JP2023156178A - resin composition - Google Patents

Abstract

To provide a resin composition comprising a polyester resin having improved heat resistance.SOLUTION: There is provided a resin composition comprising a polyester resin obtained by reaction of a maleic acid anhydride-modified polyolefin with a polyol, wherein (a) a resin composition contains a plasticizer and/or (b-1) a polyester resin further has a carbon-nitrogen bond in the structure or (b-2) a polyester resin is obtained by reaction with at least one nitrogen-containing compound selected from the group consisting of a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, a cyanate compound, a urea compound, a urethane compound, an amide compound and a cyanide compound.SELECTED DRAWING: None

Description

The present invention relates to a resin composition.

Urethane resins are used as sealants in a variety of locations, both indoors and outdoors, because they can be cured even in low-temperature environments due to the high reactivity of isocyanates.
However, the use of isocyanates has been increasingly restricted in recent years due to their effects on the human body.

Therefore, as an alternative resin to urethane, a two-component mixed polyester resin using a maleic acid modified product as a curing agent has come to be used.
For example, Patent Document 1 describes a two-part curable resin composition in which the first component includes a polybutadiene polyol and an aromatic diamine, and the second component includes maleic anhydride-modified polybutadiene.

Patent No. 6974646

However, a two-component mixed polyester resin using a maleic acid modified product as a curing agent has a problem in that its use is limited because its heat resistance is lower than that of a urethane resin.
The problem to be solved by the present invention is to provide a resin composition containing a polyester resin with improved heat resistance.

As a result of intensive studies, the present inventors have found that it is possible to provide a resin composition containing a polyester resin with improved heat resistance, and have completed the present invention.

That is, the present invention includes the following.
(1) A resin composition comprising a polyester resin formed by a reaction between a maleic anhydride-modified polyolefin and a polyol,
(a) the resin composition contains a plasticizer;
and/or (b-1) the polyester resin further has a carbon-nitrogen bond in its structure, or (b-2) the polyester resin contains a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, A resin composition further comprising a reaction with at least one nitrogen-containing compound selected from the group consisting of a cyanate compound, a urea compound, a urethane compound, an amide compound, and a cyanide compound.
(2) The resin composition according to (1), wherein the plasticizer is a hydrocarbon plasticizer or an ester plasticizer.
(3) The resin composition according to (1), wherein the plasticizer is a naphthenic hydrocarbon or an aromatic hydrocarbon.
(4) The resin composition according to (1), wherein the carbon-nitrogen bond is an amide bond, a urethane bond, and/or a urea bond.
(5) (a) The resin composition contains a plasticizer,
and (b-1) the polyester resin further has a carbon-nitrogen bond in its structure, or (b-2) the polyester resin contains a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, a cyanate compound The resin composition according to (1), further comprising a reaction with at least one nitrogen-containing compound selected from the group consisting of , urea compounds, urethane compounds, amide compounds, and cyan compounds.
(6) The resin composition according to any one of (1) to (5), further comprising an inorganic filler.

According to the present invention, a resin composition with improved heat resistance can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

(Resin composition)
The resin composition that is one aspect of the present embodiment includes a polyester resin formed by reacting a maleic anhydride-modified polyolefin with a polyol.
In the resin composition of the present embodiment, heat resistance is improved because the resin composition is at least one of the following (a), (b-1), or (b-2).
(a) The resin composition contains a plasticizer.
and/or (b-1) the polyester resin further has a carbon-nitrogen bond in its structure.
Alternatively, (b-2) at least the polyester resin is selected from the group consisting of a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, a cyanate compound, a urea compound, a urethane compound, an amide compound, and a cyanide compound. Consists of a further reaction with one compound.

In one aspect of this embodiment, the resin composition may be (a) and (b-1) or (a) and (b-2), in which case the resin composition is maleic anhydride-modified. A resin composition comprising a polyester resin formed by a reaction between a polyolefin and a polyol,
(a) the resin composition contains a plasticizer,
and (b-1) the polyester resin further has a carbon-nitrogen bond in its main chain structure, or (b-2) the polyester resin contains a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound , a further reaction with at least one compound selected from the group consisting of cyanate compounds, urea compounds, urethane compounds, amide compounds, and cyanide compounds,
It may be a resin composition.

(polyester resin)
The polyester resin contained in the resin composition is a resin obtained by reacting a maleic anhydride-modified polyolefin with a polyol and connecting them through an ester bond.
Therefore, the polyester resin has within its structure an ester bond obtained by reacting a maleic anhydride-modified polyolefin with a polyol.
As the maleic anhydride-modified polyolefin and polyol, commercially available products may be used, or they may be prepared according to or in accordance with conventionally known methods.

The maleic anhydride-modified polyolefin is, for example, a compound obtained by modifying a polyolefin rubber such as polybutadiene rubber (preferably liquid polybutadiene rubber) with maleic anhydride.
The maleic anhydride-modified polyolefin is not particularly limited, but for example, maleic anhydride-modified polybutadiene, maleic anhydride-modified polypropylene, etc. can be used, and maleic anhydride-modified polybutadiene is particularly preferred.

The number average molecular weight (Mn) of the maleic anhydride-modified polyolefin is not particularly limited, but is preferably 2,000 or more and 10,000 or less, and within the range, it may be 2,500 or more and 6,000 or less.
Further, the number of maleic acids in the maleic anhydride-modified polyolefin is preferably 2 or more, and may be 20 or less, 15 or less, 12 or less, or 10 or less.

The acid value of the maleic anhydride-modified polyolefin is preferably 10 to 200 mgKOH/g, more preferably 10 to 120 mgKOH/g, and even more preferably 30 to 100 mgKOH/g.

