JP2009221466A - Modified polyolefin resin composition and method for producing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyolefin resin composition which excels in solubility in a non-aromatic solvent and is good in adhesion to an olefin substrate hard to adhere. <P>SOLUTION: The modified polyolefin resin composition is characterized by being obtained by graft copolymerization of (A) a modified polyolefin resin having a carboxyl group with (B) an ethylenically unsaturated compound containing at least styrenes (a) and N-substituted (meth)acrylamide (b). The N-substituted (meth)acrylamide (b) is preferably N,N-dimethylacrylamide and/or N,N-diethylacrylamide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to sheet-like materials, films and formed articles such as homopolymers of olefins such as polyethylene, polypropylene and polybutene, and copolymers with other copolymerizable monomers based on these olefins. Modified polyolefin resin that has an ethylenically unsaturated compound efficiently added to a modified polyolefin resin having a carboxyl group, which has excellent adhesive properties and is excellent in solubility in polar solvents such as alcohols and ester solvents. Relates to the composition.

Homopolymers of olefins such as polyethylene, polypropylene and polybutene and copolymers with other copolymerizable monomers based on these olefins (hereinafter collectively referred to as “polyolefins”) It is relatively inexpensive and has good moldability, heat resistance, water resistance, solvent resistance, mechanical properties, appearance, etc., and is copolymerized or blended with different polymers to form various alloys. It can be made into a composite material in combination with an inorganic material, or laminated on a metal, and can be made into a material that can exhibit more excellent features. Therefore, it is processed into various molded products and used in various fields. Furthermore, various molded products using these polyolefins are bonded to other materials, and the surfaces of the molded products are painted or printed. However, since the polyolefin resin is composed of saturated hydrocarbons and has poor chemical reactivity and low polarity, the adhesiveness, paintability, printability and the like are insufficient.

In order to solve these problems, it is effective to give a polar group to a part or all of the polyolefin, a method of treating the polyolefin resin with radiation such as an electron beam or ozone, or a radical such as an organic peroxide. A method is known in which an ethylenically unsaturated compound such as an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a derivative thereof is modified by graft reaction in the presence of a generator (see, for example, Patent Documents 1 to 3). .

Polyolefins that have been acid-modified by graft reaction of ethylenically unsaturated compounds such as unsaturated carboxylic acids or their anhydrides are used as compatibilizers and adhesives for polyolefins and other resins, dispersants and adhesives for inorganic materials, and metals. It can be used as an adhesive, a primer such as a polyolefin substrate, an additive for ink and paint, and the like. However, from the viewpoint of performance, aromatic solvent varnishes of chlorinated polyolefins are often used as primers for polyolefin base materials and additives for inks and paints (for example, Patent Documents 4 to 6). In recent years, there are environmental problems due to organic halogens, and the use of high-performance acid-modified polyolefins instead of chlorinated polyolefins has been studied (for example, Patent Documents 7 to 9).

However, the acid-modified polyolefin has a drawback of low solubility in a solvent. Therefore, it is necessary to use a non-polar aromatic solvent such as toluene or xylene as a solvent used for dissolution. However, from the viewpoint of reducing environmental burdens in recent years, a resin that can be dissolved in a solvent other than an aromatic solvent has been demanded. As a solution to these problems, studies have been conducted to graft a limited ethylenically unsaturated compound to polyolefin (for example, Patent Documents 10 to 12).

JP 49-010890 A Japanese Patent Application Laid-Open No. 64-087611 Japanese Patent Laid-Open No. 01-282207 Japanese Patent Publication No. 50-010916 Japanese Patent Laid-Open No. 10-168123 Japanese Patent Laid-Open No. 11-315185 Japanese Patent Laid-Open No. 05-194926 JP 2001-139642 A Japanese Patent Laid-Open No. 2002-212241 Japanese Patent Laid-Open No. 2003-064111 JP 2004-277617 A Japanese Patent Laying-Open No. 2005-163030

However, the modified polyolefin resin obtained by grafting an ethylenically unsaturated compound that has been studied in the past is still insufficient in the graft copolymerization efficiency to the polyolefin, so that a polymer of an ethylenically unsaturated compound is easily generated. Insufficient adhesion to non-polar substrates. In particular, it is difficult to dissolve in an ester-based or alcohol-based highly-used solvent that is frequently used as a non-aromatic solvent, and there is a problem that the intended use is limited.

In view of the above circumstances, the present invention provides a resin composition having excellent adhesion to a nonpolar substrate and further exhibiting excellent solvent solubility in a non-aromatic solvent. And

As a result of intensive studies, the inventors have used a graft copolymer of an ethylenically unsaturated compound having styrenes and N-substituted (meth) acrylamide as essential components for the modified polyolefin resin having a carboxyl group, It has been found that it has excellent adhesion to non-polar substrates and also exhibits excellent solvent solubility in non-aromatic solvents.

Specifically, the present invention can be solved as follows.
That is, the present invention graft-polymerizes an ethylenically unsaturated compound (B) containing at least styrenes (a) and N-substituted (meth) acrylamide (b) to a modified polyolefin resin (A) having a carboxyl group. A modified polyolefin resin composition (C) (Invention 1) obtained by

In the modified polyolefin resin composition (C) of the first aspect of the present invention, the N-substituted (meth) acrylamide (b) is N, N-dimethylacrylamide and / or N, N-diethylacrylamide. Modified polyolefin resin composition (C) (Invention 2).

Further, the present invention provides the modified polyolefin resin composition (C) according to the first or second aspect of the present invention, wherein the ethylenically unsaturated compound (B) contains styrenes (a), N-substituted (meth) acrylamide (b) and A modified polyolefin resin composition (C) comprising at least a saturated carboxylic acid ester (c) (Invention 3).

The present invention also provides the modified polyolefin resin composition (C) according to any one of the first to third aspects, wherein the ethylenically unsaturated compound (B) contains at least 40 parts by weight of styrenes (a) and N-substituted (meta ) A modified polyolefin resin composition (C) characterized by containing at least 10 parts by weight of acrylamide (b) (Invention 4).

Further, the present invention provides the modified polyolefin resin composition (C) of the invention 3, wherein the ethylenically unsaturated compound (B) comprises 40 to 80 parts by weight of styrenes (a), N-substituted (meth) acrylamide (b 10) to 20 parts by weight, and a modified polyolefin resin composition (C) (Invention 5), which contains 10 to 40 parts by weight of an unsaturated carboxylic acid ester (c).

The present invention also provides a resin composition (D) (invention 6) obtained by blending the modified polyolefin resin (A) having a carboxyl group and the modified polyolefin resin compositions (C) of the inventions 1 to 5.

In the present invention, the modified polyolefin resin (A) having a carboxyl group and the modified polyolefin resin composition (C) of the invention 1 to invention 5 are mixed in an organic solvent at 100 to 200 ° C. to remove the solvent. A method for producing a resin composition (D) (Invention 7).

In addition, the present invention provides the resin composition according to the invention 6 or the invention 7, wherein the modified polyolefin resin (A) having a carboxyl group contains 50 parts by weight or less with respect to 100 parts by weight of the modified polyolefin resin composition (C). Method for producing product (D) (Invention 8).

ADVANTAGE OF THE INVENTION According to this invention, the modified polyolefin resin composition which provides the solubility to the non-aromatic solvent which was difficult conventionally, and has favorable adhesiveness to an olefin base material can be provided.

