are the characteristics of the copolymer of the present invention, are impaired, which is not preferable.

The olefin polymer in the composition of the present invention specifically means, for example, the following. It is a polymer or copolymer of α-olefin represented by ethylene, propylene, butene, 4-methylpentene-1 and the like, and includes relatively low molecular weight polymers to high molecular weight polymers. The density includes low density products of about 0.86 to high density products of about 0.97, and includes substantially amorphous and highly crystalline products.

Taking polyethylene as an example, a low-density homopolymer having many long-chain branches produced by a high-pressure method, a copolymer of ethylene and vinyl acetate, acrylic acid, methacrylic acid, acrylate, methacrylate, etc., a low-pressure method. Examples of the produced high-density polyethylene or a copolymer of ethylene and another olefin, a high-density polyethylene or a copolymer of ethylene and another olefin produced by a medium pressure method, and the like.

Polypropylene includes polypropylene having stereoregularity, that is, isotactic polypropylene and syndiotactic polypropylene having high crystallinity, and atactic polypropylene having low crystallinity. As a polymer of an olefin higher than propylene, there is a polymer of butene-1, which is also included from a highly stereoregular crystalline polymer to an amorphous polymer. Further, polymers of higher olefins include poly-4-methylpentene-1. In addition, various olefin polymers are used without limitation on the type of α-olefin.

Copolymers of ethylene and propylene, ethylene and butene-1, and ethylene and hexene-1 can also be used. In this case, either a random copolymer or a block copolymer can be used. For example, ethylene and propylene can be used. Ethylene-propylene rubber obtained by polymerization in the presence of a Ziegler-based catalyst, and optionally, dicyclopentadiene, ethylidene norbornene, or 1,4 as an unsaturated component.
-A terpolymer containing hexadiene (EPDM
Etc.) are also included.

Further, a mixture thereof, an alloy or the like can be used. The copolymer obtained by copolymerizing the polymerizable reactant and the vinyl monomer can be blended with the olefin polymer as follows. As the mixing device, any known kneading machine such as a Brabender blast graph, an extruder, a strong screw type kneading machine, and a roll can be used. The temperature depends on the type of raw material, but in the case of high density polyethylene, for example, 150 to 2
It can be carried out at 50 ° C. The mixing ratio is selected so as to effectively exhibit the characteristics of the composition of the present invention described below, but is usually in the range of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polyolefin. Chosen from within.

The constitutional requirements of the composition of the present invention have been described above with reference to preferable examples. In the composition of the present invention, a colorant, a stabilizer, other additives and a filler which have been generally used in the past are further blended. It goes without saying that it is good. As the filler, sand, natural silica such as quartz, wet method, synthetic silica produced by a dry method, kaolin, mica,
Natural silicates such as talc, clay, asbestos, synthetic silicates such as calcium silicate and aluminum silicate, metal oxides such as alumina and titania, calcium carbonate, calcium sulfate, other metal powders such as aluminum and bronze, carbon black, etc. Can be used.

The composition of the present invention obtained as described above has very good adhesiveness, coating adhesion and printability when it is molded into a film, sheet, plate or other shape. .

[0055]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In the following examples, T peel strength was measured by cutting a 25 mm wide strip-shaped sample from an adhesive sheet and using a Tensilon UTM-III-100 type tensile tester manufactured by Toyo Baldwin Co., Ltd. Under the conditions of, the tensile speed was measured at 50 mm / min. Further, in the following examples, the number average molecular weight means a value in terms of polystyrene by the GPC method.