In maleic anhydride-modified polybutadiene, the content% (composition ratio) of 1,2 vinyl groups in the butadiene skeleton is preferably within the range of 5 to 80%, more preferably within the range of 10 to 60%, and 15 to 30%. % is more preferable.

The above-mentioned physical property values such as the molecular weight and acid value of the maleic anhydride-modified polyolefin may be measured by conventionally known methods, or may be the values listed in the product catalog.

Maleic anhydride-modified polybutadiene is not particularly limited, but specifically, Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon13 sold as the Ricon (registered trademark) series (CRAY VALLEY). 1MA17, POLYVEST (registered trademark) POLYVEST MA75 sold as (EVONIK), POLYVEST EP MA 120, AL-15MA sold as Lithene ultra (registered trademark) (synthomer), PM4-7.5MA, N4-5000-10MA, N4-B- 10MA etc. are mentioned.

The maleic anhydride-modified polyolefin in the polyester resin may be used alone or in combination of two or more.

The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups that is used in the production of polyester resin, but examples include diols, triols, polyhydric alcohols having four or more hydroxyl groups, polyether polyols, and polyester polyols. , polylactone polyol, polycarbonate polyol, polyolefin polyol, and the like.
Among them, polyester polyols, polycarbonate polyols, and polyolefin polyols are preferably used, and polyester polyols and polyolefin polyols are more preferably used. The polyester polyol and the polyolefin polyol may each be used as a single substance, each may be used individually, and two or more types may be used, and both the polyester polyol and the polyolefin polyol may be used individually or in two or more types. Furthermore, castor oil polyol may be used as the polyester polyol.
Polyether polyols, polyester polyols, polylactone polyols, and polycarbonate polyols are not particularly limited, but for example, polyols described in JP 2020-143186A may be used, and polyester polyols are not particularly limited, but For example, a polyol described in JP-A-2019-183125 may be used.

Examples of diols include compounds having two hydroxyl groups in the molecule, such as ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), dipropylene glycol, 1,3-propanediol, and 1,3-butane. Diol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-butyl-2 -Ethyl-1,3-propanediol, 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1, 5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, cyclohexane 1,4-diol, cyclohexane 1, Examples include 4-dimethanol.

Examples of the triol include compounds having three hydroxyl groups in the molecule, such as trimethylolpropane, glycerin, 1,2,4-butanetriol, hexanetriol, and benzyltriol.
As the polyol, for example, pentaerythritol or the like may be used as a polyhydric alcohol having four or more hydroxyl groups in the molecule.

Examples of polyether polyols include polymers of diols with ether bonds, and specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Examples of the polyester polyols include esterification products of polyols such as sebacic acid polyester polyols and adipic acid polyester polyols with dicarboxylic acids, and esterification products of dimer acid and castor oil polyols.

As the polyol in the polyester polyol, the compounds described above as polyols may be used, but for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1 ,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1, Examples include 8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, and octadecanediol.

Examples of dicarboxylic acids in polyester polyols include succinic acid, methylsuccinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecane. Diacid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, Examples include hexahydroisophthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-biphaeldicarboxylic acid, and acid anhydrides thereof.
Examples of sebacic acid-based polyester polyols include polyester polyols containing at least an acid component containing sebacic acid and a polyol, and examples of adipic acid-based polyester polyols include polyester polyols containing at least an acid component containing adipic acid and a polyol. can be mentioned.

Examples of dimer acids include dimers obtained by polymerizing unsaturated fatty acids such as linoleic acid, oleic acid, elaidic acid, and tall oil fatty acids.
The castor oil polyol may be, for example, castor oil, partially dehydrated castor oil, partially acylated castor oil, castor oil, hydrogenated castor oil, or modified products thereof.
When the castor oil polyol is a modified product, it is a polyester polyol obtained by transesterification of castor oil, partially dehydrated castor oil, partially acylated castor oil, castor oil, hydrogenated castor oil, and polyether polyol or polyol. Common examples include esters of castor oil fatty acids, hydrogenated castor oil fatty acids, and polyether polyols and polyols.

The polyester polyol is not particularly limited, but specifically, the URIC H series (for example, H-30, H-102, H-420) sold as URIC (Ito Oil Co., Ltd.), the URIC AC series ( For example, AC-005), URIC Y series (eg, Y-403, Y-406), and the like.

Examples of polylactone polyols include polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and δ-valerolactone.

Examples of polycarbonate polyols include polymers of polyols and carbonates.
As the polyol in the polycarbonate polyol, the compounds described above as polyols may be used, but examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentane. Diol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1, 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexane Examples include triol, polypropylene glycol, and the like.

Examples of the carbonates in the polycarbonate polyol include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, phosgene, and the like.

As a method for preparing a polycarbonate polyol, for example, a dealcoholization reaction or a dephenolization reaction between a polyol and a carbonate may be performed, or a transesterification reaction or the like may be performed using a polyalcohol on a high molecular weight polycarbonate polyol. .
Polycarbonate polyols are not particularly limited, but specifically, they are sold as Duranol (Asahi Kasei Corporation), ETERNACOLL (registered trademark) UH, UHC, UC, UM, PH, UP series (Ube Industries, Ltd.) Examples include polycarbonate diol.
Among these, monopolymerized or copolymerized polycarbonate diols using 1,5-pentanediol or 1,6-hexanediol as the main skeleton may be mentioned, and caprolactane-modified polycarbonate diols may be used.

Examples of the polyolefin polyol include polybutadiene polyol, polyisoprene polyol, and the like, with polybutadiene polyol being preferably used.
The polyolefin polyol may be a hydrogenated polyolefin polyol.

