JP2914794B2 - Adhesive composition for heat resistant resin lining - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for a heat-resistant resin lining, and more particularly, to a heat-resistant synthetic resin such as a chlorinated vinyl chloride resin, for example, on the inner surface of a metal tube such as a steel tube and / or the like. Also, the present invention relates to a heat-resistant resin-lined adhesive composition that can be suitably used when lining the outer surface, and a heat-resistant synthetic resin-lined metal tube obtained therefrom.

[0002]

2. Description of the Related Art Resin-lined metal pipes in which the inner surface of a metal pipe such as a steel pipe is lined with, for example, vinyl chloride resin, prevent corrosion of the inner surface of the metal pipe by a corrosive fluid and prevent contamination of the inner surface of the metal pipe by rust. Widely used for the purpose. In general, a method for manufacturing such an inner surface lining metal pipe is to insert a synthetic resin pipe such as a vinyl chloride pipe into the metal pipe, introduce compressed air into the pipe, press the synthetic resin pipe to the inner surface of the metal pipe, and appropriately pressurize the pipe. The lining is firmly bonded with a special adhesive. Such an adhesive is arbitrarily selected and lined depending on the type of the metal tube to be used.

[0003] Various adhesives are known for the lining of the inner surface (or outer surface) of the metal tube as described above, and are appropriately used depending on the material of the metal tube and the type of synthetic resin to be used. Typically, a vinyl chloride resin-lined steel pipe is made of, for example, an ethylene-vinyl acetate copolymer, polyamide, polyester, or a synthetic rubber-based hot melt adhesive, and furthermore, a styrene-butadiene-styrene triblock copolymer. An adhesive comprising a cumarone-indene resin and a terpene resin or a terpene phenol resin further blended with the resin has been proposed (JP-A-52-120781 and JP-A-52-120781).
No. 1202072).

However, in recent years, the demand for heat-resistant resin-lined metal tubes suitable for transporting high-temperature fluids, in which a heat-resistant synthetic resin such as chlorinated vinyl chloride resin is lined on the inner surface of a metal tube such as a steel tube, has been increasing. Therefore, development of an adhesive suitable for manufacturing such a lining tube is desired.

[0005]

Accordingly, the present invention is excellent in various stability as an adhesive composition suitable for heat-resistant resin lining of a metal tube, and has a high adhesive strength by thermosetting, particularly An object of the present invention is to develop a heat-resistant resin lining adhesive composition that can exhibit excellent heat-resistant adhesive strength and practical durability.

[0006]

According to the present invention, (A)
An epoxy resin mixture comprising (A ₁ ) 40 to 95% by weight of a liquid epoxy resin and (A ₂ ) 60 to 5% by weight of a non-liquid epoxy resin
100 parts by weight (provided that the sum of (A ₁ ) and (A ₂ ) is 100% by weight), 5 to 150 parts by weight of (B) acrylonitrile-butadiene copolymer, and (C) epoxy group There is provided an adhesive composition for a heat-resistant resin lining, comprising as essential components 0 to 50 parts by weight of an acrylic resin and 1 to 10 parts by weight of a (D) curing agent.

Further, according to the present invention, the component (A),
There is provided a heat-resistant synthetic resin-lined metal tube obtained by bonding a heat-resistant synthetic resin to an inner surface and / or an outer surface of a metal tube using an adhesive composition comprising (B), (C) and (D).

Hereinafter, the present invention will be described in detail. The adhesive composition for a heat-resistant resin lining of the present invention contains an epoxy resin mixture (A) composed of a liquid epoxy resin (A ₁ ) and a non-liquid epoxy resin (A ₂ ) as a main component.

In the present invention, the liquid epoxy resin (A ₁ ) refers to a liquid epoxy resin (A ₁ ) which contains substantially no diluent such as an organic solvent.
A liquid epoxy resin at room temperature (about 20 ° C.) refers to an epoxy resin, and a non-liquid epoxy resin (A ₂ ) refers to an epoxy resin other than the liquid epoxy resin (A ₁ ). Such non-liquid epoxy resin
Examples of (A ₂ ) include a wax, a solid, a flake, a powder and a solution thereof in an organic solvent.

The non-liquid epoxy resin (A ₂ ) in the present invention
Is used in the range of 5 to 70% by weight, preferably 8 to 60% by weight, based on 100% by weight of the epoxy resin mixture (A). 70% by weight of non-liquid epoxy resin (A ₂ )
Above, the compatibility and blending stability of the epoxy resins (A ₁ ) and (A ₂ ), the acrylonitrile-butadiene copolymer (B), and the acrylic resin (C) having an epoxy group optionally blended. And the heat-resistant adhesive strength and practical durability of the obtained adhesive composition may be insufficient. On the other hand, if the amount is less than 5% by weight, the obtained adhesive composition This is not preferable because the adhesive strength, heat-resistant adhesive strength and practical durability of the product may be insufficient.

The type of epoxy resin used as the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ) in the present invention is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin And bisphenol type epoxy resins such as bisphenol AD type epoxy resin and hydrogenated bisphenol A type epoxy resin. In addition to these, for example, novolak-type epoxy resins such as phenol novolak-type epoxy resin and cresol novolak-type epoxy resin; for example, glycidyl alkyl ether-based epoxy resins such as polyalkylene polyol (such as neopentyl glycol) and polyglycidyl ether; , Tetraglycidyldiaminodiphenylmethane, triglycidyl-
Glycidylamine-based epoxy resins such as p-aminophenol, triglycidyl-m-aminophenol, and tetraglycidyl-m-xylenediamine; for example, glycidyl ester-based epoxy such as diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate Resins; cyclic aliphatic epoxy resins such as vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate ;
For example, epoxy resins such as triglycidyl isocyanurate and glycidyl glycidoxyalkylhydantoin can be used. Further, halides of these epoxy resins; epoxy group-containing resins obtained by reacting these epoxy resins with polybasic acids or polyester polycarboxylic acids; polyglycidyl esters of polyester polycarboxylic acids; polyglycidyl ethers of polyester polyols; Various epoxy resins can be exemplified.

Among the above epoxy resins, bisphenol A type epoxy resins and novolak type epoxy resins are preferably used from the viewpoints of easy availability and good adhesive properties of the obtained adhesive composition. Use is particularly preferred.

In the present invention, if necessary, from the viewpoint of workability in using the obtained adhesive composition, the viscosity may be lowered without lowering the solid content of the adhesive composition. Thus, an epoxy resin reactive diluent can be compounded and used.

Examples of such an epoxy resin reaction diluent include monofunctional diluents such as epichlorohydrin, butyl glycidyl ether, octylene oxide, styrene oxide and phenyl glycidyl ether; for example, diglycidyl ether and 2-glycidyl phenyl Glycidyl ether, vinylcyclohexene diepoxide, 3,4-epoxy-6-methylcyclohexenemethyl-3 ', 4'-epoxy-6'-methylcyclohexenecarboxylate, 3,4-epoxycyclohexenemethyl-3', 4'- Bifunctional diluents such as epoxycyclohexene carboxylate; trifunctional diluents such as 2,6-diglycidylphenol glycidyl ether; and the like.

