JPH1036437A - Copolymer and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having a high strength and heat resistance as well as a sufficient flexibility and being useful as an adhesive, a coating material, a sealant or the like by forming a copolymer based on a specified unsaturated fatty acid or its derivative and a thermoplastic resin. SOLUTION: This invention provides a copolymer formed by bonding a residue A of a linear thermoplastic resin molecule having a number-average molecular weight of 1,000 or above to a group D corresponding to a residue derived by removing R<1> or R<2> from an unsaturated fatty acid represented by formula I or a derivative thereof and having a structure represented by any one of formula II to VI. In formula I, R<1> is a 1-10C alkyl; R<2> is H or a 1-10C alkyl; m and n are each 1-10; and the order in which the m groups and the n groups are bonded is arbitrary. In formula II, D is bonded to one molecular terminal of A. In formula III, Ds are bonded to both molecular terminals of A. In formula IV, k is an integer of 2 or greater; and kDs are bonded to one molecular terminal of A in a manner of forming a broom top. In formula V, k and k' are each an integer of 2 or greater, and k Ds and k'Ds are bonded to their respective molecular terminals in a manner of forming broom tops, In VI, K" is an integer of 1 or greater, and k"Ds are grafted onto any site of the molecular chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymer based on an unsaturated fatty acid or a derivative thereof and a thermoplastic resin, and a use thereof.

[0002]

2. Description of the Related Art SIS (styrene-isoprene-styrene block copolymer), SBS (styrene-butadiene-styrene block copolymer), S-EP-S
Styrene blocks based on polymer conjugated dienes such as (partially hydrogenated styrene-isoprene-styrene block copolymer) and S-EB-S (partially hydrogenated styrene-butadiene-styrene block copolymer) Copolymers are widely used in coatings and adhesives as thermoplastic elastomers. An important advantage of the styrene block copolymer based on these polymer conjugated dienes is
Unlike materials with a high crosslinking point concentration, such as polyols / isocyanates, polyols / melamines, acid anhydrides / epoxy compounds, epoxy resins / amine compounds, and acrylic oligomers / acrylic monomers that cure with heat or radiation, the polystyrene segments are pseudo-crosslinked. The point is that it becomes a point. However, an important limitation of styrene block copolymers was their inability to provide high heat resistance. This is because the pseudo-crosslinking of the styrene block copolymer is caused by the physical association of the styrene segments in the polymer, and it is eliminated at a temperature close to or higher than the glass transition temperature of polystyrene, and the cohesive strength is reduced. Is lost. In order to solve this problem, UV, EB
For example, a method of radically crosslinking a double bond derived from a conjugated diene by using a method such as oxygen crosslinking by adding a dryer is used. However, even if these methods are adopted, a composition using a conventional styrene block copolymer cannot maintain sufficient strength and heat resistance. this is,
The conventional styrene block copolymer has a small number of double bonds derived from the conjugated diene that contribute to crosslinking, and the conjugated diene block segment is not at the end of the block copolymer molecule, and the styrene block segment has a crosslinking point. It is considered that a sufficient cross-linking point cannot be obtained by covering the conjugated diene block segment to be formed.

[0003]

The inventors of the present invention have studied to solve the above problems, and found that a coating using a copolymer based on an unsaturated fatty acid having a specific structure or a derivative thereof, and a thermoplastic resin. Agents and adhesives,
It has been found that crosslinking has high strength and heat resistance while maintaining sufficient flexibility.

[0004]

That is, the present invention relates to a method for producing a chain thermoplastic resin having a number average molecular weight of 1,000 or more from an unsaturated fatty acid represented by the following general formula (1) or a derivative thereof to R ¹ or The present invention relates to a copolymer having any of the following structures (a) to (e), to which a group D corresponding to a residue excluding R ² is bonded.

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The present invention also provides a copolymer wherein A in the above formula is any of a polyester or polycarbonate residue, a styrene-containing polymer residue, a polyether residue, and a polyolefin residue. Things. Further, the present invention relates to an adhesive composition, a coating composition, a sealant composition, and a resin composition containing the copolymer. Hereinafter, the present invention will be described in detail.