Furthermore, the modified polyolefin resin composition produced by the method for producing a modified polyolefin according to the present invention suppresses the generation of unreacted residues and by-products compared to the modified polyolefin resin composition produced by a conventional production method. As a result, the performance degradation of the modified polyolefin resin composition is small, and the modification reaction proceeds efficiently, so that the modification rate can be easily increased. Therefore, high performance can be exhibited as an additive for inks and paints, a primer and an adhesive for polyolefin base materials, a compatibilizer for polyolefin base materials and other resins, and a modifier for polyolefin base materials. Moreover, in order to show the outstanding solubility to a non-aromatic solvent, it can contribute to environmental load reduction.

The configuration of the present invention will be described in more detail as follows.

<< Modified polyolefin resin having carboxyl group (A) >>
The modified polyolefin resin (A) having a carboxyl group used in the present invention may be any modified polyolefin resin having a carboxyl group in the molecule, for example, a polyolefin obtained by modifying a polyolefin with an unsaturated carboxylic acid. A modified polyolefin resin having a carboxyl group obtained by modification using unsaturated carboxylic acids, (meth) acrylic acid alkyl ester, and organic peroxide is a polyolefin-based resin, compatibility with a substrate, adhesion It is more preferable because the property is improved.

The polyolefin used in the modified polyolefin resin (A) having a carboxyl group of the present invention is an α-olefin copolymer containing at least ethylene and propylene. As the α-olefin, ethylene, propylene, 1-butene, 1 -Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-dodecadecene, 4-methyl-1-pentene and the like. Examples of the copolymer include a random copolymer, a block copolymer, a graft copolymer, and a mixture thereof. In particular, ethylene-propylene and ethylene-propylene-1-butene copolymers are preferable because they have good compatibility and adhesion with a resin mainly composed of polyolefin and a substrate, and the resin itself is flexible.

The density of the polyolefin used in the present invention is preferably from 0.85 g / cm ^{3 to} 0.89 g / cm ³ . Polyolefin resins having a density of less than 0.85 g / cm ³ are not common and only polyolefins having insufficient strength can be obtained. Therefore, the density is preferably 0.85 g / cm ³ or more. When the density is 0.89 g / cm ³ or less, the crystallinity of the polyolefin is low, and the (meth) acrylic acid alkyl ester and unsaturated carboxylic acids used when introducing a carboxyl group are easily compatible with the polyolefin. Therefore, the reaction efficiency is improved, and the unreacted residue and the generation of by-products can be suppressed.

The molecular weight of the polyolefin preferably has a weight average molecular weight of 10,000 or more and 200,000 or less. Compared with the case where the weight average molecular weight is less than 10,000, when the weight average molecular weight is 10,000 or more and 200,000 or less, the cohesive force is increased, and the effect is improved when performing adhesion, surface modification or the like. Therefore, it is preferable. Compared with the case where the weight average molecular weight is larger than 200,000, when the weight average molecular weight is 10,000 or more and 200,000 or less, the fluidity is improved. Therefore, unsaturated carboxylic acids used for introducing a carboxyl group and It is preferable because the (meth) acrylic acid alkyl ester can be easily dispersed uniformly, the reaction efficiency can be improved, and unreacted residues and generation of by-products can be suppressed. Further, even when the weight average molecular weight is greater than 200,000, the molecular weight is 10,000 or more and 200,000 by a known method such as degrading in the presence of heat or radical to prepare the molecular weight within an appropriate range. By setting it to 000 or less, it can be used as a preferred polyolefin.

Further, the ethylenically unsaturated group containing at least a styrene (a) and an N-substituted (meth) acrylamide (b) in a modified polyolefin resin (A) having a carboxyl group obtained from a polyolefin having a weight average molecular weight of greater than 200,000. The modified polyolefin resin composition obtained by graft copolymerization of the compound (B) has poor solubility in non-aromatic solvents and may not be sufficiently soluble in non-aromatic solvents. .

Unsaturated carboxylic acids used in the modified polyolefin resin (A) having a carboxyl group of the present invention are unsaturated carboxylic acids other than (meth) acrylic acid alkyl esters and derivatives thereof, preferably acrylic acid, methacrylic acid, Unsaturated monobasic acids such as crotonic acid and cinnamic acid, unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride, and unsaturated dibasic Acid and methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 2-butanol, t-butanol, cyclohexanol, 2-ethylhexanol, n-octanol, n-dodecyl alcohol, n-octadecyl Alcohol, ethylene glycol monoethyl ether, ethyl Group of monoesters with methyl glycol mono-i-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and the like, methylamine, dimethylamine, ethylamine Amides and imides with diethylamine, n-propylamine, i-propylamine, n-butylamine, cyclohexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, aniline, benzylamine, etc. And at least one compound selected from the group consisting of Maleic anhydride and / or its derivatives are particularly preferred because they have poor homopolymerization and the grafting reaction easily proceeds.

The amount of the unsaturated carboxylic acid used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyolefin. Compared to the case where the content is less than 0.5 parts by weight, when the content is 0.5 parts by weight or more and 30 parts by weight or less, the modified polyolefin can be provided with sufficient polarity, and the resin or base material mainly composed of polyolefin It is preferable because the compatibility and adhesion are improved, and when it is 1 part by weight or more and 20 parts by weight or less, the compatibility and adhesiveness are further improved. Moreover, compared with the case where the amount is more than 30 parts by weight, when the amount is 0.5 part by weight or more and 30 parts by weight or less, the efficiency of the reaction for adding unsaturated carboxylic acids is improved, so that the generation of by-products is suppressed. Preferably, the amount is 1 part by weight or more and 20 parts by weight or less, and the reaction efficiency is further improved and generation of by-products is suppressed.

When the unsaturated carboxylic acids are reacted, it is particularly preferable to use a (meth) acrylic acid alkyl ester in combination because the grafting reaction is facilitated and the amount of unreacted products and ungrafted oligomers is easily suppressed.

The (meth) acrylic acid alkyl ester is an acrylic acid alkyl ester or a methacrylic acid alkyl ester, preferably methyl acrylate or methacrylic acid which is an ester with a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Methyl acid, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-acrylate -Butyl, i-butyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2 -Ethylhexyl, acrylic It is at least one compound selected from n-octyl acid, n-octyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate and the like at high temperature In order to carry out the reaction, n-butyl acrylate, n-butyl methacrylate, which is an ester of an alcohol having a linear, branched or cyclic alkyl group having a boiling point of 150 ° C. or higher and 4 or more carbon atoms and acrylic acid or methacrylic acid. Butyl, i-butyl acrylate, i-butyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-acrylate Ethylhexyl, 2-ethylhexyl methacrylate, acrylic acid - octyl methacrylate n- octyl, acrylic acid n- dodecyl, methacrylic acid n- dodecyl, acrylic acid n- octadecyl, preferably from the reaction of methacrylic acid n- octadecyl and the like to be added to the polyolefin easily proceeds. These may be used alone or in a combination of two or more.

The amount of the (meth) acrylic acid alkyl ester is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyolefin. Compared with the case where the content is less than 0.5 parts by weight, when the content is 0.5 parts by weight or more, the copolymerization with the grafted unsaturated carboxylic acid proceeds and the generation of by-products is suppressed. Preferably, the amount is 1 part by weight or more, since the graft chain copolymerization further proceeds and generation of by-products is suppressed. In addition, when the amount is 30 parts by weight or less compared to the case where the amount is more than 30 parts by weight, the amount of by-products such as a homopolymer of (meth) acrylic acid alkyl ester is reduced, and preferably 20 parts by weight or less. In some cases, the amount of by-products is further reduced, which is preferable.

