JP7235881B2 - Coated wire sealing composition and coated wire - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coated wire sealing composition and a coated wire. More specifically, the present invention relates to a composition that is widely used as a sealant for coated wires in wiring of various electrical systems such as automobiles, home appliances, and OA (Office Automation) equipment, and a coated wire comprising a cured product of the composition. It is.

2. Description of the Related Art In automobiles, home electric appliances, office automation equipment, and the like, various electrical systems are wired by electric wires, and the harness portions thereof have conventionally been caulked or sealed.

As conventional coated wire sealing compositions, those described in Patent Documents 1 and 2 are known.
Patent Document 1 discloses a coated electric wire sealing composition comprising an alkyl-2-cyanoacrylate, a 2-cyanoacrylate having an ether bond in an ester residue, and a (meth)acrylate having two or more (meth)acryloyloxy groups. Are listed.
Patent Document 2 describes a coated electric wire sealing composition containing 2-cyanoacrylate containing 10% by mass or more of alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms in the main chain. there is

JP-A-9-118839 WO2018/216737

According to one embodiment of the present invention, there is provided a coated wire sealing composition that achieves both water resistance and thermal shock resistance under high temperature and high humidity conditions and provides a cured product that is also excellent in heat resistance.
According to another embodiment of the present invention, there is provided a coated wire comprising a cured product of the coated wire sealing composition.

The present invention includes the following aspects.
<1> A 2-cyanoacrylate compound containing 10% by mass or more of an alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms with respect to the total mass of the 2-cyanoacrylate compound, and a thickener and a viscosity at 25° C. of 20 mPa·s to 120 mPa·s.
<2> The coated wire sealing composition according to <1>, wherein the content of the thickener is 1 part by mass to 12 parts by mass with respect to 100 parts by mass of the content of the 2-cyanoacrylate compound.
<3> The coated wire sealing composition according to <1> or <2>, wherein the thickener is a copolymer containing a monomer unit composed of a (meth)acrylic monomer.
<4> The coated wire sealing composition according to any one of <1> to <3>, wherein the thickener is an elastomer.
<5> The coated wire sealing composition according to any one of <1> to <4>, wherein the thickener has a weight average molecular weight of 50,000 or more.
<6> After the tip of a capillary tube with an inner diameter of 1.05 mm and a length of 120 mm was immersed in a bath of the coated wire sealing composition with a depth of 30 mm for 2 seconds and pulled out, the capillary tube was turned in the longitudinal direction. The coating according to any one of <1> to <5>, wherein the suction length is 7 mm or more and 35 mm or less when left standing for 24 hours in a state where it is installed horizontally with respect to the direction of gravity. A composition for wire sealing.
<7> Any one of <1> to <6>, wherein the cured product of the coated wire sealing composition has a storage modulus at 80° C. of 9.0×10 ⁵ Pa or more and 1.5×10 ⁸ Pa or less. or a coated wire sealing composition according to any one of the above.
<8> The 2-cyanoacrylate compound is 2-octyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, n-octyl-2-cyanoacrylate, n-hexyl-2-cyanoacrylate, n-butyl The coated wire sealing composition according to any one of <1> to <7>, which is at least one compound selected from the group consisting of -2-cyanoacrylate and isobutyl-2-cyanoacrylate. .
<9> The 2-cyanoacrylate compound contains an alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms and/or a 2-cyanoacrylate having an ether bond in the ester residue <1> to <8> The coated wire sealing composition according to any one of 8>.
<10> The 2-cyanoacrylate compound contains an alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms,
The content of the alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms is 10% by mass or more and 90% by mass or less with respect to the total mass of the 2-cyanoacrylate compound, <1>- <9> The coated wire sealing composition according to any one of <9>.
<11> The 2-cyanoacrylate compound contains a 2-cyanoacrylate having an ether bond in the ester residue,
Any of <1> to <10>, wherein the content of the 2-cyanoacrylate having an ether bond in the ester residue is more than 0% by mass and 50% by mass or less with respect to the total mass of the 2-cyanoacrylate compound. or a coated wire sealing composition according to any one of the above.
<12> The thickener is a copolymer obtained by copolymerizing at least one monomer selected from the group consisting of ethylene, propylene, isoprene and butadiene with a (meth)acrylate compound. The coated wire sealing composition according to any one of <1> to <11>.
<13> The thickener copolymerizes at least one monomer selected from the group consisting of ethylene, propylene, isoprene and butadiene, a (meth)acrylate compound, and a monomer having a carboxy group. The coated wire sealing composition according to any one of <1> to <12>, which is a copolymer consisting of
<14> The coated wire sealing composition according to any one of <1> to <13>, further comprising a phthalic anhydride derivative represented by the following formula (1).

In formula (1), each R ¹ independently represents an alkyl group, an acyl group, an acyloxy group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a chlorine atom, a bromine atom or an iodine atom, and n is 1 to 4. represents an integer of

<15> The coated wire sealing composition according to any one of <1> to <14>, further comprising a plasticizer.
<16> The coated wire sealing composition according to <15>, wherein the content of the plasticizer is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the 2-cyanoacrylate compound. .
<17> (meth) further comprising a (meth)acrylate having two or more acryloyloxy groups,
The content of the (meth)acrylate having two or more (meth)acryloyloxy groups is 1% by mass or more and 35% by mass or less with respect to the total mass of the coated wire sealing composition <1> to <16> The coated wire sealing composition according to any one of 16>.
<18> A coated wire comprising a cured product of the coated wire sealing composition according to any one of <1> to <17>.

According to one embodiment of the present invention, it is possible to provide a coated wire sealing composition that achieves both water resistance and thermal shock resistance under high temperature and high humidity conditions and provides a cured product that is also excellent in heat resistance.
Further, according to another embodiment of the present invention, it is possible to provide a coated wire comprising a cured product of the composition for sealing a coated wire.

The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, "-" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit, respectively.
In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good. Moreover, in the numerical ranges described in this specification, the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present invention, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Moreover, in the present invention, a combination of two or more preferred aspects is a more preferred aspect.
Further, in the present specification, "(meth)acrylic" represents both or either acrylic and methacrylic, "(meth)acryloyl" represents both or either acryloyl and methacryloyl, and "(meth) ) acrylate" refers to both acrylate and/or methacrylate.
As used herein, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. means
An embodiment of the invention is described in detail below.

(Composition for coated wire seal)
The coated wire sealing composition of the present disclosure (hereinafter also simply referred to as the “composition”) contains an alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms in the total mass of the 2-cyanoacrylate compound. On the other hand, it contains a 2-cyanoacrylate compound containing 10% by mass or more and a thickener, and has a viscosity at 25° C. of 20 mPa·s to 120 mPa·s.
In addition, the coated wire sealing composition of the present disclosure can be suitably used as a coated wire sealing composition in wire harnesses for automobiles, home electric appliances, OA equipment, etc. It can be used particularly preferably as a product.