These are, for example, Khajura E, GE-10
0, BGE, YED-111, YED-122, YED-205 [(trade name): Yuka Shell Epoxy Co., Ltd.], DYO26, XN1034
[(Trade name): Nippon Ciba Geigy Co., Ltd.], Epolite 400E, Epolite 400P, Epolite 4000, Epolite 40E, Epolite 70P, Epolite 1500NP [(trade name): manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.], etc. ing.

The amount of such a reactive diluent is based on 100 parts by weight of the epoxy resin mixture (A) [total amount of the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ )].
For example, the amount may be 0 to 30 parts by weight, preferably about 0 to 20 parts by weight. When the amount is 30 parts by weight or less, the adhesive strength and the heat-resistant adhesive strength of the obtained adhesive composition are not insufficient, so that it is preferable.

Further, these epoxy resin reaction diluents include:
From the viewpoint of toxicity and the like, the epoxy resin may be blended in advance. Epoxy resins containing such a reaction diluent include, for example, Epicoat 815 and Epicoat 815.
815XA, Epicoat 819 (trade name: Yuka Shell Epoxy Co., Ltd.), Araldide GY257, Araldide GY
1252JP [(trade name): manufactured by Nippon Ciba Geigy Co., Ltd.] and the like, which are mixed with a liquid epoxy resin.

The adhesive composition for a heat-resistant resin lining of the present invention is prepared by adding acrylonitrile to an epoxy resin mixture (A) comprising the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ). It comprises butadiene copolymer (B) as an essential component.

As such an acrylonitrile-butadiene copolymer (hereinafter sometimes abbreviated as NBR) (B), a monomer mainly composed of butadiene and acrylonitrile is used, for example, an aqueous emulsion copolymer at elevated pressure. Can be exemplified.

The amount of butadiene to be used is generally 50 to 100% by weight of the total of the monomer components constituting NBR (B).
It may be 85% by weight, preferably 65-75% by weight. When the amount is 85% by weight or less, the compatibility with the epoxy resin is excellent, and the resulting adhesive composition has excellent heat-resistant adhesive strength, which is preferable. On the other hand, the amount used is 50% by weight. Above, for example, methyl ethyl ketone, and the like, since it has excellent solubility in an organic solvent that can be suitably used in the present invention as described below, an adhesive composition having an appropriate viscosity and solid content can be easily produced. preferable.

The amount of acrylonitrile used is NB
It is generally 15 to 50% by weight, preferably 25 to 35% by weight, based on 100% by weight of the total of the monomer components constituting R (B). When the amount is 15% by weight or more, the compatibility with the epoxy resin is excellent, and the resulting adhesive composition has excellent heat-resistant adhesive strength, so that it is preferable. When the content is not more than% by weight, the solubility in an organic solvent as described below, which can be suitably used in the present invention, is excellent, and thus it is preferable.

In the emulsion copolymerization, a part of butadiene is replaced with another conjugated diolefin monomer.
For example, isoprene, chloroprene, and the like, and part of acrylonitrile can be replaced with another vinyl cyanide monomer, such as methacrylonitrile.

NBR that can be used in the present invention
In addition to these conjugated diolefin-based monomers and vinyl cyanide monomers, other comonomers copolymerizable with these monomers can be used as necessary.

These comonomers include, for example, (a)
(B) carboxyl group-containing monomer; (c) monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule And a monomer other than the carboxyl group-containing monomer; and the like.

Examples of the monomer (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, and n-octyl. C ₁ -C ₂₀ alkyl ester monomers of acrylic acid such as acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, stearyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-
Butyl methacrylate, n-hexyl methacrylate,
n- octyl methacrylate, i- octyl methacrylate, 2-ethylhexyl methacrylate, i- nonyl methacrylate, n- dodecyl methacrylate, i- dodecyl methacrylate, C ₁ -C ₂₀ alkyl ester monomers of methacrylic acid, such as stearyl methacrylate can be used .

As the carboxyl group-containing monomer (b),
For example, C such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, and fumaric acid (preferably acrylic acid, methacrylic acid, and itaconic acid)
Of ₃ -C ₅ alpha, beta-unsaturated mono- - or di - carboxylic acid (hereinafter sometimes referred to as ethylene-based acid);
For example, alpha of C ₄ -C _5, such as maleic acid, anhydrides of β- unsaturated dicarboxylic acids; for example, mono-n- butyl maleate, mono-n- butyl fumarate, C ₄ -C _5, such as monoethyl itaconate Of α, β-unsaturated dicarboxylic acid of
₁ -C ₁₂ monoalkyl ester monomer; e.g., sodium acrylate, ethylene α-carboxylic acids or C ₄ -C _5, beta-unsaturated ammonium salt of the dicarboxylic acid monoalkyl ester monomers such as ammonium methacrylate Alternatively, an alkali metal salt can be used. Of these, the use of acrylic acid, methacrylic acid and / or itaconic acid is particularly preferred.

Further, as the monomer (c), for example,
Acrylamide, methacrylamide, diacetone acrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylacrylamide, N-methylacrylamide, Nn-butoxymethylacrylamide (preferably acrylamide, methacrylamide) and the like Amides of ethylene-based carboxylic acids or derivatives thereof; for example, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether,
Epoxy group-containing monomers such as glycidyl methallyl ether and glycidyl vinyl ether (preferably, glycidyl acrylate and glycidyl methacrylate);
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, allyl alcohol,
Hydroxyl-containing monomers such as methallyl alcohol (preferably, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate); for example, aminoethyl acrylate, N, N-dimethyl Aminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate (preferably, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate) and the like Esters of ethylene-based carboxylic acids with saturated alcohols having amino groups; for example, divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol Monomers having two or more radically polymerizable unsaturated groups such as methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate, allyl methacrylate; for example, vinyl mercaptan, allyl And mercapto group-containing monomers such as mercaptans; and the like.

The amount of these monomers used is generally based on 100% by weight of the total of the monomer components constituting NBR (B).
(Meth) acrylic ester monomer (a) 0 to 20% by weight; carboxyl group-containing monomer (b) 0 to 5% by weight; at least one radical polymerizable unsaturated group in the molecule 1
Monomer (c) other than the carboxyl group-containing monomer, which is a monomer having three functional groups, and 0 to 5% by weight;

The NBR (B) is prepared by subjecting these monomers to emulsion copolymerization in a known manner, for example, in an aqueous medium in the presence of a surfactant and / or a protective colloid to obtain an NBR latex. It can be produced by a method such as separating and precipitating a copolymer from a latex by an appropriate method.

The weight average molecular weight of NBR (B) used in the present invention is generally 50,000 or more, preferably 100,000 to 1,000,000, and the glass transition point (hereinafter sometimes abbreviated as Tg). ) Is generally -40 ° C to 5 ° C, preferably-
The temperature is preferably from 35C to -20C.