As a use ratio of the (meth) acrylic acid alkyl ester and the unsaturated carboxylic acid, the molar ratio of the (meth) acrylic acid alkyl ester to the unsaturated carboxylic acid is (meth) acrylic acid alkyl ester / unsaturated carboxylic acid = 0.5 to 2.0 is preferable. Compared with the case where the molar ratio is less than 0.5, when the molar ratio is 0.5 to 2.0, copolymerization and grafting of (meth) acrylic acid alkyl ester and unsaturated carboxylic acids are carried out. Since both occur efficiently, compatibility with the polyolefin-based resin and the base material is improved and adhesion is preferable, and since ungrafted unsaturated carboxylic acids are reduced, they are derived from unsaturated carboxylic acids. Since generation | occurrence | production of byproducts, such as an unreacted substance and a black foreign material, can be suppressed, it is preferable. Further, when the molar ratio is 0.5 to 2.0, compared with the case where the molar ratio is larger than 2.0, the grafting of the (meth) acrylic acid alkyl ester and the unsaturated carboxylic acid is performed. Copolymer is reduced, grafting efficiency is improved, polyolefin resin as the main component, compatibility with the base material and good adhesion are preferable, and ungrafted (meth) acrylic acid Since alkyl ester is reduced, generation of by-products such as unreacted products derived from (meth) acrylic acid alkyl esters, ungrafted polymers and black foreign matters can be suppressed, which is preferable.

In the modified polyolefin resin (A) having a carboxyl group, an ethylenically unsaturated compound other than the above (meth) acrylic acid alkyl ester and unsaturated carboxylic acid is used as long as the effect of the present invention is not impaired. It can be used simultaneously with esters and unsaturated carboxylic acids. Examples of the ethylenically unsaturated compound include styrene monomers such as styrene, α-methylstyrene, and divinylbenzene, olefins such as ethylene, propylene, and butene, alkadienes such as butadiene and isoprene, vinyl acetate, and vinyl propionate. And vinyl ethers such as vinyl ester, isobutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether. These may be used alone or in a combination of two or more. The amount of the ethylenically unsaturated compound used is 15 parts by weight or less when the total amount of the (meth) acrylic acid alkyl ester and the unsaturated carboxylic acid is 100 parts by weight in order not to inhibit the effects of the present invention. Is preferred.

The method for modifying the polyolefin in the modified polyolefin resin (A) having a carboxyl group can be carried out by a known method. For example, the polyolefin is dissolved in an organic solvent at a temperature equal to or higher than the softening point, and unsaturated carboxylic acids and Solution method in which (meth) acrylic acid alkyl ester and organic peroxide are added and reacted, polyolefin is melted at the softening point or higher, and unsaturated carboxylic acids, (meth) acrylic acid alkyl ester and organic peroxide are added and mixed Kneading the polyolefin, unsaturated carboxylic acids, (meth) acrylic acid alkyl ester, and organic peroxide at a temperature above the softening point of the polyolefin using a Banbury mixer, kneader, extruder, etc. Methods and the like. As addition methods of unsaturated carboxylic acids, alkyl (meth) acrylates and organic peroxides, batch addition, addition after diluting in organic solvent, divided addition, continuous addition method by dropping, etc. can be selected as appropriate. The order of addition can also be selected as appropriate. The modification reaction may be performed in multiple stages, and in that case, the respective reactors and reaction types can be used in appropriate combinations. In addition, a decompression step can be provided at the end of the reaction to remove residual unsaturated carboxylic acids, (meth) acrylic acid alkyl ester, organic peroxide, decomposition product of organic peroxide, organic solvent, and the like.

The organic peroxide that can be used in the present invention may be a peroxide having a carbon atom in the skeleton of the compound, and is preferably a peroxide capable of generating a radical having a hydrogen abstracting effect. Specifically, ketone peroxide , Peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxy dicarbonates, alkyl peroxy carbonates, specifically, diisobutyryl peroxide, cumyl peroxy neodecanate Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanate, di (4-t- Butylcyclohexyl) peroxy Dicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanate, dimethoxy Butyl peroxydicarbonate, t-butylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxypivalate, di (3,3,5-trimethylhexanoyl) peroxide, di-n- Octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoyl peroxy ) Hexane, t-hexylperoxy-2-ethylhexanate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanate, dibenzoyl peroxide, t-butylperoxyisobutyrate 1,1-di (t-butylperoxy) -2-methylcyclohexanate, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-di (T-butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexane) propane, t-hexylper Oxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,3,5-trimethyl Ruhexanate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmono Carbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t -Butyl peroxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t Butyl cumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butylhydro A peroxide etc. are mentioned. These may be used alone or in a combination of two or more.

The organic peroxide preferably has a structure that does not contain a hydroxyl group and an aromatic ring, and the modification obtained when an organic peroxide having a structure that does not contain a hydroxyl group and an aromatic ring is used. This is preferable because the polyolefin is less colored. The reaction of adding unsaturated carboxylic acids and (meth) acrylic acid alkyl ester to polyolefin is carried out in order to make unsaturated carboxylic acids, (meth) acrylic acid alkyl ester and organic peroxide compatible with polyolefin. It is necessary to carry out at a temperature higher than the softening point of softening and melting. On the other hand, in performing the addition reaction, it is preferable to suppress degradation of polyolefin by organic peroxide as much as possible. preferable. For this reason, it is preferable that the 1-hour half-life decomposition temperature of an organic peroxide is the range of 110-160 degreeC. In particular, t-butylperoxy-2-ethylhexyl monocarbonate, di-t-hexyl peroxide, di-t-butyl peroxide and the like are preferable because the one-hour half-life decomposition temperature is in the range of 110 to 160 ° C.

The amount of the organic peroxide used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyolefin. Compared with the case where the content is less than 0.1 parts by weight, when the content is 0.1 parts by weight or more and 10 parts by weight or less, the efficiency of the reaction of adding unsaturated carboxylic acids and (meth) acrylic acid alkyl ester is increased. In order to improve, it is preferable, and when it is 0.2 weight part or more and 5 weight part or less, since the efficiency of reaction improves further, it is preferable. In addition, when the amount is 0.1 parts by weight or more and 10 parts by weight or less as compared with the case where the amount is more than 10 parts by weight, since the cleavage of the polyolefin chain by radicals generated by the organic peroxide is suppressed, the low molecular weight component And the compatibility and adhesiveness are improved, and the amount of 0.2 part by weight or more and 5 parts by weight or less is preferable because the generation of low molecular weight components is further suppressed.

When the modified polyolefin resin (A) having a carboxyl group is prepared by the solution method, examples of the organic solvent include saturated aliphatic hydrocarbons such as hexane, heptane, and octane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclohexane Saturated alicyclic hydrocarbons such as heptane and methylcycloheptane, aromatic hydrocarbons not containing ethylenic double bonds such as toluene, xylene and ethylbenzene, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Alkylene glycol alkyl ether alkylates such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Does not contain ethylenic double bonds such as dialkylene glycol alkyl ether alkylates, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate etc. Esters, ketones that do not contain ethylenic double bonds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; And ethers that do not contain a heavy bond. These organic solvents may be used alone or in combination.