As a result of intensive studies by the present inventors, a composition for coated wire seals has been developed that, by adopting the above configuration, provides both water resistance and thermal shock resistance under high temperature and high humidity conditions and provides a cured product that is excellent in heat resistance. I found what I can offer.
Although the action mechanism of this excellent effect is not clear, it is presumed as follows.
By containing a 2-cyanoacrylate compound containing 10% by mass or more of an alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms with respect to the total mass of the 2-cyanoacrylate compound, durability against humidity is high. and a cured product with sufficient flexibility is obtained, and the viscosity at 25 ° C. is 20 mPa s to 120 mPa s, so that flexibility, especially flexibility at low temperatures It is presumed to be excellent in heat resistance and also excellent in heat resistance.
In addition, the coated wire sealing composition of the present disclosure contains an alkyl-2-cyanoacrylate having an alkyl group with 4 or more carbon atoms in an amount of 10% by mass or more relative to the total mass of the 2-cyanoacrylate compound, and By including a sticky agent, the resulting cured product has excellent bending resistance.

<Various physical property values of the composition or cured product>
-viscosity-
The coated wire sealing composition of the present disclosure has a viscosity of 20 mPa·s to 120 mPa·s at 25° C., and the obtained cured product has water resistance, cold/hot shock resistance, heat resistance, and From the viewpoint of bending resistance, it is preferably 25 mPa·s to 100 mPa·s, more preferably 30 mPa·s to 80 mPa·s, and particularly preferably 35 mPa·s to 60 mPa·s.

The method for measuring the viscosity of the coated wire sealing composition of the present disclosure at 25 ° C. is an E-type viscometer (cone plate type viscometer) TVE-20H type viscometer (salt water / flat plate method, Toki Sangyo Co., Ltd. (manufactured) to measure the viscosity under the following conditions.
-Measurement condition-
Cone shape: angle 1°34′, radius 24 mm
Temperature: 25°C ± 0.5°C

－Suction length－
The coated wire sealing composition of the present disclosure has a viscosity of 20 mPa s to 120 mPa s, and the obtained cured product has water resistance and cold/hot shock resistance under high temperature and high humidity conditions, heat resistance, and bending resistance. , The tip of a capillary tube with an inner diameter of 1.05 mm and a length of 120 mm was immersed in the bath liquid of the coated wire sealing composition with a depth of 30 mm for 2 seconds and pulled up, and then the longitudinal direction of the capillary tube was set in the direction of gravity. The suction length when left standing for 24 hours in a state where it is installed in a horizontal direction is preferably 7 mm or more and 35 mm or less, more preferably 10 mm or more and 32 mm or less, and 13 mm or more and 25 mm or less. is particularly preferred.
In addition, the measurement of the suction length is performed at 23° C.±0.5° C., and a capillary tube made of borosilicate glass is used.

- Storage modulus -
The cured product of the coated wire seal composition of the present disclosure preferably has a storage modulus at 80° C. of 9.0×10 ⁵ Pa or more and 1.5×10 ⁸ Pa or less, and preferably 9.0×10 ⁵ Pa. It is more preferably 5.0×10 ⁷ Pa or more, and particularly preferably 9.0×10 ⁵ Pa or more and 5.0×10 ⁶ Pa or less.

The storage modulus at 80° C. of the cured product of the coated wire sealing composition of the present disclosure shall be measured as follows using MCR 301 manufactured by Anton Paar.
After applying a curing accelerator solution (5 wt% N,N'-dimethylparatoluidine ethanol solution) to both sides of the upper and lower parallel plates and drying, apply an appropriate amount of the composition to the lower plate, and immediately attach the upper plate. lower the After that, it is left at 25° C. for 2 hours, and the storage modulus at 80° C. is measured under the conditions of 0.1% strain, 1 Hz frequency, 2° C./min heating rate, and 300 μm initial gap.

<2-cyanoacrylate compound>
The coated wire seal composition of the present disclosure is a 2-cyanoacrylate compound containing 10% by mass or more of an alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms with respect to the total mass of the 2-cyanoacrylate compound. including.
Even if the coated wire sealing composition of the present disclosure contains only an alkyl-2-cyanoacrylate having an alkyl group with 4 or more carbon atoms as the 2-cyanoacrylate compound, it does not contain an alkyl group with 4 or more carbon atoms. It may contain an alkyl-2-cyanoacrylate having and other 2-cyanoacrylate compounds.

The content of the 2-cyanoacrylate compound in the coated wire sealing composition of the present disclosure is, from the viewpoint of water resistance and thermal shock resistance under high temperature and high humidity conditions, heat resistance, and bending resistance of the obtained cured product, It is preferably 50% by mass to 99.8% by mass, more preferably 70% by mass to 99.5% by mass, and 80% by mass to 99% by mass, relative to the total mass of the composition. More preferably, it is particularly preferably 85% by mass to 97% by mass.

<<Alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms>>
Various alkyl-2-cyanoacrylates having an alkyl group with 4 or more carbon atoms in the main chain can be used as a component of the composition of the present disclosure. Although the upper limit of the number of carbon atoms in the main chain is not particularly limited, it can be, for example, 12 or less. The upper limit of the number of carbon atoms in the main chain is preferably 8 or less. Specific examples include n-butyl-2-cyanoacrylate, 2-butyl-2-cyanoacrylate, isobutyl-2-cyanoacrylate (2-methylpropyl-2-cyanoacrylate), n-hexyl-2-cyanoacrylate, n-heptyl-2-cyanoacrylate, 1-methylpentyl-2-cyanoacrylate, n-octyl-2-cyanoacrylate, 2-octyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, n-nonyl- 2-cyanoacrylate, isononyl-2-cyanoacrylate, n-decyl-2-cyanoacrylate, isodecyl-2-cyanoacrylate, n-undecyl-2-cyanoacrylate, and n-dodecyl-2-cyanoacrylate. . These can be used individually by 1 type, and can also use 2 or more types together.

Among these, 2-octyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, n-octyl-2-cyanoacrylate, n-hexyl-2-cyanoacrylate, isobutyl-2-cyanoacrylate and n-butyl -It is preferable to include at least one compound selected from the group consisting of 2-cyanoacrylates, because the obtained cured product has excellent water resistance and thermal shock resistance under high temperature and high humidity conditions, as well as excellent heat resistance. In addition, the composition of the present disclosure preferably contains at least one compound selected from the group consisting of 2-octyl-2-cyanoacrylate and isobutyl-2-cyanoacrylate as the 2-cyanoacrylate compound. preferable.
From the viewpoint of water resistance under high temperature and high humidity conditions, it is also preferable to use 2-octyl-2-cyanoacrylate and isobutyl-2-cyanoacrylate together.