In the general formula (1) representing an unsaturated fatty acid or a derivative thereof as one of the starting materials of the copolymer of the present invention, R ¹ and R ² each have 1 to 1 carbon atoms.
Examples of the alkyl group of 0 include a methyl group, an ethyl group,
A propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like. Among them, R ¹ is preferably an alkyl group having 2 to 5 carbon atoms, and R ² is an ethyl group. Is preferred.

The unsaturated fatty acids represented by the general formula (1) and derivatives thereof are preferably those having 16 to 22 carbon atoms as an unsaturated fatty acid, and particularly preferred are those having a carbon number of 16 to 22. 20 to 22, m is 4 to 6, and n is 1 to 7. Specific examples of unsaturated fatty acids include hexadecatrienoic acid having 16 carbon atoms (6,10,14-hexadecatrienoic acid,
6,9,12-hexadecatrienoic acid, 7,10,13
-Hexadecatrienoic acid), hexadecatetraenoic acid,
Octadecatetraenoic acid having 18 carbon atoms (4, 8, 12,
15-octadecatetraenoic acid) H 21 eicosapentaenoic acid (6,9,12,15,18-hene eicosapentaenoic acid) having 21 carbon atoms, eicosatetraenoic acid (5,8,11,14) having 20 carbon atoms. -Eicosatetraenoic acid,
4,8,12,16-eicosatetraenoic acid), eicosapentaenoic acid (5,8,11,14,17-eicosapentaenoic acid, 4,8,12,15,18-eicosapentaenoic acid), carbon number 22 docosatetraenoic acid (1
0,13,16,19-docosatetraenoic acid), docosapentaenoic acid (7,10,13,16,19-docosapentaenoic acid), docosahexaenoic acid (4,7,10,
13,16,19-docosahexaenoic acid, 4,8,1
2,15,18,21-docosahexaenoic acid, 4,8,
11, 14, 17, 20-docosahexaenoic acid). These are obtained from natural fats and oils such as fish oil, and can be used in any of high-purity products, mixtures thereof, or distillation residues containing these unsaturated fatty acids and derivatives thereof.

These unsaturated fatty acids and derivatives thereof have a higher double bond concentration than the conventionally used conjugated double bond block of the styrene block copolymer. And the adhesive containing it,
When a sealant, a coating composition, or the like is used, the crosslink density increases, and strength and heat resistance can be improved.

In the copolymer of the present invention, a group D corresponding to the residue obtained by removing R ¹ or R ² from the unsaturated fatty acid represented by the above general formula (1) or a derivative thereof, especially R ² is removed. Further, the following group (1 ′) is preferably bonded to a chain thermoplastic resin molecule residue.

[0010]

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A chain thermoplastic resin having a number average molecular weight of 1,000 or more, which forms the copolymer of the present invention together with the unsaturated fatty acid represented by the general formula (1) or a derivative thereof, is melted by heating to have an arbitrary shape. Are generically referred to. Here, the term “chain” means that it is substantially a chain when viewed from the whole molecule, and it may be a polymer having a short-chain branch or another polymer grafted to a thermoplastic resin which is an original chain. . Hereinafter, a thermoplastic resin which is substantially chain-shaped and used for producing the copolymer of the present invention is simply referred to as a thermoplastic resin. Specific examples of the thermoplastic resin include polyolefin resins, polyamide resins such as nylon 46, nylon 6, and nylon 66; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; and crystalline thermoplastic polymers such as polyamide elastomer and polyester elastomer. Coalescing, ABS resin,
AES resin, AAS resin, rubber-modified polymer such as MBS resin, acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer, polystyrene, polymethyl methacrylate, polycarbonate, amorphous thermoplastic polymer such as polyphenylene oxide, Alternatively, a graft polymer in which another polymer is graft-polymerized to a polymerized unit having an α-monoolefin having 2 to 8 carbon atoms as a main repeating structural unit, for example, an acrylonitrile-styrene copolymer is graft-polymerized to an ethylene-propylene copolymer Graft polymer obtained by graft-polymerizing an acrylonitrile-styrene copolymer onto an ethylene-butene copolymer, and a graft polymer obtained by graft-polymerizing a butyl acrylate-methyl methacrylate copolymer onto an ethylene-butene copolymer. And a graft polymer obtained by graft polymerization of a methyl methacrylate copolymer to an ethylene-butene copolymer, and preferred thermoplastic resins include polyester resins, polymers containing styrene as a structural unit, polyethers, and polyolefin resins. No.

