JPH0633027A - Adhesive for synthetic resin lining and synthetic resin-lined pipe using the same - Google Patents

Abstract

PURPOSE:To provide a new adhesive capable of improving the sustainable adhesiveness between synthetic resin pipe and metallic pipe. CONSTITUTION:Firstly, 100 pts.wt. of a 2wt.% maleic acid anhydride-modified SEBS is incorporated with 5 pts.wt. of 3'-glycidoxypropyltrimethoxysilane followed by hot-melt mixing at 150 deg.C to graft the silane compound to the SEBS to obtain a silane-modified block copolymer 1. Then, a composition comprising 100 pts.wt. of the silane-modified copolymer, 30 pts.wt. of a 5C-based petroleum resin (trade name: Quinton D 200, produced by Nippon Zeon Co., Ltd.), and N 0.01 pts.wt. of dibutyltin dilaurate, is hot-melted and kneaded at 150 deg.C to obtain the objective hot-melt adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin lining adhesive suitable for producing a synthetic resin lining pipe by bonding a synthetic resin pipe to the inner surface of a metal pipe, and a synthetic resin using the adhesive. More specifically, the present invention relates to a synthetic resin lining adhesive that can enhance the durable adhesion between a synthetic resin pipe and a metal pipe, and a synthetic resin lining pipe having excellent durable adhesion.

[0002]

2. Description of the Related Art Conventionally, a synthetic resin lining pipe has been manufactured by a method called an expansion method or a contraction method.

In the swelling method, an adhesive is interposed between the outer peripheral surface of the synthetic resin tube and the inner peripheral surface of the metal tube, and the synthetic resin tube is expanded by heating and pressurizing the two to bond them together. (For example, JP-A-56-55227, JP-A-58-58)
12720, JP-A-59-59418 and the like). On the other hand, in the diameter reduction method, the diameter of the metal pipe is reduced by a roll or the like with an adhesive agent interposed between the outer peripheral surface of the synthetic resin pipe and the inner peripheral surface of the metal pipe, whereby the outer periphery of the synthetic resin pipe is reduced. The surface and the inner peripheral surface of the metal pipe are pressure-bonded to each other.

In the conventional method for producing a synthetic resin lining pipe as described above, as the adhesive, a polyamide or polyester adhesive, a butadiene-styrene block copolymer elastomer hot-melt adhesive, and a styrene-butadiene-styrene triad are used. An adhesive containing a block copolymer as a main component (Japanese Patent Publication No. 2-37378), an adhesive containing a polyolefin containing a carboxylic acid group or an acid anhydride group in the molecule as a main component (JP-A-58-12720), A block copolymer comprising at least two vinyl aromatic compound-based polymer blocks and at least one conjugated diene compound-based polymer block B is hydrogenated to give a conjugate in the polymer. Hydrogenated block copolymers obtained by hydrogenating at least 80% of aliphatic double bonds based on diene compounds To 100 parts by weight of an epoxy group-containing unsaturated compound 0.01 to 20 parts by weight of the graft to the resulting adhesive (Kokoku 3─23582) or the like has been used.

[0005]

However, in the conventional synthetic resin lining pipe manufactured by using the above-mentioned adhesive, heat resistance and durability adhesion between the synthetic resin pipe and the metal pipe are not sufficient. There was a problem. That is, when the cooling / heating cycle test was repeated for the obtained synthetic resin lining pipe, there was a problem that peeling was likely to occur at the bonded portion between the synthetic resin pipe and the metal pipe.
Also, in the conventional method of manufacturing a synthetic resin lining pipe,
The method using a solvent-type adhesive as the adhesive also has a problem that the working environment is contaminated by the organic solvent, and a lot of working space and steps are required for drying the solvent.

Therefore, an object of the present invention is to solve the problems in the conventional method for producing a synthetic resin lining pipe, and to improve the durable adhesion between the synthetic resin pipe and the metal pipe. An object of the present invention is to provide an adhesive for lining and a synthetic resin lining tube having excellent durability.

[0007]

Means for Solving the Problems The inventors of the present application have made earnest studies to improve the durable adhesion between a synthetic resin lining tube and a metal tube in a synthetic resin lining tube, and as a result, have been modified with a specific silane compound as an adhesive. It was found that durable adhesiveness can be enhanced by using a specific block copolymer,
The present invention has been accomplished.