When the molecular weight is 1,000,000 or less, a suitable coating viscosity can be obtained without significantly lowering the solid content of the solution of the adhesive when the resulting adhesive composition is applied. On the other hand, when the composition solution is not less than the lower limit value, when the composition solution is applied to a metal tube or a heat-resistant synthetic resin, cissing hardly occurs, and the adhesive strength of the obtained adhesive layer is also reduced. It is also preferable because of good practical durability.

It is preferable that the Tg is 5 ° C. or less, since the practical durability of the obtained adhesive layer is good.
On the other hand, a temperature of −40 ° C. or higher is preferable because the heat resistance is excellent.

In the present invention, the average molecular weight (number average)
And weight average) and a Tg, respectively, gel permeation chromatography (hereinafter, sometimes abbreviated as GPC) and differential scanning calorimeter (Differential
(Scanning Calorimeter).

As such NBR (B), for example,
NIPPON 1072, NIPPON 1072J, NIPPON DN63
1, NIPPON DN300, NIPPON 1043, NIPPON 104
2 [or more, manufactured by Zeon Corporation], JSR N230N, JSR N23
3. A commercially available product such as JSR N241 (both manufactured by Nippon Synthetic Rubber Co., Ltd.) can be preferably used.

The amount of NBR (B) used in the present invention is determined by the above-mentioned liquid epoxy resin (A ₁ ) and non-liquid epoxy resin.
5 to 150 parts by weight, preferably 8 to 120 parts by weight, based on 100 parts by weight of the epoxy resin mixture (A) comprising (A ₂ ).

If the amount of NBR (B) used exceeds 150 parts by weight, the viscosity of the resulting adhesive composition solution becomes too high, and the solid content of the composition solution must be excessively low during coating. However, there is a disadvantage that the heat-resistant adhesive strength and the practical durability also decrease.
If the amount is less than the above lower limit, the viscosity of the obtained adhesive composition solution becomes unsuitable, and coating becomes difficult such as repelling when applied to a metal tube or a heat-resistant synthetic resin. It is also not preferable because the adhesive strength and the practical durability decrease.

The adhesive composition for a heat-resistant resin lining of the present invention is characterized in that the epoxy resin mixture (A) comprising the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ) is treated with the NBR ( Along with B), an acrylic resin (C) having an epoxy group can be further contained, if necessary.

Such an acrylic resin (C) can be obtained by using the above-mentioned N
The same monomer (a) as the monomer (a) exemplified as the monomer component of BR (B), and a monomer (b) having an epoxy group (b) It is obtained by copolymerization as a component. Such monomers (b), wherein as the, C ₁ -C ₂₀ alkyl ester monomers of C ₁ -C ₂₀ alkyl ester monomers and methacrylic acid acrylic acid. The amount of the monomer (A) used is, for example, based on 100% by weight of the total amount of the monomer components constituting the acrylic resin (C) (hereinafter, may be abbreviated as the total amount of the monomers), for example, It is good to be about 50 to 85% by weight, preferably about 65 to 85% by weight. By suitably selecting and using the monomer (a) in the above-mentioned usage amount range, a suitable balance with the adhesive strength of the obtained adhesive composition can be achieved.

The acrylic resin (C) is the same as the monomer (A)
In addition, a monomer (b) having an epoxy group is copolymerized. Examples of such a monomer (b) include the aforementioned NBR (B)
Among the monomers (C) exemplified as the monomer component of (a), they are the same as the epoxy group-containing monomers, for example, (meth) acrylic acid esters of epoxy group-containing alcohols such as glycidyl acrylate and glycidyl methacrylate Kind;
Examples thereof include (meth) allyl ethers or vinyl ethers of epoxy group-containing alcohols such as glycidyl allyl ether, glycidyl methallyl ether, and glycidyl vinyl ether; and preferred are (meth) acrylic acid esters of epoxy group-containing alcohols. The amount of the monomer (b) used is, for example, about 5 to 50% by weight, preferably about 10 to 40% by weight, based on 100% by weight of the total amount of the monomers. When the copolymerization amount of the monomer (b) is 50% by weight or less, the copolymerization reaction easily proceeds smoothly, without causing gelation, and a homogeneous copolymer is obtained, It is preferable because the adhesive strength of the obtained adhesive composition is excellent. On the other hand, when the copolymerization amount is 5% by weight or more, the compatibility with the epoxy resin and the blending stability do not decrease, and the adhesive strength, particularly the heat resistant adhesive strength, is excellent, which is preferable.

The acrylic resin (C) is a monomer
Along with (A) and (B), a monomer having a hydroxyl group (C) can be copolymerized, if necessary. Such a monomer (c) is the same as the hydroxyl group-containing monomer among the monomers (c) exemplified as the monomer component of the NBR (B). Hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate,
(Meth) acrylic acid esters of polyhydric alcohols such as polypropylene glycol mono (meth) acrylate; and unsaturated lower alcohols such as allyl alcohol and methallyl alcohol; (Meth) acrylic acid esters, and among these, use of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate is particularly preferable. The amount of the monomer (c) used is, for example, 0 to 50% by weight, preferably 0 to 20% by weight, more preferably 5 to 20% by weight based on 100% by weight of the total amount of the monomer.
It is an amount of about weight%. The copolymerization amount of the above monomer (c) is 50
When the amount is less than 10% by weight, smoothness of the copolymerization reaction is not hindered, gelation does not occur, and a homogeneous copolymer is obtained, and the adhesive strength of the obtained adhesive composition is excellent. Is preferred. On the other hand, when the copolymerization amount is 5% by weight or more, the compatibility with the epoxy resin and the compounding stability are particularly excellent, and the adhesive strength, particularly the heat-resistant adhesive strength, is preferably maintained.

The acrylic resin (C) comprises the monomer
(B) together with (b), if necessary,
The same carboxyl group-containing monomer (d) as the monomer (b) exemplified as the monomer component of R (B) can be copolymerized. As the monomer (d), it said as the ethylenic carboxylic acids, alpha of _{C 4 ~C 5, β- C 1} ~C 12 monoalkyl ester monomer and these ethylenically unsaturated carboxylic acids dicarboxylic acids or C ₄ ~C ₅ α, and an ammonium salt or alkali metal salt of β- unsaturated dicarboxylic acid monoalkyl ester monomer.
The amount of the monomer (d) can be, for example, about 0 to 15% by weight, preferably about 0 to 10% by weight, based on 100% by weight of the total amount of the monomers.

The acrylic resin (C) comprises the monomer
In addition to (a) and (b), if necessary,
A monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, as exemplified as the monomer component of BR (B), other than the carboxyl group-containing monomer The monomer (c) obtained by removing the monomers (b) and (c) from the monomer (c) is copolymerized. Examples of such a monomer (e) include, as described above, an amide of an ethylene-based carboxylic acid or a derivative thereof, an ester of an ethylene-based carboxylic acid and a saturated alcohol having an amino group, and two or more radical polymerizable monomers. Monomer groups such as a monomer having an unsaturated group and a monomer having a mercapto group can be exemplified. The amount of the monomer (d) used is 1
For example, an amount of about 0 to 15% by weight, preferably about 0 to 10% by weight with respect to 00% by weight can be exemplified.