The thermoplastic resin used in the present invention has a number average molecular weight of at least 1,000, preferably at least 1,000.
00000 or less. When the number average molecular weight is less than 1,000, the number of double bonds in the obtained copolymer is too large, so that the cured product becomes hard and good processability cannot be obtained. On the other hand, if the number average molecular weight is 200000 or more, it is difficult to bond (hereinafter, also referred to as coupling) between the unsaturated fatty acid derivative represented by the general formula (1) and the thermoplastic resin, which is not desirable. In the present invention, the “number average molecular weight” is calculated using gel permeation chromatography and using a standard polystyrene calibration curve.

Examples of the polyester resin include polyester produced by reacting a carboxylic acid component and a glycol component, and polycaprolactone produced by polymerizing lactones. As the carboxylic acid component,
Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, fats such as hymic acid and 1,6-cyclohexyldicarboxylic acid Examples thereof include trivalent or higher valent acids such as aromatic carboxylic acids, trimellitic acids, and pyromellitic acids, and lower alkyl esters and acid anhydrides thereof. One or more of these acids can be used. As the glycol component, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol,
Examples include xylylene glycol, hydrogenated bisphenol A, bisphenol A, their ethylene oxide or propylene oxide adducts, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and the like, and one or more of these can be used. In addition, a hydroxy acid such as dimethylolpropionic acid can be used simultaneously with the above carboxylic acid and glycol components. As the lactones, ε-caprolactone, valerolactone, and the like are preferable, and one or more of these can be used. The polyester resin is produced by blending a carboxylic acid component and a glycol component and / or a lactone, and performing an esterification reaction or a transesterification reaction by a known production method, for example, a melting method or a solvent method.

The polycarbonate used in the present invention is:
Known methods such as direct reaction of bisphenols with phosgene (phosgene method, interfacial polymerization method), transesterification reaction of bisphenols or diol component with diallyl carbonate (ester exchange method), or ring-opening polymerization method of cyclic carbonate compound It is obtained by the method of. Preferably bisphenol A type polycarbonate, 1,6-
A carbonate adduct of hexanediol is exemplified.

Examples of the polymer containing styrene as a structural unit include polystyrene, AS resin, ABS resin, and AAS.
Resin, AES resin, ACS resin, MBS resin, HIP
S, styrene-butadiene resin and the like. In order to couple with the unsaturated fatty acid derivative represented by the general formula (1), it is desirable that the styrene-containing polymer has a hydroxyl group. A known method can be used to give a hydroxyl group to the polymer containing styrene. For example, there are a method of using a compound containing an SH group and a hydroxyl group in a molecule as an initiator during the production and a method of using a polymer radical initiator having a peroxide bond in a molecule, and the like. Is a macromonomer series of Toagosei Co., Ltd., and the latter is, for example, Modiper series of Nippon Yushi Co., Ltd.

Examples of the polyether include one or two compounds having an epoxy group such as ethylene oxide, propylene oxide, tetrahydrofuran, and glycidol, compounds having two or more active hydrogens,
For example, products obtained by addition polymerization of diols and diamines, for example, polyethylene ether glycol, polypropylene ether glycol, polytetramethylene glycol, and the like, and polyester polyol, polysilicon glycol, and the like to which an alkylene oxide is added can be used. Particularly preferred are ether diols having a polytetramethylene chain and polyglycerin.

Examples of polyolefins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, homopolymers such as poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene. -A copolymer such as propylene-diene rubber. In order for the unsaturated fatty acid derivative represented by the general formula (1) to couple with the polyolefin, the polyolefin desirably has a hydroxyl group. A known method can be used as a method for providing a hydroxyl group to the polyolefin. For example, there are a method of oxidizing a polyolefin and a method of hydrogenating a polydiene at a hydroxyl group end.