That is, the adhesive for synthetic resin linings according to the first aspect of the present invention is preferably used when a synthetic resin lining pipe is manufactured by a swelling method or a diameter reducing method, and has the general formula A -BA or AB (however, A is
A block consisting essentially of a monovinyl-substituted aromatic compound polymer is shown, and B is a block consisting essentially of a diolefin polymer. ), A block copolymer having a monovinyl-substituted aromatic compound polymer content of 10 to 70% by weight and a weight average molecular weight of 5,000 to 500,000, or at least one of these hydrogenated compounds, and an unsaturated carboxylic acid Acid or unsaturated carboxylic acid anhydride 0.01 to 30
The graft block of the modified block copolymer grafted in the range of wt% is further represented by the general formula R ¹ SiY ₃ (R ¹ represents a hydrocarbon group having an epoxy group or a hydrocarbonoxy group, and Y is hydrolyzable. It shows that it is modified with a silane compound represented by an organic functional group.

Block copolymers or hydrogenated products thereof In the present invention, a compound represented by the general formula ABAA or AB [A
Is a block substantially consisting of a monovinyl-substituted aromatic compound polymer (hereinafter referred to as A component), B is a block substantially consisting of a diolefin polymer (hereinafter referred to as B component)], and contains an A component. A block copolymer having an amount of 10 to 70% by weight and a weight average molecular weight of 5,000 to 500,000 or at least one of hydrogenated products thereof (hereinafter referred to as a block copolymer) is used.

The block copolymer has, for example, a structure in which an ethylene structure and a butylene structure (component B) are mixed in the middle of styrene polymer blocks (component A) at both ends, for example, a butadiene polymer block ( B
Component), which is obtained by completely adding hydrogen to the butadiene polymer part (component B) of a styrene-butadiene-styrene (SBS) type block copolymer having a structure in which styrene polymer blocks (component A) are bonded to both ends. thing,
Or styrene polymer blocks at both ends (A component)
In the middle of the mixture of ethylene structure and propylene structure (B
Component), for example, isoprene of a styrene-isoprene-styrene (SIS) type block copolymer having a structure in which styrene polymer blocks (component A) are bonded to both ends of an isoprene polymer block (component B). What is obtained by completely adding hydrogen to the polymer part (component B) is used.

The block copolymer comprises a hard block such as styrene phase (component A) and an elastic block such as ethylene-butylene phase or ethylene-propylene phase (component B).
It has a phase structure. When the content of the hard block (component A) is low, the elastic modulus and cohesive force of the resin are low, which causes problems in adhesive strength and heat resistance when used as an adhesive.
On the other hand, if the content of the hard block (component A) is too high, the elastic modulus becomes too high, resulting in loss of flexibility, resulting in a so-called hard adhesive, which lowers the fluidity and peel strength during heating. Therefore, the content of the component A in the block copolymer is 10 to 7
It is set to 0% by weight, and specifically, it is preferably 15 to 35% by weight. The weight average molecular weight of the block copolymer is 5,000 to 500,000, preferably 400.
It is suitable for synthetic resin lining that it is 00-120000.

Modified block copolymer A block copolymer is grafted with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride in an amount of 0.01 to 30% by weight to give a modified block copolymer (hereinafter referred to as an acid-modified block copolymer). Block copolymer)).

As the carboxylic acid or acid anhydride to be grafted on the block copolymer, for example, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid or acid anhydrides of these carboxylic acids are used. However, among these, dicarboxylic acid anhydride is preferable,
Maleic anhydride is particularly preferable. The content of the grafted carboxylic acid or acid anhydride component in the acid-modified block copolymer is 0.01 to 30% by weight, preferably 0.05 to 10% by weight. The reason why the amount is 0.01 to 30% by weight is that if the amount is less than 0.01% by weight, the effect of silane modification is small, and if the amount exceeds 30% by weight, the polarity of the elastic block is increased to form a two-phase structure. This is because there is a risk of hindrance.

The acid-modified block copolymer is prepared by keeping the block copolymer and the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in a molten state or in a solution state without using a radical initiator. , A block copolymer is grafted with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. The method for producing these acid-modified block copolymers is not particularly limited in the present invention, but the obtained acid-modified block copolymer contains an unfavorable component such as gel, and its melt viscosity is significantly reduced. A method that deteriorates workability is not preferable.