The content of the alkyl-2-cyanoacrylate having an alkyl group with 4 or more carbon atoms is 10% by mass or more, even if it is 10% by mass to 100% by mass, based on the total mass of the 2-cyanoacrylate compound. From the viewpoint of water resistance and thermal shock resistance under high temperature and high humidity conditions in the resulting cured product, the content is preferably 25% by mass to 100% by mass, more preferably 40% by mass to 100% by mass. , 50% to 95% by weight.

Also, the composition of the present disclosure preferably has the following aspects.
In the composition of the present disclosure, the content of isobutyl-2-cyanoacrylate as a 2-cyanoacrylate compound from the viewpoint of water resistance and thermal shock resistance under hot and humid conditions in the resulting cured product and heat resistance Is preferably more than 90% by mass and 100% by mass, more preferably 95% to 100% by mass, particularly preferably 100% by mass, based on the total mass of the 2-cyanoacrylate compound .

<<Alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms>>
Alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms can be blended into the composition of the present disclosure for the purpose of improving the heat resistance of the resulting cured product.
Various alkyl-2-cyanoacrylates having an alkyl group having 1 to 3 carbon atoms can be blended, and specific examples include methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, n- Propyl-2-cyanoacrylate, isopropyl-2-cyanoacrylate and the like. These can be used individually by 1 type, and can also use 2 or more types together.
Among these, isopropyl-2-cyanoacrylate and/or ethyl-2-cyanoacrylate are preferable, and ethyl-2-cyanoacrylate is more preferable, from the viewpoint of easily increasing the thermal shock resistance of the resulting cured product.

The content of alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms is relative to the total mass of the 2-cyanoacrylate compound, from the viewpoint of thermal shock resistance and bending resistance in the resulting cured product. , preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% by mass or less, and particularly preferably 20% by mass or more and 60% by mass or less.

<<2-cyanoacrylate having an ether bond in the ester residue>>
The composition of the present disclosure can be blended with 2-cyanoacrylate having an ether bond in the ester residue for the purpose of imparting flexibility related to thermal shock resistance to the resulting cured product. , alkoxyalkyl-2-cyanoacrylates and 2-cyanoacrylates of cyclic alkyl ethers.
The term "ester residue" refers to an atomic group that binds to the oxygen atom of the ester bond in the compound.
Moreover, the 2-cyanoacrylate having an ether bond in the ester residue is preferably a 2-cyanoacrylate having an ether bond in the group that bonds to the oxygen atom of the ester bond.

Specific examples of alkoxyalkyl-2-cyanoacrylates include methoxyethyl-2-cyanoacrylate, ethoxyethyl-2-cyanoacrylate, propoxyethyl-2-cyanoacrylate, isopropoxyethyl-2-cyanoacrylate, butoxyethyl-2 - cyanoacrylate, hexyloxyethyl-2-cyanoacrylate, 2-ethylhexyloxyethyl-2-cyanoacrylate, butoxyethoxyethyl-2-cyanoacrylate, hexyloxyethoxyethyl-2-cyanoacrylate, 2-ethylhexyloxyethoxy ethyl-2-cyanoacrylate, methoxypropyl-2-cyanoacrylate, methoxypropoxypropyl-2-cyanoacrylate, methoxypropoxypropoxypropyl-2-cyanoacrylate, ethoxypropyl-2-cyanoacrylate and ethoxypropoxypropyl-2-cyanoacrylate etc.
Specific examples of 2-cyanoacrylates of cyclic alkyl ethers include tetrahydrofurfuryl-2-cyanoacrylate.
The 2-cyanoacrylates having an ether bond in the ester residue can be used singly or in combination of two or more.

Among these, lower alkoxyethyl-2-cyanoacrylates such as methoxyethyl-2-cyanoacrylate, ethoxyethyl-2-cyanoacrylate and butoxyethyl-2-cyanoacrylate are readily available and excellent in stability. ethoxyethyl-2-cyanoacrylate is particularly preferred.

When the composition of the present disclosure contains a 2-cyanoacrylate having an ether bond in the ester residue, the content of the 2-cyanoacrylate having an ether bond in the ester residue is From the viewpoint of properties, it is preferably more than 0% by mass and 50% by mass or less, more preferably more than 0% by mass and 40% by mass or less, relative to the total mass of the 2-cyanoacrylate compound.

<Thickener>
The coated wire sealing composition of the present disclosure includes a thickening agent.
The thickening agent is not particularly limited as long as it exhibits a thickening effect, but specifically includes polymethyl (meth)acrylate, polybutyl (meth)acrylate, methyl methacrylate and methyl acrylate. copolymers, homopolymers or copolymers of various (meth)acrylates such as copolymers of methyl methacrylate and ethyl acrylate, cellulose derivatives such as hydroxypropyl cellulose and cellulose acetate butyrate, and acrylic rubbers such as polybutyl acrylate. , olefin-acrylic rubber such as ethylene-acrylic elastomer, acrylonitrile butadiene rubber (NBR), butadiene rubber (BR), and the like.
Moreover, it is preferable that the thickener does not have a polar group such as a hydroxyl group or an amino group.
Among them, as a thickener, olefin-acrylic rubber, acrylonitrile-butadiene rubber, cellulose derivative, At least one compound selected from the group consisting of acrylic rubber and butadiene rubber is preferred, at least one compound selected from the group consisting of olefin-acrylic rubber and acrylonitrile-butadiene rubber is more preferred, and olefin- Acrylic rubber is more preferred, and ethylene-acrylic elastomer is particularly preferred.

The weight average molecular weight (hereinafter also referred to as "Mw") of the thickener is 10,000 from the viewpoint of water resistance and cold/hot shock resistance under hot and humid conditions in the resulting cured product, heat resistance, and bending resistance. It is preferably 50,000 or more, more preferably 50,000 or more, still more preferably 100,000 or more and 1,000,000 or less, and particularly preferably 150,000 or more and 500,000 or less.
In the present disclosure, the weight-average molecular weight of the thickener means the value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") under the following conditions into polystyrene.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: 2 TSKgel GMHXL (manufactured by Tosoh Corporation)
Column temperature: 40°C
Eluent: Tetrahydrofuran 1.00 ml/min Detector: RI (differential refractometer)

The thickener is a copolymer containing a structural unit derived from a (meth)acrylic monomer, from the viewpoint of water resistance and cold/hot shock resistance under hot and humid conditions in the resulting cured product, and heat resistance. is preferred.
(Meth)acrylic monomers include (meth)acrylate compounds, (meth)acrylonitrile, (meth)acrylic acid, and (meth)acrylamide compounds. Specific examples of these are preferably (meth)acrylic monomers used in elastomers described later.
Among them, monomer units composed of (meth)acrylate compounds are preferable, and monomer units composed of alkyl (meth)acrylate compounds are more preferable.