The method of coupling the unsaturated fatty acid derivative represented by the general formula (1) with the thermoplastic resin is not particularly limited, but includes a transesterification method, a method in which the unsaturated fatty acid derivative is mixed with a monomer of the thermoplastic resin, and Examples thereof include a method of graft-polymerizing a thermoplastic resin from a fatty acid derivative, and a method of using a coupling agent such as diisosinate. In the latter case, the residue of the thermoplastic resin and the unsaturated fatty acid or its derivative are not directly bonded, but the copolymer of the present invention includes such a case. A method of melt-kneading an unsaturated fatty acid derivative with a thermoplastic resin and a transesterification catalyst, transesterifying an ester group of the unsaturated fatty acid derivative with a hydroxyl group of the thermoplastic resin, and distilling off by-product low molecular weight alcohol. Is most preferably used.

Known devices can be used as devices for performing the melt kneading and the distillation of by-product low-molecular components. For example, an extruder with a vent port, a static mixer type polymerization apparatus, a batch type reactor with a separating funnel, and the like,
They can be used alone or in combination.

Examples of the transesterification catalyst for transesterifying the ester group of the unsaturated fatty acid derivative with the hydroxyl group of the thermoplastic resin include tin compounds, antimony compounds, titanium compounds, aluminum compounds, zinc compounds, molybdenum compounds and zirconium compounds. However, tin compounds, titanium compounds, and antimony compounds are preferably used in terms of balance between ease of handling, low toxicity, reactivity, non-coloring property, and thermal stability. Specific examples of the tin compound include monobutyltin compounds such as stannous chloride, stannous octylate, monobutyltin oxide, and monobutyltin tris (2-ethylhexyl hexanate);
And dibutyltin compounds such as dibutyltin oxide. Examples of the titanium compound include tetrabutyl titanate and tetraisopropyl titanate, and examples of the antimony compound include antimony triacid number. These are used alone or in the presence of a mixed catalyst for 100 mm.
Hg or less, preferably 10 mmHg or less under reduced pressure.
By performing a transesterification reaction at 00 ° C to 300 ° C, preferably 150 ° C to 200 ° C, to obtain a copolymer based on an unsaturated fatty acid derivative represented by the general formula (1) and a thermoplastic resin. Can be.

The copolymer of the present invention has the formula (a) according to the number of hydroxyl groups in the thermoplastic resin molecule, the position in the molecule and the mixing ratio with the unsaturated fatty acid derivative represented by the general formula (1). One having a group D bonded to one end of a thermoplastic resin molecule like DA, one having a group D bonded to both ends of a thermoplastic resin molecule like DAD of formula (b), one having a formula (c) (D) _k- A with one end of a thermoplastic resin molecule in which k pieces of D are bonded in a broom-like form, (D) _k -A- of formula (d)
(D) _{those 'group} D also across as are k and k' of k is bonded to broom-like, more A~ of formula (e) (D)
_{k "group} D as the k" pieces, such as those obtained by grafting and the like in the molecular chain of the thermoplastic resin.

These copolymers of the present invention have an unsaturated fatty acid derivative residue at the molecular end of the thermoplastic resin. The conjugated double bond block of the conventionally used styrene block copolymer has a conjugated diene block segment covered with a styrene block segment, which makes cross-linking between molecules difficult, but the copolymer of the present invention has such an obstacle. Because of the absence of a double bond, a double bond is likely to cause a crosslinking reaction between molecules. Further, the conventional copolymer is not restricted in the terminal segment because the intermediate segment is crosslinked, but the copolymer of the present invention is used in the adhesive, sealant, and coating composition because the segment near the molecular end is crosslinked. In this case, the crosslinking property is increased, and the strength and heat resistance can be improved.