Polybutadiene polyols are not particularly limited, but specifically include R-45HT, R-15HT, which is sold as Poly bd (hydroxyl group-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.), and POLYVEST (registered trademark) (EVONIK). POLYVEST (registered trademark) HT sold, G-1000, G-2000, G-3000 sold as NISSO-PB (Nippon Soda Co., Ltd.), LBH2000, LBH sold as Krasol (CRAY VALLEY) -P2000, LBH3000, LBH-P3000, etc.
The polybutadiene polyol may be a hydrogenated polybutadiene polyol, but examples of the hydrogenated polybutadiene polyol include, but are not limited to, GI-1000, which is sold as NISSO-PB (Nippon Soda Co., Ltd.); Examples include GI-2000, GI-3000, HLBH2000 sold as Krasol (CRAY VALLEY), and HLBH-P3000.

The polyisoprene polyol is not particularly limited, but specific examples include Poly ip (hydroxyl group-terminated liquid polyisoprene, manufactured by Idemitsu Kosan Co., Ltd.).
The polyisoprene polyol may be a hydrogenated polyisoprene polyol, but examples of the hydrogenated polyisoprene polyol include, but are not particularly limited to, EPOL (hydroxyl group-terminated liquid polyolefin, manufactured by Idemitsu Kosan Co., Ltd.). It will be done.

From the viewpoint of reactivity and workability, the molecular weight of the polyol is preferably from 100 to 10,000, more preferably from 200 to 5,000, and even more preferably from 300 to 3,000. Within this range, the number average molecular weight may be 500 or more, or 800 or more.
The viscosity of the polyol at 25° C. is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and even more preferably 10 Pa·s or less.
The hydroxyl value of the polyol is preferably 10 to 1000 mgKOH/g, more preferably 20 to 500 mgKOH/g, even more preferably 40 to 300 mgKOH/g.
The average number of functional groups of the polyol is preferably 1 or more and 6 or less, more preferably 1.5 or more and 5 or less, and even more preferably 2 or more and 3 or less.
When polybutadiene polyol is used as the polyol, the iodine value of the polybutadiene polyol is within the range of 1 to 1000 g/100 g, preferably within the range of 5 to 500 g/100 g.
The molecular weight, viscosity, hydroxyl value, average number of functional groups, and iodine value of the polyol may be measured by conventionally known methods, or may be the values listed in the product catalog.

The polyols in the polyester resin may be used alone or in combination of two or more.

(Plasticizer)
In this embodiment, the resin composition can include a plasticizer.
The plasticizer is not particularly limited, and the following plasticizers may be used.
When the polyester resin in this embodiment contains a plasticizer, the plasticizer may be used alone or in combination of two or more.

Examples of the hydrocarbon plasticizer include naphthenic hydrocarbons, aromatic hydrocarbons, paraffin hydrocarbons, olefin hydrocarbons, and the like. Among these, naphthenic hydrocarbons or aromatic hydrocarbons are preferred.

The naphthenic hydrocarbon is not particularly limited as long as it has at least one saturated ring in the molecule, and examples thereof include dicyclopentadiene.
Naphthenic hydrocarbons are not particularly limited, but specifically include SUN 6 INSULATION OIL (Nippon Sun Oil Co., Ltd.), Diana Process Oil NS (90S, 100), Diana Process Oil NM (280), Diana Process Oil NP (24), 90S, 100), Diana Process Oil NR (26) (Idemitsu Kosan Co., Ltd.), SUNTHENE series (e.g. 410, 450, 4240, 250J), SUPURE series (e.g. N90, NX90) ( (Nippon Sun Oil Co., Ltd.), etc.

The aromatic hydrocarbon is not particularly limited as long as it has at least one aromatic ring in the molecule.
Aromatic hydrocarbons are not particularly limited, but specific examples include Diana Process Oil AC (460), Diana Process Oil AH (16) (Idemitsu Kosan Co., Ltd.), JSO AROMA 790 (Nippon Sun Oil Co., Ltd.) company), etc.

Examples of paraffinic hydrocarbons include isoprene, piperylene, styrene, vinyltoluene, indene, and terpene resins (α-pinene, β-pinene, (dipentene type), aromatic modified terpene resin, terpene phenol resin, etc.
Paraffinic hydrocarbons are not particularly limited, but specifically include Diana Process Oil PW (90, 380) (Idemitsu Kosan Co., Ltd.), SUNPAR series (for example, 107, 150, 2280), SUPURE series (for example, LW70, P100) (all manufactured by Nippon Sun Oil Co., Ltd.), and the like.
The hydrocarbon plasticizer may be a paraphen-naphthenic mixed hydrocarbon.

Examples of olefinic hydrocarbons include cooligomers of ethylene and α-olefin, poly-α-olefins, and hydrogenated poly-α-olefins.
The hydrogenation method is not particularly limited, and any known method can be used.
Examples of olefinic hydrocarbons include, but are not particularly limited to, α-olefins sold as Linearene 10 and Linearene 12 (Idemitsu Kosan Co., Ltd.), Durasyn (INEOS Oligomers), and Claprene (registered trademark) LIR-. 30, Polyisoprene sold as Kuraprene (registered trademark) LIR-410, Kuraprene (registered trademark) UC-102M, Kuraprene (registered trademark) LIR-290 (Kuraray Co., Ltd.), Kuraprene (registered trademark) LBR-302, Polybutadiene (Kuraray Co., Ltd.) sold as Kuraprene (registered trademark) LBR-307, Kuraprene (registered trademark) LBR-352, polystyrene butadiene (Kuraray Co., Ltd.) sold as Kuraprene (registered trademark) L-SBR-820. ), 1,2-polybutadiene homopolymer B series (eg, B-1000, B-3000) (Nippon Soda Co., Ltd.), and the like.