The modified acid-modified block copolymer with a silane compound is silane-modified with a specific silane compound to obtain a silane-modified block copolymer.

Specific silane compounds include those represented by the general formula R ¹
A silane compound represented by SiY ₃ (R ¹ represents a hydrocarbon group having an epoxy group or a hydrocarbonoxy group, and Y represents an organic functional group capable of being hydrolyzed) (hereinafter referred to as an epoxysilane compound). Used, eg 3
-Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3- (N, N-glycidyl) amino Propyl trimexisilane, 3- (N,
N-glycidyl) aminopropyldimethoxysilane, 3
-(N, N-glycidyl) aminopropyltriethoxysilane, N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (trimethoxy Silyl) propyl] amine, N-glycidyl-N, N-bis [3- (ethyldiethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (triethoxysilyl) propyl] amine and the like. Can be mentioned.

As the silane modification method of the acid-modified block copolymer, the acid-modified block copolymer and the epoxysilane compound are rolled, kneader, extruder, universal stirrer,
It suffices to mix and heat using solution mixing or the like. The reaction temperature may be a temperature at which the epoxy group can sufficiently react with the carboxylic acid or the acid anhydride, but specifically, it is 120 to 180.
The range of ° C is preferred. If the temperature is lower than 120 ° C., it takes a long time for denaturation, or an undenatured product remains. Further, when the temperature exceeds 180 ° C., the evaporation of the epoxysilane compound is remarkable. However, if a catalyst such as a tertiary amine is used, the reaction can be carried out at a lower temperature or in a shorter time.

The silane-modified block copolymer of the present invention is
Since the polarity is higher than that of a conventional silane-modified block polymer, specifically, one obtained by graft-reacting vinyl silane with a block copolymer, the adhesiveness is good. The epoxysilane compound grafted to the silane-modified block copolymer of the present invention is hydrolyzed in the presence of water to cause a cross-linking reaction between the compounds, thereby increasing the heat-resistant cohesive force. Further, it also reacts with the surface of the adherend, and the strength of the adhesive is increased. Examples of the silanol condensation reaction catalyst include dibutyltin dilaurate, dibutyltin diacetate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethylamine, dibutylamine, and fatty acids. The silanol condensation reaction is initiated by moisture in the air after the silane-modified block copolymer adhesive of the present invention is heat-sealed to the adherend.

With respect to the silane-modified block copolymer of the present invention, rosins, terpene-based resins, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, and phenol-based resins are used for the purpose of improving adhesiveness and adjusting melt viscosity. A tackifying resin such as a resin or coumarone indene resin may be added, and these tackifying resins may be added in an amount of 0 to 300 parts by weight based on 100 parts by weight of the block copolymer, if necessary. Is added. Further, fillers such as calcium carbonate, clay, talc or titanium oxide; fluidity regulators such as naphthene-based, aroma-based and paraffin-based oils; plasticizers such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP); oxidation. An inhibitor or the like can be added to the block copolymer or the like, if necessary.

The adhesive for synthetic resin linings according to the second aspect of the present invention is preferably used when a synthetic resin lining pipe is manufactured by a swelling method or a diameter reducing method, and has the general formula AB -A or AB (wherein A represents a block substantially consisting of a monovinyl-substituted aromatic compound polymer and B represents a block substantially consisting of a diolefin polymer), and monovinyl-substituted. Aromatic compound polymer content 10-70% by weight, weight average molecular weight 5
Graft block of a modified block copolymer obtained by grafting an epoxy group-containing unsaturated compound in an amount of 0.01 to 20% by weight onto a block copolymer in the range of 000 to 500000 or at least one of these hydrogenated products. Is further modified with a silane compound represented by the general formula R ² SiY ₃ (R ² represents a hydrocarbon group having an amino group or a hydrocarbonoxy group, and Y represents a hydrolyzable organic functional group). It is characterized by

Block copolymer or hydrogenated product thereof In the present invention, the same block copolymer as used in the invention of claim 1 of the present application is used as the block copolymer or hydrogenated product thereof. To be done.

Modified block copolymer The block copolymer is prepared by grafting an epoxy group-containing unsaturated compound in the range of 0.01 to 30% by weight so as to obtain an epoxy modified block copolymer (hereinafter referred to as an epoxy modified block copolymer). ) Is said.