The copolymer obtained by an addition reaction (such as transesterification) between an unsaturated fatty acid derivative and a thermoplastic resin can be crosslinked by various methods. For example, addition crosslinking of a styrene monomer using an organic peroxide and a styrene monomer, automatic oxidation crosslinking by a redox reaction with a metal dryer such as an organic acid salt of cobalt or manganese, crosslinking using a sulfur-based vulcanizing agent, UV / Electron beam and γ
Radiation crosslinking by radiation and the like. Block copolymer of the present invention, other thermoplastic resin, any curing agent,
Various components such as a curing aid, a tackifier, a plasticizer, a solvent, and a stabilizer may be added or mixed in various ways. The combined composition contains adhesives, sealants, coatings, inks,
Useful as fiber, FRP, SMC, asphalt or polymer alloy. The composition can be mixed and prepared by a known method. Usually, uniform mixing is obtained by kneading at 25 ° C. to 125 ° C. for about 3 hours. The resulting composition may be used for various applications. Alternatively, the components may be mixed in a solvent or water.

The adhesive composition of the present invention is characterized by containing the above-mentioned copolymer. This copolymer acts as a flexibility imparting agent and a strength imparting agent in the adhesive composition. The adhesive composition can consist solely of a copolymer or, more generally, from a composition comprising the copolymer together with known adhesive composition components such as adhesion-imparting resins and softeners. Become. Curing may be promoted by heating the adhesive before and after bonding to increase the adhesiveness. Alternatively, curing may be promoted by irradiating radiation before and after bonding. The adhesive composition of the present invention may be used as many different types of adhesives, such as hot melt adhesives, solvent soluble adhesives, laminating adhesives, pressure sensitive adhesives, and the like. In addition,
The adhesive also includes a pressure-sensitive adhesive.

[0025] The coating composition of the present invention is characterized by containing the above-mentioned copolymer. This copolymer functions as a flexibility imparting agent and a strength imparting agent for the coating film during coating. The coating composition of the present invention is composed of components obtained by mixing various components such as the above-mentioned copolymer, other resins for paint, optional curing agents, curing assistants, pigments, solvents, stabilizers, and the like. The composition obtained can be applied by known methods. After application, baking may be performed to enhance the curability. Also,
Irradiation after application may accelerate curing.

[0026] The sealant composition of the present invention is characterized by containing the copolymer. This copolymer acts as a flexibility-imparting agent, a strength-imparting agent, and a compatibilizer in the sealant composition. The sealant composition of the present invention includes the copolymer, bituminous substances such as asphalt, linseed oil, fatty oils such as fish oil, natural rubber, chloroprene rubber, butyl rubber, rubbers such as polybutadiene, polyvinyl acetate, polyvinyl chloride, It contains a synthetic resin such as an epoxy resin and an unsaturated polyester resin, a sealant base such as an elastomer such as polyurethane, polysulfide, silicone rubber, and SBS, and further contains an organic or inorganic filler.

[0027] The resin composition of the present invention is characterized by containing the copolymer. This copolymer acts as a flexibility-imparting agent, a strength-imparting agent, and a compatibilizer in the resin composition. The resin composition of the present invention is composed of components obtained by mixing various components such as copolymers, other thermoplastic resins, elastomers, thermosetting resins, curing agents, curing aids, pigments, plasticizers, and stabilizers. .
The obtained composition can be formed by a known method.
The resulting composition may be thermoset. The curing may be promoted by irradiating radiation.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the description in the examples, (parts) represents parts by weight. In the following, NMR is "GXS270WB" manufactured by JEOL Ltd.
And IR is "FT / IR-5300" manufactured by JASCO.
And GPC is "HPLC LC-6AS" manufactured by Shimadzu Corporation.
YSTEM "(column: polystyrene column, solvent: T
HF).

[Synthesis Example 1] 60 g of docosahexaenoic acid ethyl ester (GC purity: 70%; residue after distilling the active ingredient from fish oil, iodine value: 373) in a separable flask equipped with a 2-liter dehydrating tube, polycaprolactone (Placcel H1: Daicel Chemical Industries) 650 g was charged, and the temperature in the reaction system was raised to 1 while blowing nitrogen gas.
The temperature was increased to 70 ° C. and stirred. After 2 hours, about 6 g of ethanol was distilled out into the dehydration tube. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 450 in styrene conversion disappeared, and 630 g of a polycaprolactone adduct of docosahexaenoic acid D-1 was obtained.