The amount of the organic solvent used is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyolefin. Compared with the case where the content is less than 5 parts by weight, when the content is 5 parts by weight or more, the viscosity of the polyolefin due to the organic solvent can be suppressed, so unsaturated carboxylic acids, (meth) acrylic acid alkyl ester and organic Uniform dispersion of the peroxide is facilitated. In addition, when the organic solvent is refluxed, the (meth) acrylic acid alkyl ester, unsaturated carboxylic acids, and organic peroxide that have condensed on the ceiling and walls of the reaction tank are washed and quickly returned to the modified polyolefin. Can do. Because of these effects, it is possible to suppress the generation of by-products generated by homopolymerization of unsaturated carboxylic acids and (meth) acrylic acid alkyl esters. Therefore, compatibility and adhesion in polyolefin-based resins and substrates The coating property, printability, and dispersibility are preferable, and when the amount is 10 parts by weight or more, more uniform dispersion is easily performed, cleaning can be easily performed, and generation of by-products can be suppressed. . In addition, when the amount is 50 parts by weight or less, the concentration of the polyolefin, the unsaturated carboxylic acid, the (meth) acrylic acid alkyl ester, and the organic peroxide is increased. It is preferable because the reaction easily proceeds, and when it is 30 parts by weight or less, it is preferable because the concentration during the reaction can be further increased.

Although there is no restriction | limiting in particular in the reaction temperature which modifies polyolefin, 100-200 degreeC is preferable. The temperature is preferably higher than the temperature at which the polyolefin melts or dissolves in the organic solvent so that the unsaturated carboxylic acids and organic peroxide can be uniformly dispersed, and specifically, it is preferably performed at 100 ° C. or higher. Moreover, it is preferable that the temperature is not excessively high in order to suppress a decrease in the molecular weight of the polyolefin due to the organic peroxide, and specifically, it is preferable to carry out at 200 ° C. or lower.

In the modified polyolefin resin (A) having a carboxyl group obtained as described above, a stabilizer for adjusting the stability can be added during production according to the purpose of use. Examples of the stabilizer include sorbitol, sorbitol alkylate, hydroquinone, benzoquinone, nitrosophenylhydroxy compound, phosphite compounds such as tris (2,4-di-t-butylphenyl) phosphite, pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] and other compounds such as pentaerythritol esters. These may be used alone or in a combination of two or more.

<< ethylenically unsaturated compound (B) >>
<Styrenes (a)>
Styrenes (a) used in the present invention are specifically styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene. , Pt-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p- Examples include phenylstyrene and α-methylstyrene. These may be used individually by 1 type, and may be used in combination of 2 or more types. Of these, styrene is preferred.

The amount of the styrene (a) used is preferably at least 40 parts by weight, more preferably 40 parts by weight or more and 80 parts by weight or less in the ethylenically unsaturated compound (B). When the amount used is less than 40 parts by weight, the grafting efficiency to the modified polyolefin resin (A) having a carboxyl group may be lowered, resulting in poor solubility in a polar solvent. In addition, the glass transition temperature of the resin is lowered during resinification, and it may be difficult to take out the resin. When the amount used is more than 80 parts by weight, a by-product may be generated. Moreover, since the polarity of the obtained modified polyolefin resin falls, when dissolving in a polar solvent, the solubility in the polar solvent may be poor.

<N-substituted (meth) acrylamide (b)>
The N-substituted (meth) acrylamide (b) used in the present invention is a compound in which one or two terminal hydrogen atoms of acrylamide or methacrylamide are substituted with other substituents. Specifically, N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N-iso-propylacrylamide, Nn-butylacrylamide, N-iso-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, Nn-propylmethacrylamide, Nt-butylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmeta Acrylamide, acryloylmorpholine, diacetone acrylamide and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types. In the present invention, N, N-dimethylacrylamide and N, N-diethylacrylamide are preferable for improving the grafting reaction efficiency and ensuring the fluidity of the varnish. In particular, N, N-dimethylacrylamide improves the grafting reaction efficiency to the modified polyolefin resin (A) having a carboxyl group, compared with other N-substituted (meth) acrylamides, and is used for unreacted products and ungrafted oligomers. This is preferable because the amount produced is easily suppressed.

The amount of N-substituted (meth) acrylamide (b) used is preferably at least 10 parts by weight of the ethylenically unsaturated compound (B), more preferably 10 parts by weight or more and 20 parts by weight or less. When the amount used is less than 10 parts by weight, the grafting efficiency to the modified polyolefin resin (A) having a carboxyl group decreases, and ungrafted products and by-products of the modified polyolefin resin (A) having a carboxyl group are present. May occur. Moreover, the polarity of resin becomes low and the solubility to a polar solvent becomes poor. When the amount used is more than 20 parts by weight, the fluidity of the varnish may become poor when the obtained modified polyolefin resin is dissolved in a polar solvent in order to increase the molecular weight. Moreover, the polarity of the obtained modified polyolefin resin becomes high, and the compatibility with the resin mainly composed of polyolefin and the base material may be poor.

<Unsaturated carboxylic acid ester (c)>
The unsaturated carboxylic acid ester (c) used in the present invention is specifically (meth) acrylic acid alkyl ester, monoester or diester of unsaturated dibasic acid, and the like. As the (meth) acrylic acid alkyl ester, preferably an ester with a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, N-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, acrylic acid 2-butyl, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, methacrylic acid n-octyl, acrylic acid n-do It is at least one compound selected from syl, n-dodecyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate, and the like, and has a boiling point of 150 ° C. or higher because it reacts at high temperatures. N-butyl acrylate, n-butyl acrylate, i-butyl acrylate, i-butyl methacrylate, acrylic ester which is an ester of an alcohol having a linear, branched or cyclic alkyl group and acrylic acid or methacrylic acid 2-butyl acid, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, methacrylic acid Acid n-octyl, acrylic acid n-dodecy , Methacrylic acid n- dodecyl, acrylic acid n- octadecyl, preferably from the reaction of methacrylic acid n- octadecyl and the like to be added to the polyolefin easily proceeds.

The monoester or diester of unsaturated dibasic acid is preferably an unsaturated dibasic acid such as fumaric acid, maleic acid, itaconic acid, citraconic acid, and methanol, ethanol, n-propanol, i-propanol, n-butanol. I-butanol, 2-butanol, t-butanol, cyclohexanol, 2-ethylhexanol, n-octanol, n-dodecyl alcohol, n-octadecyl alcohol, ethylene glycol monoethyl ether, ethylene glycol mono-i-propyl ether, Monoethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc. Is an ether or diester.

These unsaturated carboxylic acid ester (c) may be used individually by 1 type, and can also use 2 or more types together. As for the usage-amount of unsaturated carboxylic acid ester (c), 10 to 40 weight part is preferable among ethylenically unsaturated compounds (B). When the amount used is less than 10 parts by weight, the grafting efficiency to the modified polyolefin resin (A) having a carboxyl group may be lowered, resulting in poor solubility in a polar solvent. When the amount used is more than 40 parts by weight, a by-product may be generated. In addition, the glass transition temperature of the resin is lowered during resinification, and it may be difficult to take out the resin.

<Other ethylenically unsaturated compounds>
In the present invention, an ethylenically unsaturated compound other than the styrenes (a), N-substituted (meth) acrylamide (b), and unsaturated carboxylic acid ester (c) is ethylenically unsaturated unless the effects of the present invention are impaired. As compound (B), it can be used simultaneously with styrenes (a), N-substituted (meth) acrylamide (b), and unsaturated carboxylic acid ester (c). Examples of the ethylenically unsaturated compound include olefins such as ethylene, propylene and butene, alkadienes such as butadiene and isoprene, vinyl esters such as vinyl acetate and vinyl propionate, isobutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, and diethylene glycol mono Vinyl ethers, vinyl ethers such as 4-hydroxybutyl vinyl ether and the like, and unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Examples thereof include unsaturated dibasic unsaturated carboxylic acids such as citraconic acid and citraconic anhydride. These ethylenically unsaturated compounds may be used alone or in combination of two or more. In order not to inhibit the effects of the present invention, the amount of the ethylenically unsaturated compound used is preferably 10 parts by weight or less when the total amount of the ethylenically unsaturated compound (B) is 100 parts by weight.