As the epoxy group-containing unsaturated compound, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether and the like are used. In the epoxy-modified block copolymer,
The content of the grafted epoxy group-containing unsaturated compound component is 0.01 to 20% by weight, preferably 0.0
It is 5 to 10% by weight. The reason why the amount is 0.01% by weight to 20% by weight is that if the amount is less than 0.01% by weight, the effect of silane modification is small, and if the amount is more than 20% by weight, the polarity of the elastic block becomes high to form a two-phase structure. This is because there is a risk of hindrance.

The epoxy-modified block copolymer is a block copolymer obtained by keeping the block copolymer and the epoxy group-containing unsaturated compound in a molten state or a solution state, with or without using a radical initiator. It is obtained by grafting an unsaturated compound containing an epoxy group on. The method for producing these epoxy-modified block copolymers is not particularly limited in the present invention, but the obtained epoxy-modified block copolymer contains an unfavorable component such as gel, and its melt viscosity is significantly reduced. A method that deteriorates workability is not preferable.

The modified epoxy-modified block copolymer with a silane compound is silane-modified with a specific silane compound to obtain a silane-modified block copolymer. Specific silane compounds include the general formula R ² S
A silane compound represented by iY ₃ (R ² represents a hydrocarbon group having an amino group or a hydrocarbonoxy group, and Y represents an organic functional group capable of being hydrolyzed) (hereinafter referred to as an aminosilane compound) is used. To be done.

Examples of aminosilane compounds include N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylethyldiethoxysilane, p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, p- [N- (2-
Aminoethyl) aminomethyl] phenethylmethyldimethoxysilane, N, N-bis [(methyldimethoxysilyl) propyl] amine, N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N
-Bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (trimethoxysilyl) propyl] amine, N- [3-trimethoxysilyl) propyl] diethylenetriamine, N-[(3- Trimethoxysilyl) propyl] triethylenetetramine, N-3-trimethoxysilylpropyl-m-phenylenediamine, N-3-methyldimethoxysilylpropyl-m-phenylenediamine and the like are used.

The silane modification method of the epoxy group-modified block copolymer includes an epoxy-modified block copolymer,
Roll with aminosilane compound, kneader, extruder,
Mixing and heating may be performed using a universal stirrer, solution mixing, or the like. The reaction temperature may be a temperature at which the epoxy group and the amino group can sufficiently react, but specifically, 120 to 180 ° C.
Is preferred. If the temperature is lower than 120 ° C., it takes a long time for denaturation, or an undenatured product remains. Further, when the temperature exceeds 180 ° C., the evaporation of the aminosilane compound is remarkable. However, if a catalyst such as a tertiary amine is used, the reaction can be carried out at a lower temperature or in a shorter time.

The silane-modified block copolymer of the present invention is
Since the polarity is higher than that of a conventional silane-modified block polymer, specifically, one obtained by graft-reacting vinyl silane with a block copolymer, the adhesiveness is good.

The aminosilane compound grafted to the silane-modified block copolymer of the present invention is hydrolyzed in the presence of water to cause a cross-linking reaction between them, thereby enhancing the heat-resistant cohesive force. Further, it also reacts with the surface of the adherend, and the strength of the adhesive is increased. As the silanol condensation reaction catalyst, the same one as used in the invention of claim 1 of the present application is used.

To the silane-modified block copolymer of the present invention, the same tackifying resin and filler as in the invention of claim 1 of the present application may be added for the purpose of improving adhesiveness and adjusting melt viscosity. it can.

Further, the invention described in claim 3 is a synthetic resin lining pipe in which a synthetic resin pipe is attached to an inner surface of a metal pipe by using the adhesive for synthetic resin lining according to claim 1 or 2. Is.

In the present invention, as the metal tube, iron,
A tube made of what is generally called a metal such as steel, stainless steel, aluminum, copper, zinc, etc. is used. The inner surface where the synthetic resin tube of the metal tube is pasted together is sandblasted,
It is preferable to perform a treatment for removing an oxide film such as rust with hydrochloric acid, sulfuric acid, nitric acid or the like, or a degreasing treatment with an alkali or the like so as to obtain a state suitable for adhesion to the synthetic resin pipe. Also, a known adhesion promoter such as a primer may be applied.