The acrylic resin (C) comprises the monomer
(A) to (e), if necessary, and further copolymerizable with these monomers (a) to (e), and the monomers (a) to (e).
Other comonomers (f) may be copolymerized. Examples of such a comonomer (f) include saturated fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate; for example, dibutyl malate, dibutyl fumarate, dibutyl itaconate , Dioctyl malate, dioctyl fumarate, dioctyl itaconate, etc., C _1-
A linear or branched alkyl ester of _C18 ; for example, an aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene, and ethylvinylbenzene; a vinyl cyanide monomer such as acrylonitrile and methacrylonitrile And the like. The amount of the comonomer (f) used is generally from 0 to 50 based on 100% by weight of the total amount of the monomers.
% By weight, preferably of the order of 0 to 30% by weight.

The number average molecular weight of the acrylic resin (C) used in the present invention is preferably 50,000 or more, particularly preferably 80,000 to 200,000. It is preferable that the number average molecular weight of the acrylic resin (C) is not less than the lower limit value, since the adhesive strength of the obtained adhesive composition is excellent. On the other hand, since it is not easy to produce a copolymer having a number average molecular weight exceeding 200,000, the number average molecular weight is preferably adjusted so as to be within the above range. The weight average molecular weight of the acrylic resin (C) is generally 100,000 or more, preferably 200,000 or more, and more preferably 300,000 to 1,000,000. When the weight average molecular weight is 100,000 or more, the adhesive strength of the composition is excellent, which is preferable.On the other hand, when the weight average molecular weight is 1,000,000 or less, the production can be relatively easily performed. It is better to adjust it.

The Tg of the acrylic resin (C) is generally 100 ° C. or lower, preferably 30 ° C. or lower, more preferably 0 ° C. or lower, particularly preferably -5 ° C. or lower. Tg is 1
A temperature of 00 ° C. or lower is preferable because the resulting adhesive composition has an excellent balance between practical durability and adhesive strength.

The amount of the acrylic resin (C) used in the present invention is based on 100 parts by weight of the epoxy resin mixture (A) composed of the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ). , 0 to 50 parts by weight, preferably 3 to 50 parts by weight, particularly preferably 10 to 30 parts by weight.
If the amount of the acrylic resin (C) exceeds 50 parts by weight, the resulting adhesive composition may be insufficient in heat resistance and practical durability, which is not preferable. On the other hand, the use of 3 parts by weight or more is preferable because the adhesive strength of the composition can be improved.

The method for polymerizing the acrylic resin (C) used in the present invention is not particularly limited, and known methods such as solution polymerization and emulsion polymerization can be employed, but the copolymer mixture obtained by polymerization is used. In producing the adhesive composition by using it, it is preferable to employ solution polymerization in which the treatment process is relatively simple and can be performed in a short time.

In the solution polymerization, generally, a predetermined organic solvent, a monomer, a polymerization initiator and a chain transfer agent used if necessary are charged into a polymerization tank, and the mixture is stirred in a nitrogen stream or at the reflux temperature of the organic solvent. The reaction is carried out for several hours while heating. In this case, at least a part of the organic solvent, the monomer, the polymerization initiator and / or the chain transfer agent may be sequentially added.

As the above-mentioned organic solvent for polymerization, for example,
Aromatic hydrocarbons such as benzene, toluene, xylene and aromatic naphtha; for example, n-hexane, n-heptane,
aliphatic or alicyclic hydrocarbons such as n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, and turpentine oil; for example, ethyl acetate, n-butyl acetate, n-amyl acetate And esters such as 3-methoxybutyl acetate, methyl benzoate, cellosolve acetate and butyl cellosolve acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and methyl cyclohexanone; ethylene glycol methyl ether, ethylene glycol ethyl ether And glycol ethers such as ethylene glycol butyl ether; for example, tyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyi; Alcohol, i- butyl alcohol, s- butyl alcohol, t- butyl alcohol; and the like. These organic solvents can be used alone or in combination of two or more.

The adhesive composition for a heat-resistant resin lining of the present invention may be used, if necessary, in the aforementioned liquid epoxy resin.
It can be a solution of a solvent mainly composed of a polar organic solvent capable of dissolving (A ₁ ), the non-liquid epoxy resin (A ₂ ) and a curing agent (D) described below. In such a case, among the above-mentioned organic solvents for polymerization, a boiling point of 50 to 150 ° C., particularly 60 ° C. which can be easily replaced with a polar organic solvent by volatilizing the organic solvent for polymerization from the obtained copolymer solution. It is preferred to use an organic solvent at 100100 ° C.

As such an organic solvent, toluene,
Particularly preferred examples include n-hexane, ethyl acetate, acetone, methyl ethyl ketone, methyl alcohol, and n-propyl alcohol.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate and t-butylperoxy. Organic peroxides such as bivalate; for example, 2,2'-azobis-i-butyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2, An azo compound such as 4-dimethylvaleronitrile; and the like can be used alone or in combination. These polymerization initiators are generally used in an amount of about 0.01 to 1.0 part by weight, preferably about 0.02 to 0.5 part by weight, based on 100 parts by weight of the total amount of the monomers.

Examples of the chain transfer agent include:
Cyanoacetic acid; C of cyanoacetic acid₁~ C ₈Alkyl ester
Bromoacetic acid; C of bromoacetic acid₁~ C₈Alkyl S
Ters; for example, anthracene, phenanthrene, full
Aromatic compounds such as orene and 9-phenylfluorene
And the like; for example, p-nitroaniline, nitrobenzene, di
Nitrobenzene, p-nitrobenzoic acid, p-nitrofe
Aromatic nitro compounds such as phenol and p-nitrotoluene
And the like; for example, benzoquinone, 2,3,5,6-tetrame
Benzoquinone derivatives such as tyl-p-benzoquinone;
Borane derivatives such as ributylborane; for example, carbon tetrabromide
Element, carbon tetrachloride, 1,1,2,2-tetrabromoeta
, Tribromoethylene, trichloroethylene, bromo
Trichloromethane, tribromomethane, 3-chloro-1
-Halogenated hydrocarbons such as propene;
And aldehydes such as furaldehyde; C₁~ C₁₈No
Lucyl mercaptans; for example, thiophenol, tolu
Aromatic mercaptans such as enmercaptan; mercap
Toacetic acid; Mercaptoacetic acid C₁~ C_TenAlkyl ester
Class; C₁~ C₁₂A hydroxyalkyl mercaptan;
For example, terpenes such as binene and terpinolene;
I can do it.

When the above-mentioned chain transfer agent is used, its amount is preferably about 0.005 to 3.0 parts by weight per 100 parts by weight of the total amount of the monomers. The polymerization temperature is generally about 30 to
180 ° C, preferably in the range of about 60-150 ° C. The acrylic resin solution suitably used in the present invention thus obtained usually contains 20 to 90% by weight of the acrylic resin.