<< Modified polyolefin resin composition (C) >>
The modified polyolefin resin composition (C) obtained by graft copolymerization of the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is obtained by using an ethylenically unsaturated compound (A) having a carboxyl group. The amount of the modified polyolefin resin (A) having a carboxyl group is preferably 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the total amount of the saturated compound (B). When the amount used is less than 5 parts by weight, the compatibility with the resin mainly composed of polyolefin and the substrate and the adhesiveness may be lowered. In addition, when the amount used is more than 30 parts by weight, the fluidity of the varnish may be poor when dissolved in a polar solvent.

The method of graft-copolymerizing the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group can be carried out by a known method, and the preparation of the modified polyolefin resin (A) having a carboxyl group Similar to the method, for example, a modified polyolefin resin (A) having a carboxyl group is heated to a temperature above the softening point and dissolved in an organic solvent, and an ethylenically unsaturated compound (B) and an organic peroxide are added and reacted. Method, melting method in which a modified polyolefin resin (A) having a carboxyl group is heated to a temperature above the softening point and melted, and an ethylenically unsaturated compound (B) and an organic peroxide are added and mixed to react with each other, having a carboxyl group The modified polyolefin resin (A), the ethylenically unsaturated compound (B) and the organic peroxide are mixed with a Banbury mixer, kneader, extruder, etc. And use, and a method of kneading with a softening point above the temperature of the modified polyolefin resin (A) having a carboxyl group. As addition method of ethylenically unsaturated compound (B) and organic peroxide, batch addition, addition after diluting into solution, divided addition, continuous addition method by dropping, etc. can be selected as appropriate, and the order of addition is also selected appropriately. it can. The modification reaction may be performed in multiple stages, and in that case, the respective reactors and reaction types can be used in appropriate combinations. In addition, a decompression step can be provided at the end of the reaction to remove the remaining ethylenically unsaturated compound (B), the organic peroxide, the decomposition product of the organic peroxide, and the organic solvent. In particular, from the viewpoint of productivity, after preparing the modified polyolefin resin (A) having a carboxyl group, an ethylenic polymer containing at least styrenes (a) and N-substituted (meth) acrylamide (b) continuously. A solution method capable of graft copolymerizing the saturated compound (B) is preferred.

The reaction temperature for graft-modifying the modified polyolefin resin (A) having a carboxyl group with the ethylenically unsaturated compound (B) is not particularly limited, but is preferably 100 to 200 ° C. It is preferable that the temperature is higher than the temperature at which the modified polyolefin resin (A) having a carboxyl group is melted or dissolved in an organic solvent so that the ethylenically unsaturated compound (B) and the organic peroxide can be uniformly dispersed. Is preferably carried out at 100 ° C. or higher. Moreover, it is preferable that the temperature is not excessively high in order to suppress a decrease in the molecular weight of the modified polyolefin resin (A) having a carboxyl group due to peroxide, and specifically, it is preferably performed at 200 ° C. or lower.

Moreover, the organic peroxide used when graft-copolymerizing the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is used when preparing the modified polyolefin resin (A) having a carboxyl group. Possible organic peroxides can be used. These may be used alone or in a combination of two or more.

Among organic peroxides, organic peroxides containing structures that generate alkoxy radicals with a slow β-cleavage rate are preferred, and organic peroxides containing structures that generate alkoxy radicals with a low β-cleavage rate are used. In this case, the graft efficiency of the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is improved, and the solubility of the resulting modified polyolefin resin composition in a nonpolar solvent is improved. In addition, the reaction of grafting the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is carried out by modifying the ethylenically unsaturated compound (B) and an organic peroxide with a modified polyolefin resin having a carboxyl group ( In order to make it compatible with A), it is necessary to carry out at a temperature higher than the softening point at which the modified polyolefin resin (A) having a carboxyl group is softened and melted. Since it is preferable to suppress degradation of the polyolefin by as much as possible, a temperature range as low as possible is preferable. Therefore, the one-hour half-life decomposition temperature of the organic peroxide is preferably in the range of 110 to 160 ° C. In particular, t-butyl peroxy-isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, etc. Is preferable because the one-hour half-life decomposition temperature is in the range of 110 to 160 ° C.

The amount of the organic peroxide used is preferably 1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the total amount of the modified polyolefin resin having a carboxyl group (A) and the ethylenically unsaturated compound (B). In particular, it is more preferably 5 parts by weight or more and 15 parts by weight or less. Compared to a case where the content is less than 1 part by weight, a case where the content is 1 part by weight or more and 20 parts by weight or less is preferable because the efficiency of the reaction for grafting the ethylenically unsaturated compound (B) is improved. This is preferable because the stability of the polar solvent varnish is improved. When the amount is 5 parts by weight or more and 15 parts by weight or less, the reaction efficiency and the stability of the nonpolar solvent varnish are further improved, which is preferable. Moreover, compared with the case where there are more than 20 weight part, when it is 1 weight part or more and 20 weight part or less, the production | generation of the by-product derived from an ethylenically unsaturated compound (B) and the modified polyolefin resin which has a carboxyl group ( Since the decrease in the molecular weight of A) is suppressed, the compatibility with the resin mainly composed of polyolefin and the base material is improved, and the adhesiveness is preferably improved. Since generation | occurrence | production of a product and the fall of molecular weight are suppressed, it is more preferable.

In addition, there is no particular limitation on the method of using the organic peroxide, but in order to improve grafting efficiency and suppress side reactions, a part is charged simultaneously with the modified polyolefin resin (A) having a carboxyl group, and the remainder is a monomer. At the same time, it is preferable to add in multiple portions, add dropwise over time, or add the entire amount in multiple portions simultaneously with the monomer, or drop over time.

Moreover, the organic solvent used when carrying out the graft copolymerization of the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group by a solution method is used at the time of preparing the modified polyolefin resin (A) having a carboxyl group. The said organic solvent which can be used can be used. These may be used alone or in a combination of two or more.

Among organic solvents, saturated alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and methylcycloheptane in which the modified polyolefin resin (A) having a carboxyl group dissolves, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons containing no ethylenic double bond are preferred. In addition, the reaction of grafting the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is carried out by modifying the ethylenically unsaturated compound (B) and an organic peroxide with a modified polyolefin resin having a carboxyl group ( In order to make it compatible with A), the molecular weight of the modified polyolefin resin (A) having a carboxyl group due to the organic peroxide is reduced more than the softening point and melting point of the modified polyolefin resin (A) having a carboxyl group. Therefore, ethylcyclohexane, toluene, xylene, and ethylbenzene having a boiling point in the range of 100 to 200 ° C. are preferable.

The amount of the organic solvent used is preferably 50 parts by weight or more and 200 parts by weight or less, particularly 75 parts by weight with respect to 100 parts by weight of the total amount of the modified polyolefin resin (A) having a carboxyl group and the ethylenically unsaturated compound (B). More preferably, the amount is at least 150 parts by weight. Since the high molecular weight of the modified polyolefin resin composition can be suppressed when the content is 50 parts by weight or more compared to the case where the content is less than 50 parts by weight, the stability of the polar solvent varnish is improved. Is preferable. Compared with the case where the amount is more than 200 parts by weight, when the amount is 200 parts by weight or less, the grafting reaction of the ethylenically unsaturated compound (B) to the modified polyolefin resin (A) having a carboxyl group is likely to proceed. It is also preferable because generation of by-products can be suppressed. When the amount is 150 parts by weight or less, the generation of by-products is further suppressed, and the grafting reaction easily proceeds, which is preferable.