Further, the thickener is preferably an elastomer from the viewpoint of water resistance, thermal shock resistance, heat resistance, and bending resistance under hot and humid conditions in the resulting cured product.
The “elastomer” in the present disclosure refers to those having rubber-like elasticity at around room temperature (20° C.±15° C.), or having a dynamic viscoelasticity loss tangent (tan δ) peak of 20° C. or less measured at a frequency of 1 Hz. is not particularly limited as long as it is in
Elastomers having rubber-like elasticity at around room temperature include acrylic acid ester copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene-acrylic acid ester copolymers, acrylonitrile-butadiene copolymers, acrylonitrile- Butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, ethylene-acrylate copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer , polyurethane-based copolymers, polyester-based copolymers, fluorine-based copolymers, polyisoprene-based copolymers, and chloroprene-based copolymers. These may be used individually by 1 type, and may use 2 or more types together.
A core-shell type elastomer can also be used as the elastomer having a dynamic viscoelasticity loss tangent (tan δ) peak of 20° C. or less measured at a frequency of 1 Hz.
In the core-shell type elastomer, the glass transition point (hereinafter also referred to as “Tg”) of the polymer constituting the core and/or shell is preferably 20° C. or lower, more preferably −10° C. or lower.
Examples of the core phase monomer for forming such a polymer include acrylic acid esters, and acrylic acid esters having an alkyl group having 2 to 8 carbon atoms are preferred.
On the other hand, the shell phase forming the outermost layer is not particularly limited as long as it is a polymer component that is compatible with or easily dispersed with the 2-cyanoacrylate compound. Formation is preferred.
Examples of monomers that form glassy polymers include methyl methacrylate and styrene.

Among these elastomers that can be used as thickeners, preferred are monomers whose homopolymers are sparingly soluble in 2-cyanoacrylate compounds, and monomers whose homopolymers are soluble in 2-cyanoacrylate compounds. and a copolymer obtained by copolymerizing a monomer capable of forming a polymer of (excluding the following monomer having a carboxy group). This copolymer has a poorly soluble segment formed by polymerizing a monomer whose homopolymer can be a polymer that is poorly soluble in a 2-cyanoacrylate compound, and a polymer whose homopolymer is soluble in a 2-cyanoacrylate compound. It is preferable to have a soluble segment formed by polymerizing a monomer.

There are no particular restrictions on the monomers that can form a homopolymer that is sparingly soluble in the 2-cyanoacrylate compound, and examples thereof include ethylene, propylene, isoprene, butadiene, chloroprene, 1-hexene and cyclopentene. These monomers may be used alone or in combination of two or more.
The monomer capable of forming the poorly soluble polymer is preferably at least one monomer selected from the group consisting of ethylene, propylene, isoprene, butadiene and chloroprene, and ethylene, propylene, isoprene and butadiene. At least one monomer selected from the group consisting of is more preferable.

Further, the monomer capable of forming a homopolymer soluble in the 2-cyanoacrylate compound is not particularly limited, and examples thereof include acrylic acid ester, methacrylic acid ester, vinyl chloride, vinyl acetate, vinyl ether, styrene and acrylonitrile. , acrylic acid esters and methacrylic acid esters.
Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-acrylate heptyl, n-octyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxyethyl acrylate and ethoxypropyl acrylate; These monomers may be used alone or in combination of two or more.
Furthermore, methacrylic acid esters include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-hexyl methacrylate, and methacrylic acid. Examples include n-heptyl, n-octyl methacrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, ethoxyethyl methacrylate and ethoxypropyl methacrylate. These monomers may be used alone or in combination of two or more.
Moreover, you may use acrylic acid ester and methacrylic acid ester together.

There is no particular limitation on the ratio of the sparingly soluble segment formed by polymerizing the monomer capable of forming the poorly soluble polymer and the soluble segment formed by polymerizing the monomer capable of forming the soluble polymer.
When the sum of the monomer units forming the poorly soluble segment and the monomer units forming the soluble segment is 100 mol%, the amount of the monomer units forming the poorly soluble segment is preferably 5 mol% to 90 mol%. , More preferably 10 mol% to 80 mol%, still more preferably 30 mol% to 80 mol%, particularly preferably 40 mol% to 80 mol%, most preferably 50 mol% to 75 mol% is.
When the sum of the monomer units forming the poorly soluble segment and the monomer units forming the soluble segment is 100 mol%, the amount of the monomer units forming the soluble segment is preferably 10 mol% to 95 mol%, more preferably is 20 mol % to 90 mol %, more preferably 20 mol % to 70 mol %, particularly preferably 20 mol % to 60 mol %, most preferably 25 mol % to 50 mol %.
When the ratio of each segment is within the above range, the copolymer can be appropriately dissolved in the 2-cyanoacrylate compound, and a composition having both high shear adhesive strength and the like and excellent durability. can do.
The ratio of each segment can be calculated from the integral value of protons measured by proton nuclear magnetic resonance spectroscopy (hereinafter referred to as “ ¹ H-NMR”).

Furthermore, among the above elastomers that can be used as thickeners, particularly preferred are monomers whose homopolymers are sparingly soluble in 2-cyanoacrylate compounds, and monomers whose homopolymers are soluble in 2-cyanoacrylate compounds. and a monomer having a carboxyl group. In this copolymer, a monomer having a carboxy group may be copolymerized in a small amount.
Monomers having a carboxy group are not particularly limited either, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and cinnamic acid. These monomers may be used alone or in combination of two or more.
As the monomer having a carboxy group, acrylic acid and methacrylic acid are preferably mentioned, and either one of them may be used or both of them may be used.
A segment having a carboxy group obtained by copolymerizing the monomer having a carboxy group becomes a segment soluble in a highly hydrophilic 2-cyanoacrylate compound. When the elastomer is a copolymer having a carboxyl group, a composition exhibiting superior adhesion durability is provided.

The proportion of segments having carboxy groups is also not particularly limited.
A segment having a carboxy group is formed when the sum of the monomer units forming the poorly soluble segment, the monomer units forming the soluble segment, and the monomer units forming the segment having a carboxy group is 100 mol%. The amount of monomer units is preferably 0.1 mol % to 5 mol %, more preferably 0.3 mol % to 4 mol %, still more preferably 0.4 mol % to 3 mol %, and particularly preferably is 0.5 mol % to 2.5 mol %, most preferably 0.5 mol % to 2.3 mol %.
When the ratio of the segment having a carboxy group is within the above range, the curability is excellent, and the resulting cured product has excellent hot water resistance.
The ratio of segments having a carboxy group can be measured by potentiometric titration or indicator titration according to JIS K0070 (1992).