In the present invention, as the synthetic resin for the synthetic resin pipe, a thermoplastic resin having a high adhesive property with the adhesive for the synthetic resin lining is preferably used, and examples thereof include polyvinyl chloride, polyester, acrylic resin and ethylene. Vinyl acetate copolymer, silane-modified polyethylene, carboxylic acid-modified polyethylene, polyvinyl acetal and the like are used.

[0034]

The adhesive for synthetic resin linings according to the inventions of claims 1 and 2 of the present application is constituted by using the above-mentioned specific silane-modified block copolymer, and the silane-modified block copolymer has a moisture content. Since it undergoes hydrolysis and undergoes a crosslinking reaction in the presence of, it has excellent heat-resistant cohesive strength. Therefore,
When used in the production of synthetic resin lining pipes, the heat-resistant cohesive force of the bonded portion between the synthetic resin pipe and the metal pipe is enhanced, and it also reacts with the surface of the metal pipe and the synthetic resin pipe, and the adhesive and adherend The adhesive strength with the surface is increased. Therefore, the durable adhesion between the synthetic resin pipe and the metal pipe is significantly enhanced by the silane-modified block copolymer adhesive.

The synthetic resin lining pipe of the invention described in claim 3 is formed by bonding the synthetic resin pipe to the inner surface of the metal pipe using the adhesive for synthetic resin lining according to claim 1 or 2. As a result, the heat-resistant cohesive force of the bonded portion between the synthetic resin pipe and the metal pipe is increased, and it also reacts with the surfaces of the metal pipe and the synthetic resin pipe, and the adhesive strength between the adhesive and the surface of the adherend is high. Therefore, the durable adhesion between the synthetic resin pipe and the metal pipe is excellent.

EXAMPLES The present invention will be clarified by giving Examples and Comparative Examples of the present invention. Example 1 100 parts by weight of 2% by weight maleic anhydride-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec M1913, styrene content: about 30% by weight, molecular weight: about 50,000) and 3-glycidoxypropyltrimethoxy 5 parts by weight of silane was added, and the mixture was heat-melt mixed at a temperature of 150 ° C., and an epoxysilane compound was grafted on maleic anhydride-modified SEBS to obtain a silane-modified block copolymer 1.

Next, the silane-modified block copolymer 1 and
The other components were blended in the following proportions and heat-melted and kneaded at a temperature of 150 ° C. to obtain a hot-melt adhesive. Silane-modified SEBS (silane modified copolymer 1) ... 100 parts by weight of C ₅ petroleum resin (manufactured by Nippon Zeon Co., Ltd., trade name: Quintone D200) ... 30 parts by weight of dibutyltin dilaurate ... 0.01 parts by weight

Example 2 To 100 parts by weight of 2% by weight maleic anhydride-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., Tuftec M1913), 10 parts by weight of 3-glycidoxypropyltrimethoxysilane was added, and the mixture was heat-melted at a temperature of 150 ° C. The mixture was mixed and an epoxysilane compound was grafted to obtain a silane-modified block copolymer 2. Next, instead of the silane-modified block copolymer 1,
A hot melt adhesive was obtained in the same manner as in Example 1 except that the silane modified block copolymer 2 was used.

Example 3 2 wt% maleic anhydride-modified SEPS (Kuraray Co., trade name: Septon KL-02-2, styrene content about 30)
% By weight, molecular weight: about 50,000) To 100 parts by weight, add 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and
A silane-modified block copolymer 3 was obtained by hot-melt mixing at a temperature of 50 ° C. and grafting with an epoxysilane compound.
Next, a hot melt adhesive was obtained in the same manner as in Example 1 except that the silane modified block copolymer 3 was used in place of the silane modified block copolymer 1.

Example 4 To 100 parts by weight of 2% by weight maleic anhydride-modified SEPS (manufactured by Kuraray Co., Ltd., trade name: Septon KL-02-2), 3
Add 10 parts by weight of glycidoxypropyltrimethoxysilane, heat melt mix at a temperature of 150 ° C., graft with an epoxysilane compound, and then silane-modified block copolymer 4
Got Next, a hot melt adhesive was obtained in the same manner as in Example 1 except that the silane modified block copolymer 4 was used instead of the silane modified block copolymer 1.