The modified polyolefin resin composition (C) of the present invention may be blended with the modified polyolefin resin (A) having a carboxyl group, and the polyolefin is mainly composed by blending the modified polyolefin resin (A) having a carboxyl group. It is preferable because the compatibility with the resin and the substrate and the adhesiveness are improved.

When blending the modified polyolefin resin composition (C) and the modified polyolefin resin (A) having a carboxyl group, the modified polyolefin resin (A) having a carboxyl group with respect to 100 parts by weight of the modified polyolefin resin composition (C). Preferably contains 50 parts by weight or less. When the amount used is more than 50 parts by weight, the varnish may have poor fluidity when dissolved in a polar solvent. As blending conditions, it is preferable to mix in an organic solvent at 100 to 200 ° C. and remove the solvent because of excellent solubility in polar solvents such as alcohols and ester solvents.

The modified polyolefin resin composition (C) or blend (D) thus obtained can be used, for example, as a paint binder, an ink binder, or a primer, and particularly when coated on polyolefin resins and composite materials. Excellent paintability. In addition, it can be used as a heat sealant, an adhesive, and an adhesive modifier, and is particularly excellent in adhesion between a polyolefin-based resin or composite material and another resin, metal, glass or the like. In addition, when making polyolefin resins and composite materials such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, etc., compatibilizers between polyolefin resins and other resins It can also be used as a modifier such as a dispersing agent or a glass fiber sizing agent that facilitates dispersing the composite material into the polyolefin.

The modified polyolefin resin composition (C) or blend (D) of the present invention can function as a paint binder, an ink binder, a primer, an adhesive, a compatibilizer, a dispersant, or a modifier even if it is used as it is. Various additives can be added depending on the purpose of use. Additives include stabilizers such as phenol stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, antioxidants, weathering stabilizers, antioxidants, heat stabilizers, light stabilizers, Thixotropic agents, thickeners, antifoaming agents, surface conditioners, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, additives, titanium oxide, zinc oxide Transition metal compounds such as, pigments such as carbon black, glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, finely divided silica, mica , Inorganic and organic fillers such as calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, and celite.

Since the modified polyolefin resin composition (C) or blend (D) of the present invention is also excellent in compatibility with other resins, urethane resin, epoxy resin, acrylic resin, phenol resin, alkyd resin, Other resins such as silicon resin, polyacetal resin, polyester resin, polyamide resin, polyimide resin, and nitrified cotton may be blended.

Since the modified polyolefin resin composition (C) or blend (D) of the present invention is in a solid state at room temperature, it is obtained as a block, plate, rod, pellet, or strand, but is dissolved or dispersed in an organic solvent. Can also be obtained.

When the modified polyolefin resin composition (C) or blend (D) of the present invention is obtained as a dissolved or dispersed state in an organic solvent, saturated aliphatic hydrocarbons such as hexane, heptane, and octane, cyclohexane, methylcyclohexane, Saturated alicyclic hydrocarbons such as ethylcyclohexane, cycloheptane and methylcycloheptane, esters not containing ethylenic double bonds such as ethyl acetate, n-butyl acetate and isobutyl acetate, acetone, methyl ethyl ketone and methyl isobutyl Ketones that do not contain ethylenic double bonds such as ketone and cyclohexanone, ethers that do not contain ethylenic double bonds such as n-butyl ether, isobutyl ether, tetrahydrofuran, diethyl ether, ethylene glycol dialkyl ether, and dioxane, Lumpur, isopropyl alcohol, ethylene glycol, alcohols such as free of ethylenic double bonds, such as propylene glycol may be used. The solid content concentration of the modified polyolefin resin composition is not particularly limited, but the solid content concentration is preferably about 1 to 50 parts by weight for ease of handling. The solution or dispersion of the modified polyolefin resin composition may contain stabilizers, additives, pigments, fillers, etc. In this case, the stabilizers, additives, pigments, fillers, etc. are dissolved in the solvent. Or may be dispersed.

Further, when the modified polyolefin resin composition (C) or blend (D) is obtained in a state dissolved or dispersed in an organic solvent, aromatic hydrocarbons such as toluene and xylene can also be used. However, the use of aromatic hydrocarbons is not preferred due to recent environmental problems.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. In each table, all parts are parts by weight unless otherwise specified.

Production Example 1 of Modified Polyolefin Resin (A-1) Having Carboxyl Group
A 3000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube is charged with 1000 g of polyolefin (PO-1) and 200 g of xylene, and melted in an oil bath maintained at 180 ° C. in a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the inside of the flask became 170 ° C. while stirring. After the polyolefin (PO-1) was melted, 24 g of n-octadecyl methacrylate and 12 g of maleic anhydride were added, and 2 g of di-t-butyl peroxide was added while stirring to obtain a uniform state. The reaction was continued for 30 minutes while maintaining the system at 170 ° C., 24 g of n-octadecyl methacrylate and 12 g of maleic anhydride were added, and 2 g of di-t-butyl peroxide was added. Similarly, the addition of n-octadecyl methacrylate, maleic anhydride and di-t-butyl peroxide was performed 5 times in total every 30 minutes. The total amount of addition of n-octadecyl methacrylate was 120 g, and maleic anhydride was added. The total amount was 60 g, and the total amount of di-t-butyl peroxide added was 10 g.

After completion of the addition, the reaction was carried out at 170 ° C. for 2 hours, and then xylene, unreacted n-octadecyl methacrylate, maleic anhydride, di-t-butyl peroxide and di-t were reduced in the flask with an aspirator. -Removal of the low molecular weight compound decomposed by butyl peroxide for 2 hours, after completion of decompression, the reaction product is taken out and cooled, and the carboxyl group modified with pale yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acids Solid product of modified polyolefin (A-1) having The obtained modified polyolefin (A-1) had a melt viscosity (190 ° C.) of 10.2 Pa · s, a softening point of 102 ° C., and a weight average molecular weight of 78,000. The polyolefin (PO-1) has a density of 0.87 g / cm ³ , a weight average molecular weight of 92,000, a softening point of 107 ° C., a copolymer of ethylene, propylene, and 1-butene. (Degussa Japan Co., Ltd.). Moreover, said molecular weight, softening point, and melt viscosity were measured as follows. Hereinafter, the molecular weight, softening point, and melt viscosity are obtained in the same manner.

<Molecular Weight of Modified Polyolefin Resin (A) Having Polyolefin and Carboxyl Group>
The molecular weight of the raw material polyolefin and the modified polyolefin resin having a carboxyl group is a value obtained by measurement using gel permeation chromatography (manufactured by Tosoh Corporation: HLC-8120GPC, standard polystyrene).

<Softening point of polyolefin>
The softening point of the raw material polyolefin was measured by the ring and ball method according to JIS K 6863.

<Softening point of modified polyolefin resin (A) having carboxyl group>
The softening point of the modified polyolefin resin having a carboxyl group (A) is T1 / 2 by a flow tester (manufactured by Shimadzu Corporation: CFT-500D) with a weight of 0.49 Mpa, a die having an inner diameter × length = 1 mm × 10 mm. It is the value obtained by the method.

<Melt viscosity of modified polyolefin resin (A) having carboxyl group>
The melt viscosity of the modified polyolefin resin (A) having a carboxyl group is a value obtained by measuring at 190 ° C. using a flow tester (manufactured by Shimadzu Corporation: CFT-500D). The weight was 0.49 Mpa, and the die was measured with an inner diameter × length = 1 mm × 10 mm.