The ester plasticizer is not particularly limited as long as it contains an ester group, but examples include phthalate ester plasticizers, adipate ester plasticizers, castor oil ester plasticizers, and trimete ester plasticizers. and pyrolimetic acid ester plasticizers.

Examples of the phthalate ester plasticizer include dioctyl phthalate, diisononyl phthalate (diisononyl phthalate), and diundecyl phthalate.

Examples of the adipic acid ester plasticizer include dioctyl adipate, diisononyl adipate, diisodecyl adipate, and the like.

Examples of the castor oil ester plasticizer include methyl acetyl ricinoleate, butylacetyl ricinoleate, acetylated ricinoleic acid triglyceride, and acetylated polyricinoleic acid triglyceride.

Examples of trimetic acid ester plasticizers include trioctyl trimellitate, triisononyl trimellitate, and the like.

Examples of the pyrrolimetate plasticizer include tetraoctylpyromellitate, tetrasononylpyromellitate, and the like.

The content of the plasticizer can be appropriately set depending on the type of plasticizer.
From the viewpoint of insulation and hardness, the content of the plasticizer is preferably 50% by mass or less, more preferably 1 to 30% by mass, and even more preferably 10 to 30% by mass, based on 100% by mass of the resin composition. It is 30% by mass.

(carbon-nitrogen bond)
In this embodiment, the polyester resin further has carbon-nitrogen bonds in its structure.
The carbon-nitrogen bond is a bond contained in the polyester resin in addition to the ester bond formed by the bond between the maleic anhydride-modified polyolefin and the polyol.
The carbon-nitrogen bond is a bond formed by reacting a maleic anhydride-modified polyolefin and a polyol with a nitrogen-containing compound described in detail below in the production of a polyester resin. This is a bond formed by bonding an acid-modified polyolefin or polyol with a nitrogen-containing compound.
In this embodiment, it may be confirmed that the polyester resin is a resin formed by further reaction with a nitrogen-containing compound by confirming that it further has a carbon-nitrogen bond in its structure.

The carbon-nitrogen bond that the structure of the polyester resin has is a bond formed by a bond between a maleic anhydride-modified polyolefin or polyol and a nitrogen-containing compound, and includes, for example, an amide bond, a urethane bond, a urea bond, and the like. Among these, a urea bond is preferred.

The content of carbon-nitrogen bonds is not particularly limited, but can be calculated as follows, for example.
Ratio (%) of carbon-nitrogen bonds to ester groups = theoretical amount of carbon-nitrogen bonds / [theoretical amount of ester groups + theoretical amount of carbon-nitrogen bonds] x 100
During the ceremony,
The theoretical carbon-nitrogen bond amount corresponds to the number of moles of the functional group of the nitrogen-containing compound,
The theoretical ester group weight corresponds to the number of moles of hydroxyl groups in the polyol.
Note that the above calculation formula calculates the ratio of carbon-nitrogen bonds to ester groups on the assumption that all functional groups of the nitrogen-containing compound are completely reacted.
In this embodiment, the content of carbon-nitrogen bonds is 1 to 60%, preferably 1 to 30%, and more preferably 1 to 20%, as a ratio calculated by the above calculation.

The presence or absence of a carbon-nitrogen bond can be confirmed, for example, by the presence or absence of a predetermined peak in an IR spectrum obtained by FT-IR analysis.
The presence or absence of urethane bonds or urea bonds is not particularly limited, but can be confirmed by the presence or absence of peaks at 1660 to 1720 cm ^-1 and 730 to 790 cm ^-1 in the IR spectrum of FT-IR analysis.
The presence or absence of an amide bond can be confirmed, for example, by the presence or absence of a peak at 1515 to 1680 cm ^-1 in the IR spectrum of FT-IR analysis.

(Nitrogen-containing compounds)
In this embodiment, the polyester resin consists of a further reaction with a nitrogen-containing compound.
Here, the polyester resin is a polymer of a maleic anhydride-modified polyolefin, a polyol, and a nitrogen-containing compound.
The nitrogen-containing compound is not particularly limited as long as it contains a nitrogen atom in the molecule and can be introduced into the structure of the polyester resin, but in this embodiment, it is a compound that can be bonded to maleic anhydride-modified polyolefin or polyol. .
Examples of the nitrogen-containing compound include at least one selected from the group consisting of carbodiimide compounds, oxazolidine compounds, amine compounds, isocyanate compounds, melamine cyanurate compounds, cyanate compounds, urea compounds, urethane compounds, amide compounds, and cyanide compounds. Among them, carbodiimide compounds, oxazolidine compounds, amine compounds, and isocyanate compounds are preferred, carbodiimide compounds, oxazolidine compounds, and isocyanate compounds are more preferred, and carbodiimide compounds are even more preferred.
The nitrogen-containing compounds may be used alone or in combination of two or more.

When the nitrogen-containing compound is a carbodiimide compound, the carbon-nitrogen bond in the structure of the polyester resin is a urea bond.
When a carbodiimide compound is used as a nitrogen-containing compound, theoretically, an ester bond formed by the reaction of maleic anhydride and a polyol and a free carboxy group derived from maleic anhydride exist, and the carboxy group and carbodiimide group react. Forms a urea bond.
When the nitrogen-containing compound is an oxazolidine compound, an amine compound, or a melamine cyanurate compound, the carbon-nitrogen bond in the structure of the polyester resin is an amide bond.
When an oxazolidine compound is used as a nitrogen-containing compound, the oxazolidine compound is theoretically hydrolyzed and converted into an amine compound, and thus reacts with maleic anhydride to form an amide bond.
When an amine compound is used as a nitrogen-containing compound, the amine compound theoretically reacts with maleic anhydride to form an amide bond.
When a melamine cyanurate compound is used as a nitrogen-containing compound, since the melamine cyanurate compound is a salt of melamine and cyanuric acid, theoretically, the amino group of melamine and maleic anhydride react to form an amide bond.
When the nitrogen-containing compound is an isocyanate compound, the carbon-nitrogen bond in the structure of the polyester resin is a urethane bond.
When an isocyanate compound is used as a nitrogen-containing compound, a urethane bond is theoretically formed by the reaction between the isocyanate and the hydroxyl group of the polyol.
When the nitrogen-containing compound is a cyanate compound, urea compound, urethane compound, amide compound, or cyanide compound, the carbon-nitrogen bond in the structure of the polyester resin is formed as appropriate depending on the reactive group that each nitrogen-containing compound has. Ru.