A monomer whose homopolymer can be a poorly soluble polymer in a 2-cyanoacrylate compound, and a monomer whose homopolymer can be a soluble polymer in a 2-cyanoacrylate compound (however, the above monomer having a carboxy group Examples of copolymers obtained by copolymerizing ethylene/methyl acrylate copolymer, ethylene/methyl acrylate/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene /vinyl acetate copolymer, butadiene/methyl acrylate copolymer, butadiene/acrylonitrile copolymer, butadiene/acrylonitrile/acrylate copolymer, and butadiene/styrene/acrylonitrile/methyl acrylate copolymer, etc. be able to. Among them, an ethylene/methyl acrylate copolymer or an ethylene/methyl acrylate/butyl acrylate copolymer is particularly preferable.
Further, a copolymer obtained by polymerizing a monomer used in each of the above copolymers and a monomer having a carboxy group such as acrylic acid and/or methacrylic acid, such as ethylene/acrylic acid Methyl/acrylic acid copolymers, ethylene/methyl acrylate/methacrylic acid copolymers, ethylene/methyl acrylate/butyl acrylate/acrylic acid copolymers, and ethylene/methyl acrylate/butyl acrylate/methacrylic acid copolymers A polymer or the like can also be used.
These copolymers may be used alone or in combination of two or more. A copolymer not copolymerized with a monomer having a carboxy group and a monomer having a carboxy group may be used in combination with a copolymer obtained by copolymerizing.

Among them, the thickening agent is selected from the group consisting of ethylene, propylene, isoprene and butadiene from the viewpoint of water resistance, cold/hot shock resistance, heat resistance and bending resistance under high temperature and high humidity conditions in the resulting cured product. It is preferably a copolymer obtained by copolymerizing at least one monomer and a (meth)acrylate compound, and at least one selected from the group consisting of ethylene, propylene, isoprene and butadiene. More preferably, it is a copolymer obtained by copolymerizing at least a monomer, a (meth)acrylate compound, and a monomer having a carboxy group.

A thickener may be used individually by 1 type, and may use 2 or more types together.
The content of the thickener is 100 parts by mass of the content of the 2-cyanoacrylate compound from the viewpoint of water resistance, cold/hot shock resistance, heat resistance, and bending resistance under hot and humid conditions in the resulting cured product. is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 12 parts by mass, 2 parts by mass parts to 9 parts by mass are particularly preferred.

<Phthalic anhydride derivative represented by formula (1)>
From the viewpoint of water resistance and thermal shock resistance under high-temperature and high-humidity conditions in the resulting cured product, and heat resistance, the coated wire sealing composition of the present disclosure has a phthalic anhydride represented by the following formula (1). Preferably, it further contains a derivative.

In formula (1), each R ¹ independently represents an alkyl group, an acyl group, an acyloxy group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a chlorine atom, a bromine atom or an iodine atom, and n is 1 to 4. represents an integer of

Each R ¹ in formula (1) is independently an alkyl group having 1 to 4 carbon atoms, a chlorine atom or a bromine atom from the viewpoints of solubility in a 2-cyanoacrylate compound, stability of the composition and curability. is preferred, and a methyl group or a bromine atom is more preferred.
Also, n is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Specific examples of the phthalic anhydride derivative represented by the formula (1) include 3-methylphthalic anhydride, 4-methylphthalic anhydride, 4-tert-butylphthalic anhydride, and 3-hydroxyphthalic anhydride. substance, 4-hydroxyphthalic anhydride, 3-acetoxyphthalic anhydride, 4-benzoylphthalic anhydride, 4-phenylphthalic anhydride, 4-phenoxycarbonylphthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3-bromophthalic anhydride, 4-bromophthalic anhydride, 3-iodophthalic anhydride, 4-iodophthalic anhydride, 3,4-dichlorophthalic anhydride, 3,5-dichloro Phthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4-dibromophthalic anhydride, 3,5-dibromophthalic anhydride, 3,6-dibromo Phthalic anhydride, 4,5-dibromophthalic anhydride, 3,4-diiodophthalic anhydride, 3,5-diiodophthalic anhydride, 3,6-diiodophthalic anhydride, 4,5-diiodophthalic anhydride , 4-bromo-5-iodophthalic anhydride, 3,4,5-trichlorophthalic anhydride, 3,4,6-trichlorophthalic anhydride, 3,4,5-tribromophthalic anhydride, 3 ,4,6-tribromophthalic anhydride, 3,4,5-triiodophthalic anhydride, 3,4,6-triiodophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride and tetraiodophthalic anhydride.

The content of the phthalic anhydride derivative represented by the formula (1) is based on the total mass of the composition from the viewpoint of water resistance and cold/heat shock resistance under high temperature and high humidity conditions in the resulting cured product, and heat resistance. On the other hand, it is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 4% by mass, and particularly preferably 0.1% by mass to 3% by mass.

<Plasticizer>
The coated wire sealing composition of the present disclosure preferably further contains a plasticizer from the viewpoint of water resistance, thermal shock resistance, heat resistance, and bending resistance under high-temperature and high-humidity conditions in the resulting cured product.
As a plasticizer, as a thickener, in particular, a copolymer containing a large amount of monomers capable of forming the poorly soluble polymer, that is, a copolymer having many poorly soluble segments (e.g., a proportion of the poorly soluble segment is 65 mol % or more copolymer), the solubility of the copolymer can be improved by containing an appropriate amount.
Plasticizers include acetyl triethyl citrate, acetyl tributyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and diheptyl phthalate. , dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl) camphorate, 2-ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, caproic acid triglyceride, 2-ethylhexyl benzoate, and dipropylene glycol dibenzoate.
Among these, acetyl tributyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol, because of their good compatibility with 2-cyanoacrylate compounds and high plasticization efficiency. At least one compound selected from the group consisting of dibenzoates is preferred.

Only one plasticizer may be used, or two or more plasticizers may be used in combination.
The content of the plasticizer is not particularly limited, but from the viewpoint of water resistance and cold/hot shock resistance under hot and humid conditions in the resulting cured product, heat resistance, and bending resistance, the content of the 2-cyanoacrylate compound It is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and 0.01 to 7 parts by mass with respect to 100 parts by mass. is particularly preferred.