Production examples 2 to 4 of modified polyolefin resins (A-2 to A-4) having a carboxyl group
Into a 3000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, the polyolefin and organic solvent shown in Table 1 are placed, and the polyolefin is melted in an oil bath maintained at 180 ° C. in a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the inside of the flask became 170 ° C. while stirring. After the polyolefin in the flask is melted, the addition of (meth) acrylic acid alkyl ester, unsaturated carboxylic acid and organic peroxide shown in Table 1 is added every 30 minutes while stirring to obtain a uniform state. / 5 in total 5 times. After completion of the addition, the reaction was carried out at 170 ° C. for 2 hours, and the pressure inside the flask was reduced with an aspirator, while the organic solvent and unreacted (meth) acrylic acid alkyl ester, maleic anhydride, organic peroxide and organic peroxide were used. After removing the low molecular weight compound decomposed for 2 hours, after completion of decompression, the reaction product is taken out and cooled, so that the carboxyl group modified with pale yellow (meth) acrylic acid alkyl ester and unsaturated carboxylic acid is removed. A solid product of modified polyolefin (A-2 to A-4) was obtained. Table 1 shows the melt viscosity (190 ° C.), softening point, and weight average molecular weight of the resulting modified polyolefins (A-2 to A-4).

The polyolefin (PO-2) in Table 1 has a density of 0.87 g / cm ³ , a weight average molecular weight of 118,000, a softening point of 108 ° C., a copolymer of ethylene, propylene and 1-butene. A certain VESTLAST 792 (manufactured by Degussa Japan Co., Ltd.), polyolefin (PO-3) has a density of 0.87 g / cm ³ , a weight average molecular weight of 38,000, a softening point of 90 ° C., and a weight of ethylene and propylene. LICOCENE PP1502 (manufactured by Clariant Japan Co., Ltd.), which is a coalescence.

<Glass Transition Temperature of Modified Polyolefin Resin Composition (C)>
The glass transition temperature of the modified polyolefin resin composition (C) is a value obtained by measurement using a differential scanning calorimeter (manufactured by Seiko Instruments Inc .: EXTAR6000).

<Molecular weight of modified polyolefin resin composition (C)>
The molecular weight of the modified polyolefin resin composition (C) is a value obtained by measurement using gel permeation chromatography (manufactured by Tosoh Corporation: HLC-8120GPC, standard polystyrene).

Example 1
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 100 g of modified polyolefin resin (A-1) having a carboxyl group and 1100 g of xylene were placed, and the flask was stirred while stirring in a nitrogen atmosphere. The temperature of the oil bath was adjusted to 140 ° C. After the modified polyolefin resin (A-1) having a carboxyl group is dissolved, 850 g of styrene, 150 g of N, N-dimethylacrylamide and 100 g of di-t-butyl peroxide are added over 3 hours while stirring to obtain a uniform state. The reaction was conducted dropwise. After completion of the dropping, the reaction was carried out at 140 ° C. for 3 hours, and then the inside of the flask was decompressed with an aspirator, while xylene, unreacted styrene, N, N-dimethylacrylamide, di-t-butyl peroxide and di-t- Removal of the low molecular weight compound in which butyl peroxide was decomposed was performed for 2 hours, and after completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of the modified polyolefin resin composition. The modified polyolefin resin composition (C-1) obtained had a glass transition temperature of 73 ° C. and a weight average molecular weight of 22,100.

(Examples 2 to 11)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, a modified polyolefin resin having a carboxyl group and an organic solvent are added so as to have the ratio shown in Table 2, and stirred in a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the inside of the flask became the reflux temperature of the organic solvent. After the modified polyolefin resin having a carboxyl group was dissolved, the ethylenically unsaturated compound and the organic peroxide shown in Table 2 were dropped and reacted over 3 hours while stirring to obtain a uniform state. After completion of the dropping, the reaction is performed at the reflux temperature of the organic solvent for 3 hours, and then the organic solvent, the unreacted ethylenically unsaturated compound, the organic peroxide, and the organic peroxide are decomposed while reducing the pressure in the flask with an aspirator. The low molecular weight compound was removed for 2 hours, and after completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of the modified polyolefin resin composition. Table 2 shows the glass transition temperatures and weight average molecular weights of the resulting modified polyolefin resin compositions (C-2) to (C-11).

(Comparative Example 1)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 50 g of modified polyolefin resin (A-1) having a carboxyl group and 1050 g of xylene were placed, and the flask was stirred while stirring in a nitrogen atmosphere. The temperature of the oil bath was adjusted to 140 ° C. After the modified polyolefin resin (A-1) having a carboxyl group was dissolved, 1000 g of styrene and 100 g of di-t-butyl peroxide were dropped and reacted over 3 hours while stirring to obtain a uniform state. After completion of the dropwise addition, the reaction was carried out at 140 ° C. for 3 hours, and then xylene, unreacted styrene, di-t-butyl peroxide and di-t-butyl peroxide were decomposed while reducing the pressure in the flask with an aspirator. The molecular compound was removed for 2 hours, and after completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of the modified polyolefin resin composition. The obtained modified polyolefin resin composition had a glass transition temperature of 64 ° C. and a weight average molecular weight of 9,700. Table 2 shows the glass transition temperature and the weight average molecular weight of the modified polyolefin resin composition obtained.

(Comparative Examples 2 and 3)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, a modified polyolefin resin having a carboxyl group and an organic solvent are added so as to have the ratio shown in Table 2, and stirred in a nitrogen atmosphere. The temperature of the oil bath was adjusted so that the inside of the flask became the reflux temperature of the organic solvent. After the modified polyolefin resin having a carboxyl group is dissolved, the ethylenically unsaturated compound and the organic peroxide are dropped and reacted over a period of 3 hours so as to be in a uniform state by stirring. It was. After completion of the dropping, the reaction is performed at the reflux temperature of the organic solvent for 3 hours, and then the organic solvent, the unreacted ethylenically unsaturated compound, the organic peroxide, and the organic peroxide are decomposed while reducing the pressure in the flask with an aspirator. The low molecular weight compound was removed for 2 hours, and after completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of the modified polyolefin resin composition. Table 2 shows the glass transition temperature and the weight average molecular weight of the modified polyolefin resin composition obtained.

(Comparative Example 4)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 1000 g of xylene was placed, and the temperature of the oil bath was adjusted so that the temperature in the flask was 140 ° C. while stirring in a nitrogen atmosphere. . At 140 ° C., 600 g of styrene, 200 g of N, N-dimethylacrylamide, 200 g of 2-ethylhexyl acrylate, and 100 g of di-t-butyl peroxide were dropped and reacted over 3 hours. After completion of the dropping, the reaction was carried out at 140 ° C. for 3 hours, and then the inside of the flask was decompressed with an aspirator, while xylene, unreacted styrene, N, N-dimethylacrylamide, 2-ethylhexyl acrylate, and di-t-butyl par Removal of the low molecular weight compound in which oxide and di-t-butyl peroxide were decomposed was performed for 2 hours. After completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of a styrene acrylic resin composition. The resulting styrene acrylic resin composition had a glass transition temperature of 53 ° C. and a weight average molecular weight of 9,500. Table 2 shows the glass transition temperature and the weight average molecular weight of the obtained styrene-acrylic resin composition.