The adhesive composition for a heat-resistant resin lining of the present invention is prepared by reacting the above-mentioned NBR (A) with the epoxy resin mixture (A) comprising the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ). A curing agent (D) is contained as an essential component together with B) and an acrylic resin (C) optionally used.

The curing agent (D) includes a liquid epoxy resin (A ₁ ) and a non-liquid epoxy resin in the molecule of the curing agent.
A compound having a reactive group that reacts with the epoxy group or the hydroxyl group in (A ₂ ) and the acrylic resin (C), or a compound that generates such a reactive group by heating or the like (hereinafter referred to as a crosslinkable curing agent) And a compound having a group capable of acting as a catalyst for a ring-opening polymerization reaction of the epoxy group or a reaction between the epoxy group or the hydroxyl group and a crosslinkable curing agent in a curing agent molecule (hereinafter, referred to as a compound). , And a catalytic curing agent).

Among the above-mentioned crosslinkable curing agents, curing agents which cause an addition reaction with the above-mentioned epoxy group include, for example, linear aliphatic primary or secondary amines; alicyclic, aromatic or heterocyclic-containing fatty acids. Primary or secondary amines of aromatic group; aromatic primary or secondary amines; polyamidoamines obtained by reacting a polymer of unsaturated fatty acid such as linoleic acid or linolenic acid with polyamines; mercaptan-based compounds A polybasic acid such as a polymer of unsaturated fatty acid or octadecanedicarboxylic acid; and an active hydrogen compound-based curing agent.

As the curing agent that causes an addition or condensation reaction with the hydroxyl group in the liquid epoxy resin (A ₁ ), the non-liquid epoxy resin (A ₂ ) and the acrylic resin (C), for example, a phenol resin ( Resole type); amino resin; polyisocyanate; blocked polyisocyanate and the like.

Further, like an acid anhydride, a compound which firstly undergoes an addition reaction to a hydroxyl group in a resin component and then undergoes an addition reaction between a generated carboxyl group and an epoxy group can be used. Further, as the catalytic curing agent, aliphatic, alicyclic or aromatic tertiary amines or salts thereof; imidazoles or salts thereof; amine amide curing agents; Lewis acids or Bronsted acid salts; urea derivatives In addition, the above unsaturated fatty acid polymer, polybasic acid such as octadecanedicarboxylic acid, and acid anhydride also have an action as an epoxy group ring-opening polymerization catalyst.

As will be described later, these various curing agents are prepared in advance using the liquid epoxy resin (A ₁ ), the non-liquid epoxy resin,
(A ₂ ), NBR (B) and an acrylic resin (C) to be used if necessary are preferably blended with a resin component. In this case, from the viewpoint of the pot life of the blend, etc. The use of a high temperature activated curing agent is preferred.

Among such high temperature activated curing agents, those which can be suitably used in the present invention include, as crosslinkable curing agents, one of a high temperature activated type alicyclic ring, aromatic ring or heterocyclic-containing aliphatic. Primary or secondary amines; high-temperature activated aromatic primary or secondary amines; active hydrogen compound-based curing agents having a high melting point; acid anhydrides; and amine imide-based curing agents as catalytic curing agents; High-temperature activated tertiary amine or imidazole curing agents; tertiary amine salt or imidazole salt curing agents; urea derivative curing agents; and the like.

The above-mentioned high temperature activated alicyclic, aromatic or heterocyclic-containing aliphatic primary or secondary amines include, for example, 4-amino-2,2,6,6-tetramethylpiperidine, Bis (4-amino-3-methylcyclohexyl) methane, 2,4-dihydrazino-6-methylamino-s-triazine and the like can be exemplified.

Examples of the high temperature activated aromatic primary or secondary amines include, for example, diaminodiphenyl sulfone and diaminodiphenylmethane, and examples of the high melting point active hydrogen compound-based curing agent include, for example, dicyandiamide; Adipic hydrazide, 5-t-butylhydanthrene-1,3-di (carboxyethyl) dihydrazide [Amicure VDH (trade name); Ajinomoto Co., Ltd.], octadecane-1,18-dicarboxylic dihydrazide [Amicure LDH (trademark) Ajinomoto Co., Ltd.], Octadeca
Organic acid dihydrazides such as 7,11-diene-1,18-dicarboxylic acid dihydrazide [Amicure UDH (trade name); Ajinomoto Co., Ltd.] can be exemplified.

Examples of the acid anhydride include maleic anhydride, dodecyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic anhydride, poly (ethylene octadecanoic acid) anhydride, and poly (phenyl) anhydride. Aliphatic acid anhydrides such as hexadecanoic anhydride); for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride;
Alicyclic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylhymic anhydride;
For example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride,
Examples thereof include aromatic acid anhydrides such as ethylene glycol bis anhydride trimellitate and glycerol tris anhydride trimellitate.

Further, as amine imide-based curing agents, trialkylhydrazinium fatty acid amides [YPH103, YPH2
01, YPH208; (trade name); Yuka Shell Epoxy Co., Ltd.]
However, as a high temperature activated tertiary amine or imidazole-based curing agent, 2,4,6-tris (dimethylaminomethyl) phenol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4- Methyl imidazole and the like are tertiary amine salt or imidazole salt-based curing agents, and Amicure PN-23 and MY-24 [(trade name); Ajinomoto Co.] are Lewis acid or Bronsted acid salt-based curing agents. For example, Lewis acid salts such as boron trifluoride monoethylamine salt; for example, Bronsted acid aliphatic sulfonium salt [Opton CP-66,
CP-77; (trade name); Asahi Denka Kogyo Co., Ltd.]. Examples of the urea derivative-based curing agent include N, N-dimethylurea, N, N′-dimethylurea, and N, N ′. -Diethyl urea, N-phenyl urea, N, N-diphenyl urea, N, N, N'-triphenyl urea, N, N, N,
N'-tetraphenylurea, N-acetylurea, N,
N'-diacetyl urea, N-acetyl-N'-methyl urea, N-benzyl urea, N, N-dibenzoyl urea, N
-Benzenesulfonylurea, Np-toluenesulfonylurea, Np-toluenesulfonyl-N'-n-butylurea, Np-toluenesulfonyl-N'-i-butylurea, N, N-dimethyl-N '-(3', 4'-dichlorophenyl) urea, parabanic acid, N, N'-dimethylparabanic acid, N, N'-dimethylbarbituric acid, 5,
Examples thereof include 5'-dimethylhydantoin, 1,3-dimethyluracil, and 1,5-dimethyluracil.

Among these curing agents, from the viewpoints of pot life, storage stability, adhesion performance, and the speed of heat curing of the obtained adhesive composition, high-temperature-active crosslinkable The use of a curing agent is particularly preferred.

The amount of the curing agent (D) used depends on the components
The epoxy resin mixture (A) 10 comprising (A ₁ ) and (A ₂ )
It is 1 to 10 parts by weight with respect to 0 parts by weight. If the amount exceeds 10 parts by weight, the pot life and storage stability of the obtained adhesive composition tend to be insufficient. And the adhesive strength, heat resistant adhesive strength, practical durability and the like may be insufficient.