A carbodiimide compound is a compound having a carbodiimide group in its molecule.
The carbodiimide compound may be polycarbodiimide, monocarbodiimide or cyclic carbodiimide, but it is preferably a compound having two or more carbodiimide groups in the molecule.
Further, the carbodiimide compound may be polycarbodiimide, which is a polymer having a carbodiimide group represented by "-N=C=N-" in the molecule.
Examples of carbodiimide compounds include N,N'-di-o-tolylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, and N,N'-bis(2 ,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-di-tert-butylphenylcarbodiimide, N-triyl- N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'- Examples include dicyclohexylcarbodiimide and N,N'-di-p-tolylcarbodiimide.

The carbodiimide compound is not particularly limited, but specifically, carbodilite V-02B, carbodilite V-03, carbodilite V-04K, carbodilite V-07, carbodilite V-09, carbodilite 10M-SP, and carbodilite 10M-SP. (Nisshinbo Chemical Co., Ltd.), Stavaxol P, Stavaxol P400, Haikasil 510 (Lanxess Co., Ltd.), and the like.

An oxazolidine compound is a compound having an oxazolidine ring in its molecule. The oxazolidine compound is preferably a compound having two or more oxazolidine rings in the molecule.
Examples of the oxazolidine compound include N-hydroxyalkyl oxazolidine, oxazolidine silyl ether, carbonate oxazolidine, and ester oxazolidine. More specifically, for example, 2-isopropyl-3-(2-hydroxyethyl)oxazolidine, 2-phenyl-3-(2-hydroxyethyl)oxazolidine, 2-(1-methylbutyl)-3-(2-hydroxy Examples include ethyl)oxazolidine, 2-isopropyl-3-(2-hydroxypropyl)-5-methyloxazolidine, and the like.
Examples of oxazolidine compounds include, but are not particularly limited to, hardeners (Bayer Yakuhin Co., Ltd.), URIC LC series (for example, LC-555, LC-500) sold as URIC (Ito Oil Co., Ltd.), etc. can be mentioned.

An amine compound is a compound having an amino group in its molecule. The amine compound is preferably a compound having two or more amino groups in the molecule.
Examples of amine compounds include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, and aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, and dibutylamine. , aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine, aliphatic unsaturated amines such as triallylamine, oleylamine, aromatic substances such as aniline, laurylaniline, stearylaniline, triphenylamine, etc. group amines, pyridine, 2-aminopyridine, 2-(dimethylamino)pyridine, 4-(dimethylaminopyridine), 2-hydroxypyridine, heterocyclic compounds such as imidazole, monoethanolamine, diethanolamine, triethanolamine, Examples include 3-hydroxypropylamine.

The amine compound may be a diamine compound having two amino groups in the molecule.
Examples of diamine compounds include ethylene diamine, 1,1-methaxylylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, 4,4-diamino Fats such as heptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylene diamine, hexahydro-4,7-methanoindani dimethylene diamine, 4,4'-methylenebis(cyclohexylamine), etc. group diamines and alicyclic diamines, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfide, 4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3, 3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenz Anilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4 '-Methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5 '-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4 -aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4- aminophenoxy)-biphenyl, 1,3'-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-(p-phenyleneisopropylidene)bisaniline, 4,4 '-(m-phenyleneisopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[4-(4- Examples include aromatic diamines such as amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4,4'-methylenebis[N-(1-methylpropyl)aniline], dimethylthiotoluenediamine, diethyltoluenediamine, etc. .
The diamine compound may be an aromatic diamine known as Ettacure (Mitsui Chemicals Fine Co., Ltd.).

The amine compound may be a compound having three or more amino groups in the molecule.
Examples of such amine compounds include diethylenetriamine, triethylenetetramine, 3-methoxypropylamine, 3-lauryloxypropylamine, guanidines such as guanidine and diphenylguanidine, butyl biguanide, 1-o-tolyl biguanide, 1- Examples include biguanides such as phenylbiguanide.

An isocyanate compound is a compound having an isocyanate group in its molecule. The isocyanate compound is preferably a compound having two or more isocyanate groups in the molecule.
Examples of the isocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. , 2-methylpentane-1,5-diisocyanate, aliphatic isocyanate compounds such as 3-methylpentane-1,5-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (4,4 Hydrogenated product of '-diphenylmethane diisocyanate (HMDI), 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, alicyclic isocyanate compounds such as 1,3-bis(isocyanatemethyl)cyclohexane, tolylene diisocyanate, 2,2' -diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate , 1,4-phenylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylylene diisocyanate and the like.