<(Meth)acrylate having two or more (meth)acryloyloxy groups>
A (meth)acrylate having two or more (meth)acryloyloxy groups can be blended into the composition of the present disclosure for the purpose of imparting heat resistance and flexibility to the resulting cured product. Various (meth)acrylates having two or more (meth)acryloyloxy groups can be used, but the stability of the composition and the adhesiveness of the 2-cyanoacrylate compound are unlikely to be affected. , amino groups and the like are preferred. Although the upper limit of the number of (meth)acryloyloxy groups is not particularly limited, it can be, for example, 6 or less.

Examples of (meth)acrylates having two (meth)acryloyloxy groups include ethylene glycol di(meth)acrylate [a commercially available product is NK Ester 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. Same below], polyethylene glycol di(meth)acrylate [acrylate: Aronix M-240 (manufactured by Toagosei Co., Ltd.), etc., methacrylate: NK Ester 4G, 9G, 14G, 23G (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. ], tripropylene glycol di(meth)acrylate [Aronix M-220 (manufactured by Toagosei Co., Ltd.), etc.], neopentyl glycol di(meth)acrylate [light acrylate NP-A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.] , 1,6-hexanediol di(meth)acrylate [light acrylate 1.6HX-A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.], ethylene oxide-modified di(meth)acrylate of bisphenol A [Aronix M-211B (Toagosei Co., Ltd.), etc.], 3-(meth)acryloyloxyglycerin mono(meth)acrylate [light acrylate G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), etc.], hydrogenated dicyclopentadienyl di(meth)acrylate [Light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.], polyester (meth)acrylate represented by the following formula (A) [KAYARAD HX-220, 620 (manufactured by Nippon Kayaku Co., Ltd.), etc.], Urethane (meth)acrylate [Aronix M-1100, 1200 (manufactured by Toagosei Co., Ltd.), etc.], and bisphenol A-diepoxy-(meth)acrylic acid adduct [Viscoat #540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) ) etc.] and the like.

In formula (A), the average value of mA+nA is 2-4.

Examples of (meth)acrylates having three (meth)acryloyloxy groups include pentaerythritol tri(meth)acrylate [Aronix M-305 (manufactured by Toagosei Co., Ltd.), etc.], trimethylolpropane tri(meth)acrylate [ Aronix M-309 (manufactured by Toagosei Co., Ltd.), etc.], trimethylolpropane propylene oxide-modified tri(meth)acrylate [Aronix M-321 (manufactured by Toagosei Co., Ltd.), etc.], trimethylolpropane tri(meth)acrylate [NK Ester A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.] and the like.
Examples of (meth)acrylates having four (meth)acryloyloxy groups include pentaerythritol tetra(meth)acrylate [Aronix M-450 (manufactured by Toagosei Co., Ltd.), etc.], and five (meth)acryloyl groups. Examples of (meth)acrylates having an oxy group include dipentaerythritol penta(meth)acrylate, and examples of (meth)acrylates having six (meth)acryloyloxy groups include dipentaerythritol hexa(meth)acrylate [KAYARAD DPHA ( Nippon Kayaku Co., Ltd.)], dipentaerythritol propylene oxide-modified hexa(meth)acrylate [KAYARAD DPCA-20, 30, 60, 1209; Nippon Kayaku Co., Ltd.].
(Meth)acrylates having two or more (meth)acryloyloxy groups may be used singly or in combination of two or more.

Among these, acrylates, polyethylene glycol di(meth)acrylates and/or polypropylene glycol di(meth)acrylates represented by formula (1) are preferably used because the resulting cured product has appropriate flexibility.

The content of (meth)acrylate having two or more (meth)acryloyloxy groups is 50% by mass or less with respect to the total mass of the composition, from the viewpoint of water resistance and thermal shock resistance of the resulting cured product. It is preferably 1% by mass to 35% by mass, more preferably 1% by mass to 20% by mass, and particularly preferably 1% by mass to 15% by mass.

<Polymerization initiator>
The composition of the present disclosure may contain a polymerization initiator.
In particular, in the embodiment in which the (meth)acrylate component having two or more (meth)acryloyloxy groups is added to the composition of the present disclosure, the (meth)acrylate component having two or more (meth)acryloyloxy groups is polymerized. It is preferable to incorporate a radical polymerization initiator that promotes the
Moreover, as a polymerization initiator, a thermal polymerization initiator is preferably mentioned, and a thermal radical polymerization initiator is more preferably mentioned.
Examples of radical polymerization initiators include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides such as di-t-butyl hydroperoxide, and diacyl peroxides and peroxydicarbonates. Organic peroxides can be mentioned.
From the viewpoint of storage stability, the content of the polymerization initiator is preferably 0.1% by mass to 1% by mass, and 0.3% by mass to 0.6% by mass, based on the total mass of the composition. It is more preferable to have

<Other ingredients>
The composition of the present disclosure may contain other components in addition to the above components. Other components include known additives, and specific examples include stabilizers, polymerization accelerators, dyes, pigments, and diluents.
The content of other components is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, relative to the total mass of the composition.

Other components preferably include stabilizers.
As the stabilizer, known polymerization inhibitors and polymerization inhibitors can be used, and examples thereof include hydroquinone and sulfurous acid gas.

Moreover, as other components, a polymerization accelerator is preferably mentioned, and an anionic polymerization accelerator is more preferably mentioned.
Examples of anionic polymerization accelerators include polyalkylene oxides and derivatives thereof, crown ethers and derivatives thereof, silacrown ethers and derivatives thereof, and calixarene derivatives.

In addition to these, dyes, pigments, diluents, fillers (silica particles, etc.) and the like can also be blended.

<How to use>
The coated wire sealing composition of the present disclosure includes a single conductor covered with an insulating coating, a stranded wire consisting of several conductors covered with an insulating coating, and the like. It can be used for various coated electric wires.
Specifically, by coating the exposed portion of the covered wire and its periphery with the composition of the present disclosure and curing the composition of the present disclosure, the exposed portion of the covered wire can be sealed.
As the coating method, various methods can be employed, for example, a method of applying or injecting the composition of the present disclosure to the exposed portion of the coated wire and its surroundings, or a method of coating the exposed portion of the coated wire and its surroundings with the composition of the present disclosure. A method of immersing in
As a method for curing the coated composition of the present disclosure, a method commonly used for cyanoacrylate adhesives can be applied, and it is usually cured by moisture in the air when left to stand, and the curing speed of the composition is When it is not sufficient, the coated portion is treated with an anionic polymerization initiator such as an amine such as N,N'-dimethylaniline, triethanolamine [commercially available products include aa accelerator (manufactured by Toagosei Co., Ltd.)], etc. can also be sprayed to accelerate curing.
Among the compositions of the present disclosure, the low-viscosity composition is suitable because it easily penetrates the gap between the conductor and the coating, can sufficiently seal the coated wire, and has excellent workability. It is preferable to employ a method of soaking the exposed portion of the wire and its surroundings with the composition of the present disclosure.
More specifically, the stripped conductor of the coated wire is crimped with a specific component, and the exposed portion of the coated wire and its periphery are immersed in the composition of the present disclosure. The time for immersing the exposed portion of the coated wire and its surroundings may be appropriately selected according to the type of composition used, but it is usually about several seconds to 30 seconds.
In this method, if the curing speed is too fast and the composition does not sufficiently penetrate into the gap between the wire and the coating, a composition containing an increased proportion of the polymerization inhibitor may be used.