Comparative Example 1 SEBS (manufactured by Asahi Kasei Corporation, trade name: Tuftec H10
41, styrene content about 30% by weight, molecular weight: about 50,000)
To 100 parts by weight, 3.5 parts by weight of vinyltrimethoxysilane and 0.2 parts by weight of dicumyl peroxide were added, and 1
A silane-modified block copolymer 5 was obtained by hot-melt mixing at a temperature of 50 ° C. and grafting with a vinylsilane compound.
Next, a hot melt adhesive was obtained in the same manner as in Example 1 except that the silane modified block copolymer 5 was used in place of the silane modified block copolymer 1.

Comparative Example 2 100 parts by weight of 2% by weight maleic anhydride-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1913),
30 parts by weight of a C ₅ petroleum resin (manufactured by Nippon Zeon Co., Ltd., product name: Quinton D200) was melt-kneaded at a temperature of 150 ° C. to obtain a hot-melt adhesive.

Comparative Example 3 100 parts by weight of 2% by weight maleic anhydride-modified SEPS (Kuraray Co., trade name: Septon KL-02-2) and C ₅
Petroleum resin (manufactured by Zeon Corporation, trade name: Quinton D2)
00) 30 parts by weight are melt-kneaded at a temperature of 150 ° C.,
A hot melt adhesive was obtained.

Example 5 Epoxy-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec Z-513, styrene content about 30% by weight, molecular weight: about 50,000, epoxy modification: 0.1 mmol / g)
To 100 parts by weight, 2 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added,
The mixture was heat-melt mixed at a temperature of ° C, and the aminosilane compound was grafted onto the epoxy-modified SEBS to obtain a silane-modified block copolymer 6.

Next, the silane-modified block copolymer 6 and
The other components were blended in the following proportions and heat-melted and kneaded at a temperature of 150 ° C. to obtain a hot-melt adhesive. Silane-modified SEBS (silane-modified copolymer 6) ... 100 parts by weight C ₅ petroleum resin (manufactured by Zeon Corporation, trade name: Quinton D200) ... 30 parts by weight dibutyltin dilaurate ... 0.01 parts by weight

Example 6 1 part by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added to 100 parts by weight of epoxy-modified SEBS (manufactured by Asahi Chemical Industry Co., Ltd., trade name: Tuftec Z-513). The silane-modified block copolymer 7 was obtained by hot-melt mixing at a temperature of 150 ° C. and grafting the aminosilane compound on the epoxy-modified SEBS. Next, a hot melt adhesive was obtained in the same manner as in Example 5 except that the silane modified block copolymer 7 was used in place of the silane modified block copolymer 6.

Example 7 2 parts by weight of N- (2-aminoethyl) -3-aminopropyltriethoxysilane was added to 100 parts by weight of epoxy-modified SEBS (manufactured by Asahi Kasei Kogyo KK, trade name: Tuftec Z-513). The aminosilane compound was grafted onto the epoxy-modified SEBS by hot-melt mixing at a temperature of 150 ° C. to obtain a silane-modified block copolymer 8. Next, a hot melt adhesive was obtained in the same manner as in Example 5 except that the silane modified block copolymer 8 was used instead of the silane modified block copolymer 6.

Example 8 1 part by weight of 3-aminopropyltriethoxysilane was added to 100 parts by weight of epoxy-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec Z-513), and the mixture was heat-melt mixed at a temperature of 150 ° C. The aminosilane compound was grafted onto the epoxy-modified SEBS to obtain a silane-modified block copolymer 9. Next, a hot melt adhesive was obtained in the same manner as in Example 5 except that the silane modified block copolymer 9 was used in place of the silane modified block copolymer 6.

Comparative Example 4 100 parts by weight of epoxy-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec Z-513) and C ₅ petroleum resin (manufactured by Nippon Zeon Co., Ltd., trade name: Quinton D200) 30
Part by weight was melted and kneaded at a temperature of 150 ° C. to obtain a hot melt adhesive.

For each of the hot melt adhesives of Examples 1 to 8 and Comparative Examples 1 to 4 prepared as described above, the following two types of (1) small test piece adhesiveness evaluation and (2) lining pipe test were carried out. Adhesive performance was evaluated by the test method of.