Synthesis Example 2 Synthesis Example 1 was repeated except that the thermoplastic resin to be added to docosahexaenoic acid was 390 g of polystyrene (macromonomer HS-6: manufactured by Toagosei Co., Ltd.) having two hydroxyl groups at one molecular end. The same operation was performed to obtain 450 g of a compound D-2 in which two hexadocosaenoic acids were added to one end of polystyrene.

Synthesis Example 3 As a thermoplastic resin to be added to docosahexaenoic acid, an average molecular weight obtained by opening glycidol with stearic acid as an initiator is 2000.
Performed in the same manner as in Synthesis Example 2 except that polyglycerin was used,
420 g of compound D-3 in which hexadocosaenoic acid was added (grafted) to the side chain of polyglycerin was obtained.

[Synthesis Example 4] The thermoplastic resin to be added to docosahexaenoic acid was changed to 260 g of polyethylene (Mitsui High Wax 320MP, manufactured by Mitsui Petrochemical Co., Ltd.) having a number average molecular weight of about 4000, which had been oxidatively modified and had hydroxyl groups introduced. Was carried out in the same manner as in Synthesis Example 1, except that compound D- in which hexadocosaenoic acid was added (grafted) to the side chain of polyethylene.
4 was obtained in an amount of 300 g.

(Example 1, Comparative Example 1) Each component was mixed by a kneader at a weight ratio of each component shown in Table 1 to prepare a reactive hot melt adhesive. The adhesive was melted and introduced into the applicator, heated at a temperature of 150 ° C. in the applicator for 30 seconds before discharging, applied to stainless steel, and pressed. The test results are shown in Table 1.

[0034]

[Table 1]

The contents and evaluation methods of the compounds shown in Table 1 are described below. EP828: bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Ltd .: "Epicoat 828"), D-1: epoxidized block polymer of Synthesis Example 1, PS-2980: phenolic resin (Gunei Chemical Industry Co., Ltd.)
Manufactured by "PS-2980"), perbutyl O: t-butyl peroxyoctaate (manufactured by NOF Corporation)

Shear adhesive strength: 15 hot melt adhesives
Fused at 0 ° C for 30 seconds, width 25mm, length 7
5mm, 0.5mm thick stainless steel coated and crimped,
After 1 hour and 14 days, the bond strength was measured by the shear bond strength. The bonding area is 25 × 25 mm and the bonding thickness is 1
mm, and the pulling speed was 50 mm / min. Flexibility: The above bonded stainless steel was bent to 90 °, and those with no peeling of the bonded surface were rated as ○, and those with peeling were rated as x. Thermal stability (promoting test of storage stability): (viscosity after 80 hours x 96 hours and 100 degrees x 24 hours) / (initial viscosity)
× 100 (%). Heat resistance: A sample was prepared in the same manner as in the case of the above-mentioned shear adhesive strength, and the adhesive strength after standing at 60 ° C. and 80 ° C. for one hour in an atmosphere was measured.

(Example 2, Comparative Example 2) Short oil alkyd resin ("Veccosol ODE" manufactured by Dainippon Ink Industries, Ltd.)
-230-70 "), 100 parts, 50 parts of the block polymer D-3 obtained in Synthesis Example 3, and 5 parts of iron oxide (II) were mixed to obtain a coating composition. The obtained composition was applied to an ABS resin and baked at 80 ° C. for 20 minutes. The obtained coated plate was evaluated for a coating film after one week. Table 2 shows the results. For comparison, a composition excluding D-3 was blended and evaluated in the same manner as above. Table 2 shows the results.

[0038]

[Table 2]

The items and procedures of the evaluation test for various property values in Table 2 are as follows. Pencil hardness: In accordance with JIS K 5400 8.4, using Mitsubishi Uni (manufactured by Mitsubishi Pencil Co., Ltd.), the pencil hardness was indicated at the time when the coating film started to be damaged. Gloss: Indicated by 60-degree specular reflectance (%) according to JIS K 5400 7.6. Flexibility: According to JIS K 5400 8.1, the diameter of the mandrel was 2 mm, and the appearance of the coating when the coating was bent was visually observed.
When it was recognized, it was indicated by x. Adhesion: According to the grid tape method of JIS K 5400 8.5, cuts with a gap of 1 mm are made in a grid pattern, an adhesive tape is peeled off the grid, and adhesion of the coating film after peeling is removed. The state was visually observed and evaluated on a 10-point scale.