(coated wire)
The covered wire of the present disclosure comprises a cured product of the covered wire sealing composition of the present disclosure.
The coated wire sealing composition of the present disclosure can be suitably used for sealing exposed portions of a coated wire, particularly at the end of a coated wire, and electrically connecting two or more coated wires. It can be used more preferably for sealing the exposed portion of the connected electric wire.
The wire-exposed portion may be an end or an intermediate portion of the covered wire.
In addition, the coated wire sealing composition of the present disclosure can also be suitably used for sealing connection portions between coated wires and other members (connectors, terminals, protectors, molding tools, fixtures, substrates, etc.). can.

The electric wire in the covered electric wire is not particularly limited, and known electric wires can be used. Examples of the material of the electric wire include copper, aluminum, and alloys thereof.
The electric wire may be a single wire or a multi-strand wire, but preferably a multi-strand wire.
A coating material for the coated electric wire is not particularly limited, and a known coating material can be used.
The covering material is preferably an insulating material.
Moreover, the coating material preferably contains a resin, and more preferably contains a thermoplastic resin.
The cross-sectional shape, length, thickness of the coating, and the like of the covered electric wire are not particularly limited and can be appropriately selected.
Preferred examples of the covered electric wire of the present disclosure include wire harnesses for automobiles, home electric appliances, OA equipment, and the like, and particularly preferred examples are wire harnesses for automobiles.

EXAMPLES The present invention will be specifically described below based on examples. It should be noted that the present invention is not limited by these examples. Further, hereinafter, "parts" and "%" mean "mass parts" and "mass%", respectively, unless otherwise specified.

<How to measure the suction length>
After the tip of a capillary tube with an inner diameter of 1.05 mm and a length of 120 mm was immersed in a composition bath liquid with a depth of 30 mm for 2 seconds and pulled out, the longitudinal direction of the capillary tube was oriented horizontally with respect to the direction of gravity. The sucking length was measured when it was left standing for 24 hours in a state where it was installed so as to be
In addition, the above-mentioned suction length was measured at 23° C.±0.5° C., and a capillary tube made of borosilicate glass was used.

<Method for measuring viscosity at 25°C>
The viscosity of the composition was measured under the following conditions using a TVE-20H viscometer (salt water/flat plate method, manufactured by Toki Sangyo Co., Ltd.), which is an E-type viscometer (cone plate viscometer). .
-Measurement condition-
Cone shape: angle 1°34′, radius 24 mm
Temperature: 25°C ± 0.5°C

<Method for measuring storage elastic modulus at 80°C of cured product of coated wire sealing composition>
Anton Paar MCR 301 was used and measured as follows.
After applying a curing accelerator solution (5 wt% N,N'-dimethylparatoluidine ethanol solution) to both sides of the upper and lower parallel plates and drying, apply an appropriate amount of the composition to the lower plate, and immediately attach the upper plate. was lowered. After that, it was left at 25° C. for 2 hours, and the storage modulus at 80° C. was measured under the conditions of 0.1% strain, 1 Hz frequency, 2° C./min heating rate, and 300 μm initial gap.

(Examples 1 to 24 and Comparative Examples 1 to 10)
In Examples 1 to 3, 5 to 11, and 13 to 24, and Comparative Examples 6 to 10, the compounds having the compositions shown in Table 1 were mixed in a conventional manner to prepare coated wire seal compositions.
In Example 4, Example 12, and Comparative Examples 1 to 5, 1 part by mass of di-t-butyl hydroperoxide (perbutyl Z (manufactured by NOF Corporation) was mixed in a conventional manner to prepare a composition for a coated wire seal.

<Evaluation>
The following evaluations were performed on the obtained coated wire sealing composition. Those results are shown in Table 2.

－Electric wire sealability test (moisture heat test, thermal shock test and heat resistance test)－
Peel off 15 mm of the covered polyvinyl chloride from the tip of the soft polyvinyl chloride covered conductor (diameter of the conductor: 2.5 mm diameter of 30 copper wires twisted together, 3.5 mm outer diameter of the covered PVC) and 30 mm from the tip was immersed in the coated wire sealing composition for about 2 seconds, and then cured and hardened in an atmosphere of 23° C. and 50% humidity for 1 day or longer.
A wire sealability test was conducted on the sealed coated wires which were exposed for 50 hours in a moist heat environment of 80° C. and 95% RH (humid heat test).
On the other hand, the above sealed insulated wire was subjected to thermal shock for 100 cycles from −40° C. for 30 minutes to 120° C. for 30 minutes, and then subjected to a wire sealability test in the same manner as above (thermal shock test).
Furthermore, the above-mentioned sealed covered electric wire was also subjected to an electric wire sealing property test (heat resistance test) in the same manner as described above for those exposed to 120° C. for 96 hours.
In the wire sealability test, compressed air having a predetermined pressure shown below was sent from the unsealed side of the covered wire, and the tip of the covered wire was immersed in water to check for air leakage.
Evaluation was made from A to E depending on the airtight pressure at which air leakage occurred.
A: Airtight pressure 1.0 kg/cm ² or more B: Airtight pressure 0.8 kg/cm ² or more and less than 1.0 kg/cm ² C: Airtight pressure 0.6 kg/cm ² or more and less than 0.8 kg/cm ² D : Airtight pressure 0.4 kg/cm ² or more and less than 0.6 kg/cm ² E: Airtight pressure less than 0.4 kg/cm ²

- Bending test (bending resistance test) -
Based on the bending resistance described in JIS K5600-5-1 (1999), the sealed coated wires were measured one by one using the following equipment, and visually evaluated according to the following evaluation criteria.
<<Test equipment>>
Cylindrical mandrel bending tester manufactured by All Good Co., Ltd. Mandrel diameter: 2mmΦ
<<Evaluation Criteria>>
A: No cracks and no cracks B: No cracks, only cracks C: Both cracks and cracks

Each numerical value in the columns other than the additive (phthalic anhydride derivative represented by the formula (1)) and the initiator in Table 1 represents the content mass ratio in the composition, and the numerical value in the additive and initiator columns is , represents the content (ppm) relative to the total mass of the composition. There was no photocurable resin composition with an uncured interior (dark area).