Reference Example (A) In a flask equipped with a nitrogen inlet, polytail HA as a polyhydroxy hydrocarbon polymer (manufactured by Mitsubishi Kasei Co., Ltd.,
Number average molecular weight 2000, hydroxyl equivalent 0.934 meq /
g, iodine value 3.8, Polytail is a registered trademark) 457
g, Takenate TMI (manufactured by Takeda Pharmaceutical Co., Ltd., m-isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanate group equivalent 4.845 meq / g, Takenate is a trademark) 43 g (hydroxyl group equivalent / isocyanate group equivalent = 2 / 1), tin catalyst (Mitsubishi Kasei Dow Co., Ltd., U
L-22) (0.015 g) was charged, the inside of the flask was replaced with nitrogen, and the inside of the flask was sealed with nitrogen, followed by reaction at 60 ° C. for 6 hours to obtain a product. The reaction was completed by IR, 2250c
This was confirmed by the disappearance of absorption of isocyanate groups near m ^-1 . Also by IR, absorption of a carbon-carbon double bond was observed at 1620 cm ^-1, and it was confirmed that a polymerizable unsaturated group was introduced. The number average molecular weight of the product is 23
It was 00.

Reference Example (B) 466 g of polytail HA, methacryloyloxyethyl isocyanate (MOE) instead of Takenate TMI
I, abbreviated to Kokusan Kagaku Co., Ltd., isocyanate group equivalent 6.
(445 meq / g) 34 g (hydroxyl group equivalent / isocyanate group equivalent = 2/1), except that the same procedure as in Reference Example (A) was performed to obtain a product. Confirmation of completion of the reaction and introduction of the polymerizable unsaturated group was also carried out in the same manner as in Reference Example (A). The number average molecular weight of the product was 2400.

Reference Example (C) 470 g of Polytail HA and 30 g of Takenate TMI
A product was obtained in the same manner as in Reference Example (A) except that (hydroxyl equivalent / isocyanate equivalent = 3/1). Confirmation of completion of the reaction and introduction of the polymerizable unsaturated group was also carried out in the same manner as in Reference Example (A). The number average molecular weight of the product was 2200.

Reference Example (D) 50 g of the polymerizable reaction product obtained in Reference Example (A), 150 g of 2-hydroxyethyl acrylate, and α, α-azo were placed in a flask equipped with a stirring blade, a reflux condenser, and a gas inlet. After charging 2 g of bisisobutyronitrile (AIBN) and further adding 600 g of tetrahydrofuran as a solvent to make a uniform solution, copolymerization was carried out at 60 ° C. for 24 hours under a nitrogen stream. After the polymerization, the reaction solution was poured into methanol to precipitate a product, which was thoroughly washed with methanol and dried. The yield was about 98%. The polystyrene-equivalent number average molecular weight by GPC was 32,000.

Reference Example (E) The flask used in Reference Example (D) was charged with 10 g of the polymerizable reaction product obtained in Reference Example (A), 10 g of metaacroyloxyethyltrimethylammonium chloride, and AIBN0.
Charge 2 g, and then add 20 g of toluene and 20 g of isopropyl alcohol as a solvent, and in a nitrogen stream,
Polymerization was carried out at 0 ° C for 7 hours and further at 95 ° C for 2 hours. After the polymerization, the reaction solution was poured into methanol to precipitate a product, which was thoroughly washed with methanol and dried. Yield is about 95
%Met.

Reference Example (F) The flask used in Reference Example (D) was charged with 5 g of the polymerizable reaction product obtained in Reference Example (A), 5 g of 2-perfluorooctylethyl acrylate, 0.03 g of AIBN and 7 g of toluene. After making a homogeneous solution, under a nitrogen stream at 70 ℃ 8
Polymerized for hours. After the polymerization, post treatment was carried out in the same manner as in Reference Example (D) to obtain a product. The yield was almost 100%. The polystyrene-equivalent number average molecular weight by GPC is 23,0.
It was 00.

Reference Example (G) In the flask used in Reference Example (D), 15 g of the polymerizable reaction product synthesized in Reference Example (A), 15 g of N-vinylpyrrolidone,
2-hydroxyethyl acrylate 15g, AIBN
After charging 0.05 g and 30 g of toluene into a uniform solution, polymerization was carried out at 70 ° C. for 8 hours in a nitrogen stream. After polymerization,
Post-treatment was carried out in the same manner as in Reference Example (D) to obtain a product.