Example 3 and Comparative Example 3 30 parts of the block polymer D-4 obtained in Synthesis Example 4 and 100 parts of natural rubber
Parts, calcium carbonate 150 parts, terpene resin 60 parts, n
A sealant was prepared by mixing 50 parts of hexane and 50 parts of gasoline. The properties of the sealant were measured. Table-Results
3 is shown. For comparison, a composition obtained by removing D-4 from the above composition was blended, and the properties of the sealant were measured in the same manner as in Example 3. The results are shown in Table-3.

[0041]

[Table 3]

The items and procedures of the evaluation judgment test for various property values in Table 3 are as follows. Rubber properties: In accordance with JIS A5758, mortar was used as an adherend and tested by H-type tensile adhesion. Durability: According to the durability test method of JIS A5758, an aluminum plate is used as an adherend, and the durability is 802.
A test was performed according to 0 to determine whether the test conformed to the standard. Workability: Five workers performed a two-step evaluation of the workability during the sealing work. When three or more workers were good, the result was evaluated as ○, and the others were evaluated as ×.

(Example 4) 5 parts of the block polymer D-2 obtained in Synthesis Example 2, 40 parts of polyphenylene ether ("Noryl" manufactured by General Electronics Co., Ltd.)
Parts, 60 parts of polypropylene (“Sumitomo Noblen AW564” manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts of epoxidized styrene-butadiene copolymer (“Epofriend” manufactured by Daicel Chemical Industries, Ltd.) are dry-blended and extruded. The mixture was supplied, melt-kneaded at 300 ° C., pelletized, and formed into a test piece using an injection molding machine. The obtained test piece is J
After cutting and forming according to ISK6911, JIS
The tensile strength, the tensile elongation, the flexural modulus, and the Izod impact strength were measured according to K6911. The results are shown in Table-4.

Comparative Example 4 The procedure of Example 4 was repeated, except that the block polymer D-2 was changed to docosahexaenoic acid ethyl ester (GC purity: 70%; residue after distillation of the active ingredient from fish oil). Test pieces were prepared and mechanical properties were measured. The results are shown in Table-4.

Comparative Example 5 A test piece was prepared in the same manner as in Example 4 except that the epoxidized block polymer D-2 was omitted, and mechanical properties were measured. Table-Results
It is shown in FIG.

[0046]

[Table 4]

[0047]

According to the present invention, an adhesive having high strength and heat resistance while maintaining sufficient flexibility by using a copolymer based on an unsaturated fatty acid having a specific structure or a derivative thereof. Compositions, coating compositions, sealant compositions and resin compositions can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication // C08F 299/00 MRN C08F 299/00 MRN 299/02 MRR 299/02 MRR C09D 4/00 PDS C09D 4/00 PDS C09J 4/00 JBT C09J 4/00 JBT

Claims (9)

[Claims] 1. A chain thermoplastic resin molecule residue A having a number average molecular weight of 1,000 or more corresponds to a residue obtained by removing R ¹ or R ² from an unsaturated fatty acid represented by the following general formula (1) or a derivative thereof. A copolymer having any of the following structures (a) to (e), to which a group D is bonded. Embedded image Embedded image 2. The copolymer according to claim 1, wherein A is a residue of polyester or polycarbonate. 3. The copolymer according to claim 1, wherein A is a residue of a polymer containing styrene. 4. The copolymer according to claim 1, wherein A is a residue of a polyether. 5. The copolymer according to claim 1, wherein A is a polyolefin residue. 6. An adhesive composition comprising the copolymer according to claim 1. 7. A coating composition comprising the copolymer according to claim 1. 8. A sealant composition comprising the copolymer according to any one of claims 1 to 5. 9. A resin composition comprising the copolymer according to claim 1.