(1) Adhesion evaluation of small test piece Tensile shear strength Chlorinated vinyl chloride plate of 25 mm × 100 mm × 4 mm thickness as an adherend and 25 mm × 125 mm × thickness of 1.5
mm JIS G 3141 cold-rolled steel sheet was prepared, and the thickness of the adhesive layer was 100 using these adhesives.
˜150 μm, the bonding area was 2 × 2.5 cm, and the substrates were bonded together, and a pressure of ² kg / cm ² was applied at a temperature of 150 ° C. to bond them. After bonding, the initial normal-state adhesiveness was evaluated by measuring the tensile shear strength. In addition, the step of immersing the above-mentioned adhesive in cold water of 23 ° C for 5 minutes and then in hot water of 85 ° C for 5 minutes is set as one cycle, and after 1000 cycles, the tensile shear strength is similarly measured at 23 ° C. did. The peeling speed was 50 mm / min. The results are shown in Tables 1 and 2.

90 ° Peeling Test-a ... As an adherend, 25 mm × 125 mm × 1.6 mm thick JIS G3141 cold rolled steel plate, and 25
mm x 125 mm x 1.6 mm thick cotton canvas (No. 9) is prepared, and both are adhered so that the adhesive has a thickness of about 100 to 150 μm and the adhesion area is 25 x 100 mm. 2 kg / cm ² at a temperature of 150 ° C
Was applied to bond them. About the obtained adhesive,
By performing a 90 ° peel test (measurement temperature 23 ° C),
The initial normal state adhesiveness was evaluated. Further, after immersing the above-mentioned adhesive in hot water of 85 ° C. for 3 days, a 90 ° peeling test (measurement temperature 23 ° C.) was performed again, and the adhesiveness after dipping in hot water was evaluated. still,
The peeling speed was 50 mm / min. The results are shown in Tables 1 and 2.

B ... 25 mm × 100 as an adherend
mm × 4 mm thick chlorinated vinyl chloride plate (CPVC plate)
And a 25 mm x 125 mm x 0.6 mm thick cotton canvas (No. 9) are prepared, and the adhesive has a thickness of about 100 to 150 μm.
m and the bonding area is 25 × 80 mm, and the two are bonded together at a temperature of 150 ° C. of 2 kg /
A pressure of cm ² was applied to bond them. A 90 ° peel test was performed on the obtained adhesive to evaluate the initial normal-state adhesiveness (measurement temperature 23 ° C). Also, after immersing the above-mentioned adhesive in hot water at 85 ° C for 3 days, taking it out, and drying under reduced pressure at a temperature of 50 ° C for 8 hours, and then performing a 90 ° peel test again, the adhesiveness after hot water immersion (measurement temperature : 23 ° C.) was evaluated. The peeling speed was 50 mm / min. The results are shown in Tables 1 and 2.

(2) Lining Tube Test Production and Evaluation of Lining Tube by Diameter Reduction Method Thickness of 10 mm on the outer peripheral surface of a chlorinated vinyl chloride tube having an outer diameter of 52 mm.
The adhesive is applied so that the inner diameter becomes 0 to 150 μm, and the inner diameter 53
After inserting into a mm steel pipe and reducing the diameter of the steel pipe with a roll,
It was aged at 0 ° C for 2 hours to manufacture a synthetic resin lining steel pipe. Next, regarding the obtained synthetic resin lining steel pipe,
The initial adhesiveness was evaluated by a percussion method. That is, the inner surface of CPVC was tapped with a tapping rod, and the presence or absence of an adhesive defect was examined by the tapping sound. In addition, the synthetic resin lining pipe thus prepared was immersed in cold water at 23 ° C. for 5 minutes and immersed in hot water at 85 ° C. for 5 minutes, which was set as one cycle. After 100 cycles, the adhesion state was evaluated by a percussion method. The adhesiveness was evaluated after the thermal cycle test. The results are shown in Tables 3 and 4.

Production of lining pipe by swelling method and its
Evaluation of the outer diameter of chlorinated vinyl chloride pipe with an outer diameter of 49 mm
Adhesive is applied so that the inner diameter is from 0 to 150 μm, and the inner diameter is 5
After being inserted into a 0 mm steel pipe, it was heated to a temperature of 150 to 190 ° C. and the inside of the chlorinated vinyl chloride pipe was pressed to produce a synthetic resin lining steel pipe. The initial adhesiveness of the obtained synthetic resin-lined steel pipe was evaluated by a percussion method. Further, a cooling / heating cycle test was conducted in the same manner as in the diameter reduction method, and the adhesiveness after the cooling / heating cycle test was evaluated by a percussion method. The results are shown in Tables 3 and 4.