(Comparative Example 5)
A 3000 mL Separa flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube was charged with 1000 g of polyolefin (PO-1), 200 g of N, N-diethylacrylamide and 10 g of dicumyl peroxide, and 180 ° under a nitrogen atmosphere. Melting was carried out in an oil bath maintained at 0 ° C., and the temperature of the oil bath was adjusted so that the inside of the flask became 180 ° C. while stirring. After the polyolefin (PO-1) is melted, the reaction is carried out at 180 ° C. for 2 hours while stirring to obtain a uniform state, and then the reaction product is taken out and cooled to obtain a solid product of the modified polyolefin resin composition. Obtained. The resulting modified polyolefin resin composition had a glass transition temperature of 0 ° C. or lower and a weight average molecular weight of 109,600. Table 2 shows the glass transition temperature and the weight average molecular weight of the modified polyolefin resin composition obtained.

(Comparative Example 6)
Into a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 50 g of polyolefin (PO-2) and 1050 g of xylene are placed, and the inside of the flask becomes 140 ° C. while stirring in a nitrogen atmosphere. The temperature of the oil bath was adjusted. After the polyolefin (PO-2) is dissolved, stirring is performed to obtain a uniform state, and then 650 g of styrene, 100 g of N, N-dimethylacrylamide, 250 g of 2-ethylhexyl acrylate and 100 g of di-t-butyl peroxide are added for 3 hours. Over a period of time. After completion of the dropping, the reaction was carried out at 140 ° C. for 3 hours, and then the inside of the flask was decompressed with an aspirator, while xylene, unreacted styrene, N, N-dimethylacrylamide, 2-ethylhexyl acrylate, and di-t-butyl par The low molecular weight compound in which oxide and di-t-butyl peroxide were decomposed was removed for 2 hours. After completion of the decompression, the reaction product was taken out and cooled to obtain a solid product of the modified polyolefin resin composition. The obtained modified polyolefin resin composition had a glass transition temperature of 34 ° C. and a weight average molecular weight of 22,200. Table 2 shows the glass transition temperature and the weight average molecular weight of the modified polyolefin resin composition obtained.

<Stability of resin composition solution (stability of varnish)>
The resin compositions of Examples 1 to 11 and Comparative Examples 1 to 6 obtained as described above were adjusted to a solid content of 20% with a mixed solvent of ethyl acetate / isopropanol = 50/50, The state of the solution after standing at room temperature for 1 month was confirmed. The separation / gel was not confirmed and the viscosity was not increased ◎, the separation / gel was not confirmed but the viscosity was increased ○, the separation / gel was confirmed, but the one that can be easily dispersed by stirring is △, The separation and gel were confirmed, and those that could not be easily dispersed by stirring were evaluated as x. Tables 3 and 4 show the results.

<Adhesive strength test>
The modified polyolefin resin composition solution (prepared by the above varnish stability test) was applied to a polypropylene plate with a bar coater so that the coating thickness after drying was 10 μm. After air drying at room temperature for 30 minutes, a two-component polyurethane resin paint (Utanal (L) White, manufactured by Ohashi Chemical Industry Co., Ltd.) was applied so that the coating thickness was 100 μm. After coating, the sample was dried at 90 ° C. for 30 minutes to obtain a sample. One day after drying, the coating film was cut out at intervals of 1 cm, and applied using a tensile tester (Tribogear Type: HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a pulling speed of 100 mm / min and a pulling angle of 180 degrees. The peel strength of the film was measured to evaluate the adhesive strength. Tables 3 and 4 show the results. In addition, the adhesive strength test was not performed about the resin composition obtained by Comparative Example 1, 3 and 5 which was x by the evaluation result of the stability of a varnish.

Example 12
A 3000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube is charged with 50 g of a modified polyolefin resin (A-1) having a carboxyl group, 100 g of a modified polyolefin resin composition (C-1) and 150 g of xylene. The temperature of the oil bath was adjusted so that the temperature in the flask was 140 ° C. while stirring in a nitrogen atmosphere. After incubating at 140 ° C. for 60 minutes, xylene was removed for 2 hours while reducing the pressure in the flask with an aspirator. After completion of the pressure reduction, the reaction product was taken out and cooled to be blended to obtain a resin composition (D-1 ) The blend resin (D-1) obtained had a weight average molecular weight of 33500 and a glass transition temperature of 66.4 ° C.

(Examples 13 to 20)
In a 3000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, a modified polyolefin resin having a carboxyl group, a modified polyolefin resin composition, and an organic solvent as shown in Table 5 were placed under a nitrogen atmosphere. While adjusting the temperature of the oil bath so that the temperature in the flask becomes the temperature shown in Table 5 while stirring, the resin composition (D-2)- (D-9) was obtained. Table 5 shows the weight average molecular weight and glass transition temperature of the obtained blend resin.

<Stability of resin composition solution (stability of varnish)>
The resin compositions (D-1) to (D-9) obtained by blending as described above were adjusted to 20% with a mixed solvent of ethyl acetate / isopropanol = 50/50 at room temperature. The state of the solution after standing for 1 month was confirmed. The separation / gel was not confirmed and the viscosity was not increased ◎, the separation / gel was not confirmed but the viscosity was increased ○, the separation / gel was confirmed, but the one that can be easily dispersed by stirring is △, The separation / gel confirmed and not easily dispersible by stirring was evaluated as x. Table 6 shows the results.

<Adhesive strength test>
The blend resin solution obtained as described above (prepared by the varnish stability test) was applied to a polypropylene plate with a bar coater so that the thickness of the coating film after drying was 10 μm. After air drying at room temperature for 30 minutes, a two-component polyurethane resin paint (Utanal (L) White, manufactured by Ohashi Chemical Industry Co., Ltd.) was applied so that the coating thickness was 100 μm. After coating, the sample was dried at 90 ° C. for 30 minutes to obtain a sample. One day after drying, the coating film was cut out at intervals of 1 cm, and applied using a tensile tester (Tribogear Type: HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a pulling speed of 100 mm / min and a pulling angle of 180 degrees. The peel strength of the film was measured to evaluate the adhesive strength. Table 6 shows the results.

Claims (8)

It is obtained by graft copolymerization of an ethylenically unsaturated compound (B) containing at least styrenes (a) and N-substituted (meth) acrylamide (b) on a modified polyolefin resin (A) having a carboxyl group. Modified polyolefin resin composition (C). The modified polyolefin resin composition (C) according to claim 1, wherein the N-substituted (meth) acrylamide (b) is N, N-dimethylacrylamide and / or N, N-diethylacrylamide. The ethylenically unsaturated compound (B) contains at least a styrene (a), an N-substituted (meth) acrylamide (b), and an unsaturated carboxylic acid ester (c). Modified polyolefin resin composition (C). The ethylenically unsaturated compound (B) contains at least 40 parts by weight of styrenes (a) and at least 10 parts by weight of N-substituted (meth) acrylamide (b). 4. The modified polyolefin resin composition (C) according to any one of 3 above. The ethylenically unsaturated compound (B) is 40 to 80 parts by weight of styrenes (a), 10 to 20 parts by weight of N-substituted (meth) acrylamide (b), and 10 to 40 of unsaturated carboxylic acid ester (c). The modified polyolefin resin composition (C) according to claim 3, wherein the modified polyolefin resin composition (C) is contained in parts by weight. A resin composition (D) obtained by blending a modified polyolefin resin (A) having a carboxyl group and the modified polyolefin resin composition (C) according to claim 1. A resin composition for removing a solvent by mixing the modified polyolefin resin (A) having a carboxyl group and the modified polyolefin resin composition (C) according to claims 1 to 5 in an organic solvent at 100 to 200 ° C. D) Production method. The resin composition according to claim 6 or 7, wherein the modified polyolefin resin (A) having a carboxyl group contains 50 parts by weight or less with respect to 100 parts by weight of the modified polyolefin resin composition (C). Manufacturing method of thing (D).