Reference Example (H) 10 g of the polymerizable reaction product synthesized in Reference Example (A), 10 g of 3-methacryloxypropylmethyldimethoxysilane, and 1 g of methyl methacrylate in the flask used in Reference Example (D).
Charge 0 g, AIBN 0.1 g and toluene 20 g,
After forming a uniform solution, polymerization was carried out at 70 ° C. for 8 hours under a nitrogen stream. After the polymerization, post treatment was carried out in the same manner as in Reference Example (D) to obtain a product. The yield was 89%. The polystyrene-equivalent number average molecular weight by GPC was 180,000.
A part of the polymerization solution was applied onto a polyethylene sheet, air-dried, and allowed to stand at room temperature for 1 week, whereby a tough coating film having excellent adhesion was obtained.

Reference Example (I) 10 g of the polymerizable composition obtained in Reference Example (B) in the flask used in Reference Example (D), 4-methacryloyloxyethyl-
2-hydroxybenzophenone 10 g, AIBN 0.2
g and tetrahydrofuran 20 g were charged and polymerized at 70 ° C. for 8 hours under a nitrogen stream. After the polymerization, post treatment was carried out in the same manner as in Reference Example (D) to obtain a product. The yield was 98%. The polystyrene reduced number average molecular weight by GPC is 3
It was 5,000.

Reference Example (J) In the flask used in Reference Example (D), 100 g of the polymerizable composition obtained in Reference Example (C), 100 g of 2-hydroxyethyl methacrylate, 2 g of AIBN and 6 of tetrahydrofuran.
It was dissolved in 00 g and polymerized at 60 ° C. for 24 hours. After polymerization,
Post-treatment was carried out in the same manner as in Reference Example (D) to obtain a product.
The yield was 96%. The polystyrene reduced number average molecular weight by GPC was 19,000.

Reference Example (L) Polytail HA (manufactured by Mitsubishi Kasei Co., Ltd.) as a polyhydroxy hydrocarbon polymer was placed in a flask equipped with a reflux condenser.
Number average molecular weight 2000, hydroxyl equivalent 0.934 meq /
g, iodine value 3.8) 481 g, methyl acrylate 19
g (hydroxyl group equivalent / ester group equivalent = 2/1), p-toluenesulfonic acid 1.5 g, and toluene 500 g were charged,
The reaction was carried out at 80 ° C. for 8 hours while discharging the produced methanol. The completion of the reaction was confirmed by stopping the outflow of methanol. The content of the flask was put into a large amount of acetone to remove paratoluenesulfonic acid contained in the product, and further dried under reduced pressure at 50 ° C. for 1 hour to obtain a product. The IR, absorption of an ester bond to 1740 cm ^-1, carbon 1620 cm ^-1 - absorbed carbon double bond was observed, polymerizable unsaturated group was confirmed to have been introduced. The number average molecular weight of the product was 2300.

50 g of this polymerizable composition, methacrylic acid 2
When 150 g of hydroxyethyl and 2 g of α, α-azobisisobutyronitrile were dissolved in 600 g of tetrahydrofuran and copolymerized at 60 ° C. for 24 hours, a polymer having a number average molecular weight of 21,000 was obtained.

Reference Example (M) 487 g of polytail HA and 13 g of methyl acrylate
A product was obtained in the same manner as in Reference Example (L) except that (hydroxyl group equivalent / ester group equivalent = 3/1). The number average molecular weight of the product was 2200. When this polymerizable composition was copolymerized with 2-hydroxyethyl methacrylate in the same manner as in Reference Example (L), a polymer having a number average molecular weight of 15,000 was obtained.