Isocyanate compounds are not particularly limited, but specifically include TPA-100, TKA-100, TSA-100, TSS-100, and TSE-100 sold as Duranate (registered trademark) (Asahi Kasei Corporation). , TLA-100, Desmodur (registered trademark) N3390 (Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 1390 sold as Coronate (registered trademark) (Tosoh Corporation), Coronate (registered trademark) ) 1391, Coronate (registered trademark) 1569, Coronate (registered trademark) 1050, Coronate (registered trademark) 1057, Coronate (registered trademark) HX, Coronate (registered trademark) HK, Coronate (registered trademark) 2770 , sold as Wood Cure 220, Wood Cure 300, Takenate D170N (Takeda Pharmaceutical Company Limited), Burnock (registered trademark) DN980 (DIC Corporation), Millionate (registered trademark) (Tosoh Corporation) Millionate (registered trademark) NM, Millionate (registered trademark) MTL, Millionate (registered trademark) MR-100, Millionate (registered trademark) MR-200, Coronate (registered trademark) MX (Tosoh Corporation), Luplanate (registered trademark) Examples include Lupranate (registered trademark) MI, Lupranate (registered trademark) 20S, and Lupranate (registered trademark) M5S, which are sold as trademarks (BASF INOAC Polyurethane Co., Ltd.).

Examples of melamine cyanurate compounds include N,N'-(6-amino-1,3,5-triazine-2,4-diyl)dipropionamide, N,N'-(6-amino-1,3 ,5-triazine-2,4-diyl)dibutylamide, N,N'-(6-amino-1,3,5-triazine-2,4-diyl)dihexanamide, N,N'-(6- Examples include amino-1,3,5-triazine-2,4-diyl)dioctanamide.

Melamine cyanurate compounds are not particularly limited, but specifically include MC-4000, MC-4500, MC-6000 (all manufactured by Nissan Chemical Co., Ltd.), MCA-0, MCA-1 (all manufactured by Mitsubishi Chemical Corporation). company), etc.

A urea compound is a compound that has a urea bond in its molecule.
Examples of the urea compound include a compound obtained by reacting the above-mentioned isocyanate compound with the above-mentioned amine compound, or a prepolymer thereof. More specifically, for example, 3-phenyl-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1 , 1-dimethylurea, toluene bisdimethylurea and the like.
The urea compound is not particularly limited, but specifically, DCMU-99 (Hodogaya Chemical Industry Co., Ltd.), Omicure (registered trademark) 24 (PTI Japan Co., Ltd.), DCMU, U-CAT3512T, Examples include U-CAT3503N (all manufactured by Sun-Apro Co., Ltd.).

A urethane compound is a compound having a urethane bond in its molecule.
Examples of the urethane compound include a compound obtained by reacting the above-mentioned isocyanate compound with the above-mentioned polyol, or a prepolymer thereof.
The urethane compound is not particularly limited, but specific examples include UXE-3011, UXE-3012, and UXE-3024 (all manufactured by Nippon Kayaku Co., Ltd.).

An amide compound is a compound that has an amide bond in its molecule.
Examples of the amide compound include dicyandiamide, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-diphenylacetamide.
The amide compound is not particularly limited, but specifically, it is sold as Alflo (registered trademark) (NOF Corporation), Twaron (registered trademark), Technora (registered trademark), and Conex (registered trademark). Examples include aramid fiber (Teijin Ltd.).

A cyanide compound is a compound having a cyano group (-CN) in its molecule.
Examples of the cyanide compound include dicyandiamide and phosphazenenitrile.
The cyanide compound is not particularly limited, but specific examples include Ravitol FP-300B (Fushimi Seiyakusho Co., Ltd.).

The blending amount of the nitrogen-containing compound is not particularly limited, and can be appropriately set depending on the type of the nitrogen-containing compound.
The blending amount of the nitrogen-containing compound is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 1 to 10% by mass, based on 100% by mass of the polyester resin.

(Inorganic filler)
In this embodiment, the resin composition can include an inorganic filler.
Examples of the inorganic filler include, but are not limited to, metal hydrates, metal oxides, metal carbonate compounds, metal nitrides, zeolites, talc, carbon black, fibrous fillers, and the like.

Examples of metal hydrates include aluminum hydroxide, magnesium hydroxide, and the like. As the metal hydrate, aluminum hydroxide is preferred.

Aluminum hydroxide is not particularly limited, but specifically, B303 (average particle size 23 μm), B153 (average particle size 12 μm), B103 (average particle size 7 μm) (all Nippon Light Metal Co., Ltd.), C- 310 (average particle size 10 μm), C-301N (average particle size 1.5 μm) (all manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of metal oxides include aluminum oxide, magnesium oxide, titanium oxide, and the like.

Aluminum oxide is not particularly limited, but specifically, DAW-45 (average particle size 46.1 μm), DAW-05 (average particle size 6.4 μm), ASFP-20 (average particle size 0.3 μm) (Denka Co., Ltd.), AL-43A (average particle size 50 μm), AA-3 (average particle size 3.5 μm), AKP-50 (average particle size 0.2 μm) (Sumitomo Chemical Co., Ltd.), Examples include CB A50S (average particle size 50 μm), CB-P05 (average particle size 4 μm) (all manufactured by Showa Denko K.K.).

Examples of metal carbonate compounds include calcium carbonate, aluminum carbonate, magnesium carbonate, barium carbonate, zinc carbonate, iron carbonate, cobalt carbonate, titanium carbonate, and the like.

Examples of calcium carbonate include, but are not particularly limited to, NS#1000, NS#400, NS#100, NCC#45, NCC#410, NCC#1010 (Nitto Funka Kogyo Co., Ltd.), Hakuenka Examples include CC, Shiroenka CC-R, and Shiroenka CCR-S (all manufactured by Shiroishi Calcium Co., Ltd.).

Examples of metal nitrides include silicon dioxide (silica), boron nitride, aluminum nitride, and silicon nitride.

Examples of the zeolite include silicates of alkali metals or alkaline earth metals. Examples of the alkali metal or alkaline earth metal in the zeolite include potassium, sodium, calcium, and lithium.