[0055]

[Table 1]

[0056]

[Table 2]

In Tables 1 and 2, the interface between the bonded portions after the tensile shear strength and 90 ° peeling test was broken. Further, (*) in Tables 1 and 2 means that the adhesive portion was spontaneously peeled off before the adhesion test.

[0058]

[Table 3]

[0059]

[Table 4]

In Tables 3 and 4, the adhesion evaluation symbols have the following meanings. ◯: There is no peeling at the bonded portion. Δ: A state where a part of the adhesive portion is peeled off. ×: A state in which peeling has occurred over almost the entire adhesive area.

As is clear from Tables 1 and 3, in the adhesive containing the silane-modified block copolymer as a main component, the acid group of the acid-modified block copolymer was graft-modified with an epoxysilane compound. Compared to the case of using the adhesive of the comparative example, the small test piece is superior in adhesiveness, and when a synthetic resin lining pipe was produced, even after repeating the thermal cycle test, the steel pipe and chlorinated chloride It can be seen that almost no peeling occurred between the vinyl tube and the vinyl tube, indicating good durable adhesion.

As is clear from Tables 2 and 4, in the adhesive containing the silane-modified block copolymer of Example as a main component, the epoxy group of the epoxy-modified block copolymer was graft-modified with the aminosilane compound. Compared to the case of using the adhesive of the comparative example, the small test piece is superior in adhesiveness, and when a synthetic resin lining pipe was produced, even after repeating the thermal cycle test, the steel pipe and chlorinated chloride It can be seen that almost no peeling occurred between the vinyl tube and the vinyl tube, indicating good durable adhesion.

[0063]

As described above, since the synthetic resin lining adhesives according to the first and second aspects of the present invention are configured as described above, it is possible to bond the synthetic resin pipe to the metal pipe. When used, the grafted silane compound reacts with other silane compounds after adhesion, thereby significantly improving heat resistance and water resistance adhesion strength. Therefore, according to the present invention, it becomes possible to provide a synthetic resin lining pipe in which the durable adhesion between the synthetic resin pipe and the metal pipe is effectively enhanced.

Further, in the adhesive using the silane-modified block copolymer of the present invention, after the synthetic resin pipe and the metal pipe are adhered, distortion due to the difference in expansion coefficient between the synthetic resin pipe and the metal pipe is effective. Be absorbed. Therefore, claim 3 of the present application
In the invention of (1), a synthetic resin lining tube having excellent durability and adhesion was obtained.

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Claims (3)

[Claims] 1. A compound represented by formula A-B-A or A-B (however, A
Shows a block consisting essentially of a monovinyl-substituted aromatic compound polymer, and B represents a block consisting essentially of a diolefin polymer. ), A block copolymer having a monovinyl-substituted aromatic compound polymer content of 10 to 70% by weight and a weight average molecular weight of 5,000 to 500,000, or at least one of these hydrogenated compounds, and an unsaturated carboxylic acid Acid or unsaturated carboxylic acid anhydride 0.01 ~
The graft block of the modified block copolymer grafted in the range of 30% by weight is further represented by the general formula R ¹ SiY ₃ (R
¹ represents a hydrocarbon group having an epoxy group or a hydrocarbonoxy group, and Y represents a hydrolyzable organic functional group. ) A synthetic resin lining adhesive which is modified with a silane compound. 2. A general formula A-B-A or A-B (provided that A
Shows a block consisting essentially of a monovinyl-substituted aromatic compound polymer, and B represents a block consisting essentially of a diolefin polymer. ), A block copolymer having a monovinyl-substituted aromatic compound polymer content of 10 to 70% by weight and a weight average molecular weight of 5,000 to 500,000 or at least one of these hydrogenated compounds, and an epoxy group-containing compound. The graft block of the modified block copolymer obtained by grafting the unsaturated compound in the range of 0.01 to 20% by weight is further added with a general formula R ² SiY ₃ (R ² is a hydrocarbon group having an amino group or a hydrocarbonoxy group. Indicates
Y represents a hydrolyzable organic functional group. ) A synthetic resin lining adhesive which is modified with a silane compound. 3. A synthetic resin lining pipe, characterized in that a synthetic resin pipe is attached to the inner surface of the metal pipe by using the adhesive for synthetic resin lining according to claim 1 or 2.