Further, details of abbreviations in Table 1 are shown below.
KAYARAD HX-620: acrylate compound represented by the formula (A), mA + nA = 4, manufactured by Nippon Kayaku Co., Ltd. KAYARAD HX-220: acrylate compound represented by the formula (A), mA + nA = 2, Japan Kayaku Co., Ltd. M-305: Toagosei Co., Ltd. Aronix M-305 (pentaerythritol tri (meth) acrylate)
Vamac G: ethylene acrylic elastomer (ethylene-methyl acrylate-acrylic acid copolymer), manufactured by Du Pont, Mw = 260,000 Vamac LT: ethylene acrylic elastomer (ethylene-methyl acrylate-butyl acrylate-acrylic acid copolymer), Du Pont, Mw = 270,000 NIPOL 1072: Acrylonitrile-butadiene rubber, Nippon Zeon Co., Ltd., Mw = 160,000 CAB: Cellulose acetate butyrate, Eastman Chemical Japan, Mw => 70,000 BR-60: Acrylic resin, Mw = 70,000 ATBC: acetyl tributyl citrate DINP: diisononyl phthalate DIDP: diisodecyl phthalate 4-BrPA: 4-bromophthalic anhydride 4-MePA: 4-methylphthalic anhydride

As shown in Tables 1 and 2, the coated wire sealing compositions of Examples 1 to 24 are superior to the compositions of Comparative Examples 1 to 10 in water resistance and resistance to high temperature and high humidity in the resulting cured products. It has both thermal shock resistance and excellent heat resistance of the resulting cured product.
Further, as shown in Tables 1 and 2, the coated wire seal compositions of Examples 1 to 24 are excellent in bending resistance of the cured products obtained.

The disclosure of Japanese Patent Application No. 2019-176677 filed on September 27, 2019 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

The coated wire sealing composition of the present disclosure is excellent in workability, and the cured product thereof can maintain wire sealing properties even under severe conditions such as high temperature and high humidity and under cold/heat cycle conditions. It can be widely used as a wire sealant for wiring in various electrical systems such as home electric appliances and OA equipment.

Claims (16)

A 2-cyanoacrylate compound containing 10% by mass or more of an alkyl-2-cyanoacrylate having an alkyl group having 4 or more carbon atoms with respect to the total mass of the 2-cyanoacrylate compound;
and a thickening agent,
The thickener has a weight average molecular weight of 150,000 or more and 270,000 or less,
The content of the thickener is 2 parts by mass to 9 parts by mass with respect to 100 parts by mass of the content of the 2-cyanoacrylate compound,
Viscosity at 25 ° C. is 20 mPa s to 120 mPa s,
A composition for coated wire sealing. 2. The coated wire sealing composition according to claim 1 , wherein the thickener is a copolymer containing monomer units composed of (meth)acrylic monomers. The coated wire sealing composition according to claim 1 or 2 , wherein the thickener is an elastomer. The tip of a capillary tube having an inner diameter of 1.05 mm and a length of 120 mm was immersed in the bath liquid of the coated wire sealing composition having a depth of 30 mm for 2 seconds and then pulled out, and then the longitudinal direction of the capillary tube was oriented in the direction of gravity. The coated wire seal according to any one of claims 1 to 3 , wherein the suction length when left standing for 24 hours in a state of being horizontally set is 7 mm or more and 35 mm or less. Composition. 5. The storage elastic modulus at 80° C. of the cured product of the coated wire seal composition is 9.0×10 ⁵ Pa or more and 1.5×10 ⁸ Pa or less. 3. The composition for coated electric wire sealing according to . The 2-cyanoacrylate compounds include 2-octyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, n-octyl-2-cyanoacrylate, n-hexyl-2-cyanoacrylate, n-butyl-2- The coated wire sealing composition according to any one of claims 1 to 5 , which is at least one compound selected from the group consisting of cyanoacrylate and isobutyl-2-cyanoacrylate. Claims 1 to 6 , wherein the 2-cyanoacrylate compound contains an alkyl-2-cyanoacrylate having an alkyl group having 1 to 3 carbon atoms and/or a 2-cyanoacrylate having an ether bond in the ester residue. The coated wire sealing composition according to any one of claims 1 to 3. The 2-cyanoacrylate compound contains an alkyl-2-cyanoacrylate having an alkyl group with 1 to 3 carbon atoms,
Claims 1 to 9, wherein the content of the alkyl-2-cyanoacrylate having an alkyl group with 1 to 3 carbon atoms is 10% by mass or more and 90% by mass or less with respect to the total mass of the 2-cyanoacrylate compound. The coated wire sealing composition according to claim 7 . The 2-cyanoacrylate compound contains a 2-cyanoacrylate having an ether bond in the ester residue,
Any one of claims 1 to 8 , wherein the content of the 2-cyanoacrylate having an ether bond in the ester residue is more than 0% by mass and 50% by mass or less with respect to the total mass of the 2-cyanoacrylate compound. 2. The coated electric wire sealing composition according to claim 1. 2. The thickener is a copolymer obtained by copolymerizing at least one monomer selected from the group consisting of ethylene, propylene, isoprene and butadiene with a (meth)acrylate compound. The coated wire sealing composition according to any one of claims 9 to 9. The thickener is a copolymer obtained by copolymerizing at least one monomer selected from the group consisting of ethylene, propylene, isoprene and butadiene, a (meth)acrylate compound, and a monomer having a carboxy group. The coated wire sealing composition according to any one of claims 1 to 10 , which is a polymer. The coated wire sealing composition according to any one of claims 1 to 11 , further comprising a phthalic anhydride derivative represented by the following formula (1).

In formula (1), each R ¹ independently represents an alkyl group, an acyl group, an acyloxy group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a chlorine atom, a bromine atom or an iodine atom, and n is 1 to 4. represents an integer of The coated wire sealing composition according to any one of claims 1 to 12 , further comprising a plasticizer. 14. The coated wire sealing composition according to claim 13 , wherein the content of said plasticizer is 0.01 to 10 parts by mass with respect to 100 parts by mass of said 2-cyanoacrylate compound. (Meth) further comprising a (meth) acrylate having two or more acryloyloxy groups,
Claims 1 to 3, wherein the content of the (meth)acrylate having two or more (meth)acryloyloxy groups is 1% by mass or more and 35% by mass or less with respect to the total mass of the coated wire sealing composition. Item 15. The coated wire sealing composition according to any one of Items 14-14 . A coated wire comprising a cured product of the coated wire sealing composition according to any one of claims 1 to 15 .