Talc is not particularly limited, but specifically, SG-95, P-8, P-6, K-1 sold as Micro Ace (registered trademark), SWE sold as general-purpose talc, MS-K, MS-P, SSS, SG-2000, SG-200, SG-200N15 sold as ultrafine talc, Nano Ace D-600, Nano Ace D-800 sold as NANO ACE (registered trademark) , Nano Ace D-1000 (all manufactured by Nippon Talc Co., Ltd.).

Examples of the fibrous filler include glass fiber and carbon fiber.

The inorganic fillers may be used alone or in combination of two or more.

The content of the inorganic filler can be appropriately set depending on the type of the inorganic filler.
The content of the inorganic filler is preferably 0 to 70% by mass, more preferably 20 to 70% by mass, based on 100% by mass of the resin composition, from the viewpoint of reinforcing effect and workability.

In this embodiment, the resin composition may contain flame retardants such as halogen-based, red phosphorus, phosphate ester, phosphazene, nitrogen-based, and metal hydrates, flame retardant aids such as antimony, and antioxidants, as necessary. , a tackifier, a curing accelerator, a colorant, a chain extender, a crosslinking agent, a filler, a pigment, an ultraviolet absorber, a moisture absorbent, a fungicide, a silane coupling agent, and other additives. . Moreover, the resin composition may contain a catalyst used when manufacturing the resin.
The content of these components may be appropriately set depending on the purpose of use.

In the present embodiment, the resin composition includes a first component (sometimes referred to as "first component") that includes at least a maleic anhydride-modified polyolefin that serves as a so-called curing agent, and a second component that includes at least a polyol that serves as a base component. It may be a two-part type containing a component (sometimes referred to as a "second component"). At this time, the plasticizer, nitrogen-containing compound, inorganic filler, and other components may be contained in either the first component or the second component, and each may be divided into arbitrary amounts and contained in either. You can.

In this embodiment, the content of the nitrogen-containing compound in the resin composition can be set as appropriate, regardless of whether it is contained in the first component or the second component, or even if it is contained in both.

When the resin composition is a two-component type, the blending ratio of the first component and the second component can be changed as appropriate depending on the composition of the resin, but the blending ratio of the first component:second component is The ratio is preferably 1:5 to 5:1, more preferably 1:2 to 2:1.

(Method for manufacturing resin composition)
The method for producing the resin composition of the present embodiment is not particularly limited, but it can be produced appropriately according to or in accordance with known methods. As appropriate, the nitrogen-containing compound and other components may be mixed simultaneously or in stages.
The method for producing a two-component resin composition includes, for example, a step of preparing a first component, a step of preparing a second component, and a step of obtaining a resin composition by mixing the first component and the second component. Examples include methods including:
The method for producing a two-component resin composition may further include, for example, a step of adding a nitrogen-containing compound to the first component and/or the second component and reacting the nitrogen-containing compound.
The method for producing a two-component resin composition may further include, for example, a step of adding a nitrogen-containing compound to a resin composition in which a first component and a second component are mixed and reacting the nitrogen-containing compound.
In the present embodiment, the two-component resin composition includes the case where the first component and the second component exist independently before being mixed.

The present invention will be explained more specifically using Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

<Materials of resin composition>
The following materials were used.
(A) Maleic anhydride-modified polyolefin (A-1): Maleic anhydride-modified polybutadiene, number average molecular weight 2700, number of functional groups 2, acid value 42 mgKOH/g (Cray valley USA, LLC, product name: Ricon 130MA8)
(A-2): Maleic anhydride modified liquid polybutadiene, number average molecular weight 2900, number of functional groups 4, acid value 77 mgKOH/g (Cray valley USA, LLC, product name: Ricon130MA13)
(B) Polyol (B-1): Polyolefin polyol (hydroxyl group-terminated liquid polybutadiene), number average molecular weight 2800, iodine value 398, hydroxyl value 46 mgKOH/g (JIS K 1557), number of functional groups 2.2 (Idemitsu Kosan Co., Ltd., Product name: Poly bd R-45 HT)
(B-2): Polyester polyol, number average molecular weight 933, hydroxyl value 160 mgKOH/g, viscosity 660 mPa・s (25°C), number of functional groups 2.7 (Ito Oil Co., Ltd., product name: URIC H-30)
(B-3): Polyester polyol, average molecular weight 900, hydroxyl value 320 mgKOH/g, viscosity 1100 mPa・s (25°C), number of functional groups 5 (Ito Oil Co., Ltd., product name: URIC H-102)
(B-4): Polycarbonate polyol (polycarbonate diol), average molecular weight 1000, hydroxyl value 110 mgKOH/g, viscosity 200 mPa・s (75°C), number of functional groups 2.0 (Ube Industries, Ltd., product name: UHC50-100)
(C) Nitrogen-containing compound (C-1): Carbodiimide, viscosity 140 Pa・s (20°C), carbodiimide equivalent weight 600 (Nisshinbo Chemical Co., Ltd., product name: Carbodilite V-02B)
(C-2): Oxazolidine, viscosity 8,000 mPa・s, number of oxazolidine functional groups: 2, molecular weight 500 (Ito Oil Co., Ltd., product name: URIC LC-555)
(C-3): DETDA (diethyltoluenediamine), viscosity 280 mPa・s, amine value 631 mgKOH/g (Mitsui Chemicals Fine Co., Ltd., product name: Etacure 100 Plus)
(C-4): Isocyanate, viscosity 50 mPa・s, NCO content 32.0% (Tosoh Corporation, product name: Coronate 1390)
(D) Plasticizer (hydrocarbon plasticizer)
(D-1): Naphthenic hydrocarbon, specific gravity 0.93, pour point -20°C or less (Nippon Sun Oil Co., Ltd., product name: SUN 6 INSULATION OIL)
(D-2): Aromatic hydrocarbon, density 1.02 g/cm ³ (15°C) (Idemitsu Kosan Co., Ltd., product name: Diana Process Oil AC-460)
(ester plasticizer)
(D-3): Diisononyl phthalate, specific gravity 0.98, pour point -30°C or less (Shin Nihon Rikagaku Co., Ltd., product name: Sansocizer DINP)
(olefin plasticizer)
(D-4): Poly α-olefin, specific gravity 0.83, pour point -30°C or lower (INEOS Oligomers, product name: Durasyn PaO 160 series 168)
(E) Inorganic filler (E-1): aluminum hydroxide, average particle size 7 μm (Nippon Light Metal Co., Ltd., product name: B103)
(E-2): Calcium carbonate, average particle size 4.4 μm (Nitto Funka Kogyo Co., Ltd., product name: NCC #45)