Example 1 The improvement of the adhesiveness of the olefin polymer composition obtained from the polymer obtained in Reference Example (D) and EPDM was examined. The following compound was kneaded with a Brabender at 100 ° C. for 10 minutes and then press-vulcanized at 150 ° C. for 40 minutes to prepare an EPDM sheet.
(Parts in parentheses are parts by weight) EP57C (Nippon Synthetic Rubber Co., Ltd.)
(Made) (100) / zinc oxide (5) / stearic acid (1)
/ Carbon black FEE (50) / Naphthene oil (50) / Vulcanization accelerator CBS (1.6) / Vulcanization accelerator D
PG (0.8) / vulcanization accelerator TMTD (0.5) / sulfur (2) / polymer (2) obtained in Reference Example (D)

The EPDM sheets are attached to each other by polytail H.
(Manufactured by Mitsubishi Kasei Co., Ltd., polyhydroxy hydrocarbon polymer, hydroxyl equivalent 0.848 meq / g) 74 parts, Iso
nate143L (manufactured by Mitsubishi Kasei Dow Co., Ltd., polyisocyanate, isocyanate group equivalent 6.92 meq / g,
Isonate is a trademark, and it was pasted together with an adhesive consisting of 10 parts and cured at 120 ° C. for 1 hour. When the T peel strength of this adhesive sheet was measured, it was 8.2 kgf / 25 mm.
Therefore, the peeling condition was substrate destruction. When the same procedure is carried out without blending the polymer obtained in Reference Example (D),
The T-peel strength was 6.7 kgf / 25 mm and the state of peeling was interfacial peeling, confirming the effect of improving the adhesiveness of EPDM containing the polymer obtained in Reference Example (D).

<Example 2> An improvement in adhesiveness of an olefin polymer composition obtained from the polymer obtained in Reference Example (M) and EPDM was examined. The following compound was kneaded with a Brabender at 100 ° C. for 10 minutes and then press-vulcanized at 150 ° C. for 40 minutes to prepare an EPDM sheet.
(Parts in parentheses are parts by weight) EP57C (Nippon Synthetic Rubber Co., Ltd.)
(Made) (100) / zinc oxide (5) / stearic acid (1)
/ Carbon black FEE (50) / Naphthene oil (50) / Vulcanization accelerator CBS (1.6) / Vulcanization accelerator D
PG (0.8) / vulcanization accelerator TMTD (0.5) / sulfur (2) / polymer (2) obtained in Reference Example 2 (M)

The above EPDM sheets are connected to each other by polytail H.
(Manufactured by Mitsubishi Kasei Co., Ltd., polyhydroxy hydrocarbon polymer, hydroxyl equivalent 0.848 meq / g) 74 parts, Iso
nate143L (manufactured by Mitsubishi Kasei Dow Co., Ltd., polyisocyanate, isocyanate group equivalent 6.92 meq / g)
It was bonded with an adhesive consisting of 10 parts and cured at 120 ° C. for 1 hour. The T-peel strength of this adhesive sheet was measured and found to be 8.3 kgf / 25 mm. When the same procedure was performed without adding the polymer obtained in Reference Example (M), the T peel strength was 6.7 kgf /
It was 25 mm, and the state of peeling was interfacial peeling, and the effect of improving the adhesiveness of the EPDM containing the polymer obtained in Reference Example (M) was confirmed.

Example 3 3 parts of the copolymer obtained in Reference Example (G), 60 parts of a propylene-ethylene block copolymer having an ethylene content of 9% by weight and 40 parts of EPDM were used at 200 ° C. using a Brabender. After kneading for 4 minutes at 200 ℃
I made a heat press sheet. An adhesion test was conducted in the same manner as in Example 1 to find that the T peel strength was 7.9 k.
The value was gf / 25 mm and the substrate was destroyed. On the other hand, when the same procedure is carried out without blending the copolymer obtained in Reference Example (G),
The T-peel strength was 2.3 kgf / 25 mm, indicating interfacial peeling.