These curing agents (D) are prepared in advance by using the above-mentioned liquid epoxy resin (A ₁ ), non-liquid epoxy resin (A ₂ ), NBR
It may be blended with the resin component composed of (B) and the acrylic resin (C) used as required, or may be blended with the resin component immediately before use.

However, in order to avoid troublesome work during use, the curing agent (D) must be prepared in advance by using (A ₁ ), (A ₂ ), (B) and
It is good to mix it with the component (C). The method of blending the curing agent (D) is not particularly limited, but it is preferable to blend the curing agent (E) after dissolving the curing agent (E) in a soluble organic solvent, from the viewpoint of ease of blending and the like. .

The organic solvent is a liquid epoxy resin
(A ₁ ), a non-liquid epoxy resin (A ₂ ), NBR (B), an acrylic resin having an epoxy group used as needed (C)
And the curing agent (D).

As such an organic solvent, a polar organic solvent is generally used, and examples thereof include ketones such as methyl ethyl ketone, methyl i-butyl ketone, methyl cyclohexanone, and diacetone alcohol; for example, ethylene glycol methyl ether and ethylene glycol ethyl. Ether, ethylene glycol-i-propyl ether,
Ethylene glycol butyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme)
Glycol ethers such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol-i-propyl ether acetate; glycol esters such as dimethyl sulfoxide, dimethyl sulfone, tetramethyl sulfone, dimethyl formamide; Other aprotic polar organic solvents such as dimethylacetamide, hexamethylphosphoric triamide, N-methylpyrrolidone, and acetonitrile;

The adhesive composition for a heat-resistant resin lining of the present invention comprises an epoxy resin mixture (A) comprising the liquid epoxy resin (A ₁ ) and the non-liquid epoxy resin (A ₂ ), and the NBR (B) In addition to the essential component consisting of the curing agent (D) and the acrylic resin (C) having an epoxy group used as required, a liquid NBR can be further compounded as required.

As such a liquid NBR, those having a number average molecular weight of about 1,000 to 10,000 are preferable. For example, Hiker CTBN 1300X8, Hiker CTBN 1300X13, Hiker CT
BN 1300X31, Hiker CTBNX 1300X9 ((trade name); manufactured by Ube Industries, Ltd.), Nipol 1312, Nipol DN6
01 [(trade name); above, manufactured by Zeon Corporation], JSRN28
0 ((trade name); manufactured by Nippon Synthetic Rubber Co., Ltd.) can be suitably used.

The compounding amount of the liquid NBR depends on the resin mixture 1
0 to 15 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight. When the amount is 15 parts by weight or less, the adhesive strength and the heat resistant adhesive strength of the obtained adhesive composition are not insufficient, so that it is preferable.

The adhesive composition for a heat-resistant resin lining of the present invention may further comprise, if necessary, for example, a coumarone-indene resin, a terpene-phenol resin, a pt-t resin, as long as the excellent curing of the present invention is not impaired. -Tackifying resins such as butylphenol / acetylene resin, phenol / formaldehyde resin, terpene resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, hydrogenated hydrocarbon resin, rosin derivative, and turpentine resin; for example, ethylene-vinyl acetate -Based copolymer resin, ethylene-
Other modifying resins such as acrylic copolymer resins and ethylene-vinyl acetate-acrylic copolymer resins can be added. The addition amount of these resins is, based on 100 parts by weight of the total of the resin mixture, a tackifying resin, for example, 0 to 60 parts by weight, particularly 0 to 40 parts by weight; The amount is preferably about 0 to 20 parts by weight.

In addition to the above, the adhesive composition for heat-resistant resin lining of the present invention may be optionally used, for example, a phthalate ester such as dioctyl phthalate, a phosphate ester such as tricresyl phosphate, or polybutene. ,
Plasticizers such as process oils; organic or inorganic colorants such as titanium oxide, carbon black, phthalocyanine blue; inorganic fillers such as clay, talc, calcium carbonate, silica, aluminum hydroxide, glass powder; For example, ultrafine anhydrous silica [Aerosil
Thickeners such as 300 (trade name, manufactured by Nippon Aerosil Co., Ltd.) and activated ultrafine calcium carbonate (white luster CCR (trade name), manufactured by Shiraishi Industry Co., Ltd.); UV absorber; preservative; Known additives may be added.

As a method for producing the adhesive composition for a heat-resistant resin lining of the present invention, for example, a liquid epoxy resin (A ₁ ) and a non-liquid epoxy resin (A ₂ ) are mixed and uniformly dispersed. To this, a solution of the acrylonitrile-butadiene copolymer (B) dissolved in an organic solvent such as methyl ethyl ketone, an organic solvent solution of an acrylic resin (C) having an epoxy group, and liquid NBR and other additives used as necessary. A predetermined amount of each is mixed and mixed, and if necessary, an organic solvent is added or a part of the organic solvent is removed by a known method such as distillation, and the liquid epoxy resin (A ₁ )
Non-liquid epoxy resin (A ₂ ), acrylonitrile-butadiene copolymer (B), acrylic resin having epoxy group
(C), a mixture of various additives that are added as needed, and then, to this, a curing agent (D) and a polar organic solvent capable of dissolving and dispersing the same are further added, and if necessary, The method of adding the organic solvent and uniformly mixing can be suitably used.

The resulting organic solvent solution of the adhesive composition for heat-resistant resin lining of the present invention usually has a solid content of about 20 to 90%.
% By weight, viscosity (B-type rotational viscometer, 25 ° C, 10 RPM; below,
The measurement conditions are the same) 50 to 10,000 cps, preferably 200
It should be about 3000cps.

The adhesive composition for a heat-resistant resin of the present invention may be stored at a low temperature of, for example, 10 ° C. or lower, preferably 0 ° C. or lower, but may be stored at room temperature (about 25 ° C.). The composition has a pot life of one week or more, and the type and amount of the curing agent (D) are preferably selected so that the adhesive properties do not change.

[0080]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Reference Examples and Comparative Examples together with Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. In the following examples, the methods for measuring the compatibility of the composition, the pot life test method, and the cold / hot repetition test as the shear adhesive strength, adhesive strength, heat resistant adhesive strength and practical durability test are as follows.

(1) Composition Compatibility Test The composition solution was allowed to stand in a closed state at 25 ° C. for 24 hours, and the uniformity, transparency, and the presence or absence of sediment of the solution were visually observed.
Evaluate according to the following criteria. ○ ……… The composition solution is uniform and transparent, with no sediment. Δ ……… The composition solution was uniform, but slightly cloudy or sedimented. X: Composition solution separation or opacity, or
Lots of sediment.

(2) Composition pot life test (2-1) Appearance The composition solution was allowed to stand in a closed state at 25 ° C. for 7 days, and the condition was evaluated according to the following criteria. ◎ ……… Almost no change in appearance or viscosity. ○ ……… The appearance does not change, but the viscosity slightly increases. Δ: No change in appearance, but large increase in viscosity (fluidity). ×: Extremely high viscosity increase (no fluidity) or gelation.

(2-2) Adhesive properties Using the composition solution left in a closed state at 25 ° C. for 7 days, the shear adhesive strength and the adhesive strength were measured according to the following items (3) to (4), and the adhesive was left to stand. Compared to using the previous composition solution,
Evaluate according to the following criteria. ◎ ……… There is almost no change in shear adhesive strength and adhesive strength (decrease rate less than 10%). ○ ……… Shear adhesive strength, rate of decrease in adhesive strength, one of which is 10%
Less than 10-30% for the other. △ ……… Shear adhesive strength, adhesive strength decrease rate, 10% for one
Less than 30-50% or more for the other or both 10-30% or more. × ……… Shear adhesive strength, decrease rate of adhesive strength, 50% for one
Or more than 30%.

(3) Measurement of shear adhesive strength (3-1) Measurement of room temperature shear adhesive strength 1 mm thick steel sheet and 2 mm thick chlorinated vinyl chloride resin sheet specified in SS-41 of JIS G-3141 The surfaces of (polymerization degree 1000, chlorine content 66.5% by weight) were each washed with methanol-impregnated gauze to give a test piece adherend, and the adhesive composition solution was dried thereon so that the thickness after drying was 50 μm. And dried in a hot air circulating drier at 50 ° C. for 3 minutes, then at 70 ° C. for 5 minutes. The steel sheet and the chlorinated vinyl chloride resin sheet having the obtained adhesive layer are pressed into a test piece according to the method of JIS K-6850 so that the adhesive layers are in contact with each other, and after being cured by heating under predetermined conditions, It is left at 25 ° C. for 24 hours, and then its shear adhesive strength (kg / cm ² ) is measured under the conditions of 20 ° C., 65% RH and a tensile speed of 50 mm / min. The value of the room temperature shear adhesive strength is preferably 60 kg / cm ² or more, and particularly preferably 80 kg / cm ² or more.

(3-2) Heat-resistant Shear Adhesion The test piece was cured by heating under the specified conditions in the section (3-1).
And let stand at 25 ° C for 24 hours, then adjust to 100 ° C
After leaving it in the constant temperature bath for about 10 minutes, measure in the constant temperature bath.
Shear connection in the same manner as in the test method described in (3-1)
Wear strength (kg / cm ^Two) Is measured. The value of the heat shear adhesive strength
For example, 50kg / cm^TwoPreferably at least 60 kg / cm
^TwoThe above is particularly preferred.

(4) Measurement of Adhesive Strength (4-1) Measurement of Adhesive Strength at Room Temperature The same steel sheet and chlorinated vinyl chloride resin sheet as described in the preceding section (3-1) were used. Process the same as described in
Apply the adhesive composition solution to cover about half of its surface (3
-1) Coated and dried in the same manner as described in paragraph 1), and the obtained steel sheet and chlorinated vinyl chloride resin sheet having an adhesive layer are placed in such a manner that the adhesive layers are in contact with each other, as described in 8.2.3 of JIS Z-0237. And then cured by heating under predetermined conditions, then left at 25 ° C. for 24 hours, cut into 25 mm widths to obtain test specimens.

The measurement was performed by bending a steel plate of the test piece (the part without the adhesive) to about 90 degrees, and according to JIS Z-0237 "90 degree peeling method", 20 ° C., 65% RH, peeling speed 300 mm. The peel strength (kg / 25 mm) is measured under the conditions of / min. The adhesive strength is preferably 6 kg / 25 mm or more, and 10 kg / 25 mm or more.
It is particularly preferred that it is at least mm.

(4-2) Heat-resistant adhesive strength After the test specimen prepared in the previous section (4-1) was cured by heating under predetermined conditions, it was allowed to stand at 25 ° C. for 24 hours, and then the temperature was adjusted to 100 ° C. After leaving it in the bath for about 10 minutes, the peel strength (kg / 25 mm) is measured in the same manner as in the test method described in the above (4-1) except that the measurement is performed in the thermostatic bath. The heat-resistant adhesive strength is preferably 4 kg / 25 mm or more, particularly preferably 6 kg / 25 mm or more.

(5) Measurement of repeated cooling / heating test (5-1) Appearance In the preceding section (3-1), after the test piece was cured by heating under predetermined conditions, it was allowed to stand at 25 ° C. for 24 hours, and then heated in boiling water. After heating and cooling for 10 minutes, and then cooling in water at room temperature (about 15 ° C) for 30 minutes, the state after repeating 10 cycles is evaluated according to the following criteria. ○ ……… No change in the appearance of the bonded part. △ ……… The adhesive part peels off or floats a little. ×: The bonded portion peeled off or floated.

(5-2) Measurement of room temperature shear adhesive strength after repeated cooling and heating After the test specimen prepared in the previous section (3-1) was cured by heating under predetermined conditions, it was allowed to stand at 25 ° C. for 24 hours. The same heating / cooling cycle as described in the paragraph 5-1) is repeated 10 times, and then the shear adhesive strength (kg / cm ² ) is measured under the conditions of 20 ° C., 65% RH, and a tensile speed of 50 mm / min. . The value of the shear adhesive strength is preferably 60 kg / cm ² or more,
Particularly preferred is 80 kg / cm ² .

(5-3) Measurement of heat-resistant shear adhesive strength after repeated cooling and heating In the preceding section (5-2), the test piece was cured by heating under predetermined conditions, and then left at 25 ° C. for 24 hours. -2) Repeat the same heating and cooling cycle as described in paragraph 10 for 10 cycles, then leave it in a thermostat adjusted to 100 ° C for about 10 minutes, and then measure it in the thermostat before Measure the shear adhesive strength (kg / cm ² ) in the same manner as in the test method in 5-2).

Reference Example 1 In a separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a sequential dropping device, 37.5 parts by weight of ethyl acetate (EAc) as an organic solvent for initial addition and azobisiso 0.025 parts by weight of butyronitrile (AIBN) is added, and then 25% by weight of a monomer mixture consisting of 70 parts by weight of butyl acrylate (BA) and 30 parts by weight of glycidyl methacrylate (GMA) is added, and heated to reflux temperature ( (About 80 ° C.) for about 20 minutes.

Next, at reflux temperature conditions, 75% by weight of the remaining monomer mixture, 25 parts by weight of EAc and 0.125% of AIBN
Parts by weight of a polymerization initiator solution consisting of 12.5 parts by weight of EAc and A
After adding a polymerization initiator solution consisting of 0.25 parts by weight of IBN, 75 parts by weight of toluene was added and diluted to obtain an acrylic resin solution having a solid content of about 40% by weight and a viscosity of 2050 cps. The weight average molecular weight [Mw (average)] of this acrylic resin is about 60
The Tg was −33 ° C. Table 1 shows the obtained results.

Reference Examples 2 to 4 In Reference Example 1, except that a monomer mixture having a monomer composition shown in Table 1 was used instead of using a monomer mixture consisting of 70 parts by weight of BA and 30 parts by weight of GMA. Reference Example 1
In the same manner as in the above, an acrylic resin solution was obtained. Table 1 shows Mw (average) and Tg of the obtained acrylic resin, and solid content and viscosity of the obtained resin solution.

[0095]

[Table 1]

Example 1 In a separable flask equipped with a stirrer and a dropping device, Epicoat 828 was used as a liquid epoxy resin (A ₁ ).
[(Trade name); bisphenol A type epoxy resin (epoxy equivalent: about 190), manufactured by Yuka Shell Epoxy Co.] 75 parts by weight, Epicoat 1004 as a non-liquid epoxy resin (A ₂ )
[(Trade name); bisphenol A type epoxy resin (epoxy equivalent: about 950), manufactured by Yuka Shell Epoxy Co., Ltd.] 25 parts by weight and dimethylformamide 25 parts by weight were added, mixed with stirring, and dissolved. Next, NBR (B) was added to the obtained solution.
50 parts by weight of Nipol 1072J [(trade name); acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile content of 27% by weight, weight average molecular weight of about 340,000, Tg-24 ° C; manufactured by Nippon Zeon Co.]
A solution prepared by dissolving 5 parts by weight of dicyandiamide (DICY) (an amine-based curing agent) in 15 parts by weight of dimethylformamide as a solution dissolved in parts by weight and a curing agent (D) is added thereto. An adhesive composition was obtained. The obtained composition had a solid content of about 39% by weight and a viscosity of about 800 cps. The measurement results of basic properties such as compatibility and pot life of the composition and various physical properties are shown in Tables 2, 3 and 4.

Examples 2-3 and Comparative Examples 1-2 In Example 1, the mixing ratio of Epicoat 828, which is a liquid epoxy resin (A ₁ ), and Epicoat 1004, which is a non-liquid epoxy resin (A ₂ ), was changed. Or, Epicoat 1004
And an adhesive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of Epicoat 828 was used without using the same. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

[0098] Example 4 In Example 1, as the epoxy resin (A), the Epikote 828 is a liquid epoxy resin (A ₁₎ instead of using 75 parts by weight, the liquid epoxy resin (A ₁₎ Epikote 815
An adhesive composition was obtained in the same manner as in Example 1 except that 75 parts by weight of (trade name) bisphenol A type epoxy resin (epoxy equivalent: about 190) mixed with an epoxy reactive diluent was used. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

Example 5 In the same manner as in Example 1 except that 20 parts by weight (as solid content) of the acrylic resin obtained in Reference Example 1 was further used as the acrylic resin (C). An adhesive composition was obtained. Table 2 shows the composition of the obtained compositions.
Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

Examples 6 to 7 and Comparative Example 3 In Example 5, the reference example 1 was an acrylic resin (C).
An adhesive composition was obtained in the same manner as in Example 5, except that the amount of the acrylic resin was changed. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

Examples 8 to 10 In Example 5, the reference example 1 was used as the acrylic resin (C).
Example 5 except that each of the acrylic resins obtained in Reference Examples 2 to 4 was used instead of using the acrylic resin of Example 5.
In the same manner as in the above, an adhesive composition was obtained. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

Examples 11 and 12 and Comparative Examples 4 and 5 The same procedure as in Example 1 was carried out except that the amount of Nipol 1072J as NBR (B) was changed or the compound was not used. A composition was obtained. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties. In addition, Nipole 10
In the case of the composition not using 72J (Comparative Example 3), repelling occurred during the application of the composition to a steel plate and a chlorinated vinyl chloride resin plate. It was created.

Comparative Examples 6 and 7 An adhesive composition was obtained in the same manner as in Example 1 except that the amount of DICY as the curing agent (D) was changed or not added. Table 2 shows the composition of the obtained compositions, Table 3 shows the measurement results of basic physical properties such as viscosity, solid content, compatibility and pot life, and Table 4 shows curing conditions and various adhesive properties.

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

The adhesive composition for a heat-resistant resin lining according to the present invention comprises a liquid epoxy resin (A ₁ ) and a non-liquid epoxy resin (A ₂ ), each of which comprises a specific amount of an epoxy resin mixture (A). It is characterized in that it contains a specific amount of NBR (B) and a curing agent (D) as essential components, respectively, and further contains a specific amount of an acrylic resin (C) having an epoxy group as required.

As is clear from the above Examples and Comparative Examples, when the mixing ratio of the components (A ₁ ) and (A ₂ ) deviates from the range of the present invention and the content of the component (A ₁ ) is too large, , For example, 1
The heat-resistant adhesive strength at a high temperature such as about 00 ° C. becomes insufficient, and the practical durability is remarkably deteriorated, as can be seen particularly from the results of the repeated cooling and heating tests. On the other hand, if the component (A ₂ ) is too large, the compatibility at the time of compounding the adhesive composition becomes poor,
Further, similarly to the case where the component (A ₁ ) is too much, the heat resistance becomes insufficient and the practical durability is remarkably reduced.

On the other hand, if the amount of the component (B) is too small, the viscosity of the obtained adhesive composition solution becomes unsuitable, resulting in difficulties such as repelling when coated on a metal surface or a heat-resistant synthetic resin. On the other hand, if the amount is too large, the viscosity of the adhesive composition solution becomes too high, and there is a disadvantage that the solid content of the composition must be excessively reduced during coating, and the heat-resistant adhesive strength also decreases. In any case, the practical durability is significantly reduced. If the amount of the component (C) is too large, the heat resistance and the practical durability are both reduced. Further,
If the amount of the component (D) is too small, the curing speed at the time of heat curing is reduced, and the shear adhesive strength, heat-resistant shear adhesive strength, adhesive strength, heat-resistant adhesive strength and practical durability are all reduced. Stability decreases.

As described above, the adhesive composition for a heat-resistant resin lining of the present invention not only has excellent various stability as an adhesive composition but also obtains the adhesive obtained only by satisfying these conditions. The layer has a high degree of adhesive strength, and in particular, retains high adhesive strength even at a high temperature such as about 100 ° C. and has excellent performance such as high practical durability.

Continuation of the front page (56) References JP-A-63-304076 (JP, A) JP-A-61-69827 (JP, A) JP-A-1-201384 (JP, A) JP-A-63-227686 (JP, A) JP-A-62-43480 (JP, A) JP-A-59-4657 (JP, A) JP-A-1-221477 (JP, A) JP-A-59-232160 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C09J 163/00-163/10 B29C 63/06 B29C 63/34 C08G 59/20-59/38

Claims (2)

(57) [Claims] (A) (A ₁ ) 30 to 95% by weight of a liquid epoxy resin
And (A ₂₎ an epoxy resin 100 parts by weight of the mixture consisting of non-liquid epoxy resin 70 to 5 wt% [However, (A ₁₎ and (A ₂₎
(B) 5 to 150 parts by weight of an acrylonitrile-butadiene copolymer, (C) 0 to 50 parts by weight of an acrylic resin having an epoxy group, and (D)
An adhesive composition for a heat-resistant resin lining, comprising 1 to 10 parts by weight of a curing agent. 2. A heat-resistant synthetic resin-lined metal tube obtained by bonding a heat-resistant synthetic resin to an inner surface and / or an outer surface of a metal tube using the adhesive composition according to claim 1.