<Pre-drying of inorganic filler>
The inorganic filler was placed in a metal container and left standing at 130° C. for 16 hours using a dryer (Espec Co., Ltd., product name: Perfect Oven PH-102) to remove water adhering to the surface.
<Manufacture of resin composition>
(Preparation of resin composition)
The obtained curing agent and base agent were mixed at 2000 rpm for 2 minutes at the compounding ratio shown in Table 1 using an autorotation/revolution mixer (Thinky Co., Ltd., product name: Awatori Rentaro). The resulting mixture was defoamed to obtain a resin composition.

(Preparation of test piece A)
The prepared resin composition was poured into a mold with an inner diameter of 30 mm and a height of 10 mm, heated at 80° C. for 16 hours, and then left at room temperature for 1 day to harden to obtain a test piece A.

(Preparation of comb-shaped test piece B)
A comb-shaped test piece B was obtained in the same manner as the test piece A except that a mold having an inner diameter of 100 mm and a height of 20 mm was used.

(Heat resistance test)
According to JIS K 6253, the hardness (type A) of test piece A (inner diameter 30 mm, height 10 mm) at a temperature of 23°C was measured using a hardness meter (Kobunshi Keiki Co., Ltd., product name: Asker Rubber Hardness Meter Type A). It was measured using
After heating at 80° C. for 16 hours, the hardness of test piece A immediately after being left at room temperature for 1 day was defined as the “initial hardness”. After the initial hardness measurement, the test piece A was heated in a dryer at 100°C for 100 hours, and the hardness of the test piece after cooling to 23°C was defined as the "final hardness" and was measured in the same manner as the initial hardness. From the initial hardness and final hardness, the "hardness change rate" was calculated based on the following formula.
Hardness change rate (%) = [(final hardness - initial hardness) / initial hardness] x 10
The hardness change rate is preferably less than 40%, and may be 40% or more and less than 80%.

After the final hardness measurement, surface deterioration of test piece A was evaluated. The evaluation criteria are as follows.
Yes: The surface is altered, the surface layer is hard, and the skin is tight. Damage occurs due to contact with the tip of the hardness meter during hardness measurement (tearing of the surface layer, holes, etc.).
None: There is no deterioration of the surface layer and flexibility is maintained.

(Moisture resistance test)
A moisture resistance test was conducted after 250 hours using a pressure cooker tester (conditions: 121° C., 100% RH), and after cooling to room temperature (23° C.), the hardness of test piece A was measured and evaluated.

After the moisture resistance test, surface deterioration of test piece A was evaluated. The evaluation criteria are as follows.
Yes: The surface is altered, the surface layer is hard, and the skin is tight. Damage occurs due to contact with the tip of the hardness meter during hardness measurement (tearing of the surface layer, holes, etc.).
None: There is no deterioration of the surface layer and flexibility is maintained.

(insulation)
Using the comb-shaped test piece B, a high temperature and high humidity bias test was conducted by applying 100 V in a pressure cooker tester (conditions: 85° C., 85% RH). After 2000 hours, it was taken out, cooled to room temperature (23° C.), and then the insulation resistance value (Ω) was measured to evaluate the insulation property. The evaluation criteria are as follows.
〇: Insulation resistance value is 10GΩ or more ×: Insulation resistance value is 10GΩ or less

The results are shown in Tables 1 to 3.

Claims (6)

A resin composition comprising a polyester resin formed by reacting a maleic anhydride-modified polyolefin with a polyol,
(a) the resin composition contains a plasticizer;
and/or (b-1) the polyester resin further has a carbon-nitrogen bond in its structure, or (b-2) the polyester resin contains a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, A resin composition further comprising a reaction with at least one nitrogen-containing compound selected from the group consisting of a cyanate compound, a urea compound, a urethane compound, an amide compound, and a cyanide compound. The resin composition according to claim 1, wherein the plasticizer is a hydrocarbon plasticizer or an ester plasticizer. The resin composition according to claim 1, wherein the plasticizer is a naphthenic hydrocarbon or an aromatic hydrocarbon. The resin composition according to claim 1, wherein the carbon-nitrogen bond is an amide bond, a urethane bond, and/or a urea bond. (a) the resin composition contains a plasticizer,
and (b-1) the polyester resin further has a carbon-nitrogen bond in its structure, or (b-2) the polyester resin contains a carbodiimide compound, an oxazolidine compound, an amine compound, an isocyanate compound, a melamine cyanurate compound, a cyanate compound The resin composition according to claim 1, further comprising a reaction with at least one nitrogen-containing compound selected from the group consisting of , urea compounds, urethane compounds, amide compounds, and cyan compounds. The resin composition according to any one of claims 1 to 5, further comprising an inorganic filler.