<Example 4> 20 parts of the copolymer obtained in Reference Example (E) and 80 parts of an amorphous polyethylene copolymer (manufactured by Mitsui Petrochemical Co., Tuffmer A4085: Tuffmer is a trademark) were added to 80 parts of xylene. It was heated and dissolved at 0 ° C. to obtain a 5 wt% solution. This solution was cast on a polyethylene sheet and dried at 75 ° C. for 8 hours with a hot air dryer to form a coating film on the polyethylene sheet. The surface resistance value of this coating film was measured and found to be 7.5 × 10 ⁸ Ω / port, which was excellent in antistatic properties. On the other hand, when the same procedure was carried out without blending the copolymer obtained in Reference Example (E), the surface resistance value was 10 ¹⁶ Ω / mouth, and there was no antistatic property at all.

Example 5 1 part of the copolymer obtained in Reference Example (F) and 99 parts of high-pressure polyethylene were kneaded with a Brabender at 200 ° C. for 4 minutes and then hot pressed at 200 ° C. to give a polyethylene sheet. Created. When the contact angle of this sheet with water was measured, it was 120 degrees, and a value equivalent to that of Teflon was obtained, indicating high water repellency. On the other hand, Reference Example (F)
When the same procedure was carried out without blending the copolymer obtained in step 1, the result was 100 degrees.

Example 6 10 parts of the copolymer obtained in Reference Example (H) and 90 parts of high-pressure polyethylene were kneaded with a Brabender at 200 ° C. for 4 minutes and then hot pressed at 200 ° C. to give a polyethylene sheet. Created. 4 this sheet in boiling water
After soaking for an hour, it was air dried. The dried sheet was not deformed even when placed in an oven at 150 ° C. On the other hand, when the same operation was carried out without blending the copolymer obtained in Reference Example (H), the sheet was deformed in the oven at 150 ° C. until the shape of the sheet was not stopped.

<Example 7> The procedure of Example 1 was repeated except that the copolymer obtained in Reference Example (J) was used in place of the copolymer obtained in Reference Example (D). Where T
The peel strength was 7.8 kgf / 25 mm, and the substrate was destroyed.

Example 8 10 g of the copolymer obtained in Reference Example (I) was added to 90 parts of an amorphous polyethylene copolymer (Mitsui Petrochemical Co., Ltd., Tuffmer A4085, Tuffmer is a trademark) in xylene at 80 ° C. It was heated and dissolved in to obtain a 5% by weight solution. This solution was cast on a glass plate, dried at 75 ° C. for 8 hours with a hot air dryer, and then the film was peeled off. When the ultraviolet absorption spectrum of this film was measured, it was found that wavelengths of 360 nm or shorter were cut off. On the other hand, when the copolymer obtained in Reference Example (J) was blended in the same manner without blending,
Only the wavelength of m or less could be cut.

[0079]

EFFECT OF THE INVENTION The olefin polymer composition obtained by the method of the present invention has significantly improved adhesiveness, coating adhesion and printability without the need for primer coating or plasma treatment. Useful for plates, etc.

Claims (2)

[Claims] 1. A hydroxyl group equivalent of a polyhydroxy hydrocarbon polymer (A) having a number average molecular weight of 500 to 20,000 is added to an olefin polymer as A, and both a polymerizable unsaturated group and an isocyanate group are contained in one molecule. The polymerizable composition obtained by reacting (A) and (B) under the condition that A / B is 1.5 or more, where the isocyanate group equivalent of the compound (B) has B, is a vinyl-based monomer. An olefin-based polymer composition comprising a copolymer composition obtained by copolymerization. 2. A hydroxyl group equivalent of a polyhydroxy hydrocarbon polymer (A) having a number average molecular weight of 500 to 20,000 in an olefin polymer is A, and a polymerizable unsaturated group and a carboxyl group or a carboxyl group in one molecule. The equivalent amount of the carboxyl group or the functional group derived from the carboxyl group of the compound (C) having both functional groups derived from
As a copolymer composition obtained by copolymerizing a polymerizable composition obtained by reacting (A) and (C) under the condition that A / C is 1.5 or more with a vinyl monomer An olefin-based polymer composition comprising: