JP3452603B2 - Manufacturing method of synthetic resin lining tube - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to
How to manufacture a synthetic resin lined pipe lined with a resin pipe
Method, especially by devising an adhesive
Synthetic resin linei that can increase the durable adhesiveness between the oil tube and the metal tube
The present invention relates to a method for manufacturing a ring tube. [0002] 2. Description of the Related Art Conventionally, a synthetic resin lining pipe has been used for an expansion method.
Or it is manufactured by a method called the diameter reduction method.
You. In the swelling method, for example, JP-A-56-55227
, JP-A-58-12720, JP-A-59-5959
No. 418, between a metal tube and a synthetic resin.
The synthetic resin tube is heated and pressurized with the adhesive
The metal tube is pressed against the metal tube by expanding the diameter.
The inner peripheral surface is bonded to the outer peripheral surface of the synthetic resin tube. [0003] On the other hand, in the diameter reduction method, a metal pipe and a synthetic resin pipe are used.
With the adhesive interposed between the metal tube and roll
Reduce the diameter, press the metal tube to the synthetic resin tube,
Is bonded between the inner peripheral surface and the outer peripheral surface of the synthetic resin tube. A conventional synthetic resin lining tube as described above
In the production method described in JP-A No.
No. 55227, polyamide-based or poly-
Ester-based adhesives, described in JP-A-58-12720
Butadiene-styrene block copolymer elastomer
Stomer hot melt adhesive or unsaturated aliphatic
Polyolefin copolymerized with carboxylic acid or its anhydride
Adhesives and the like have been used. [0005] SUMMARY OF THE INVENTION
Mid or polyester adhesive or unsaturated fat
Polyolefin copolymerized with aromatic carboxylic acid or its anhydride
Using the adhesive containing
Heat resistant and hot water resistant,
In addition, there is a problem with the durable adhesion to metal pipes.
-Styrene block copolymer elastomer hot
Synthetic resin lath obtained in the same manner using
In the case of inning tubes, there is no major problem with heat resistance and hot water resistance.
No durable adhesion to synthetic resin tubes, especially at low temperatures
When dropped onto a synthetic resin tube, the synthetic resin tube peels off from the interface
And so on. Also, a conventional method of manufacturing a synthetic resin-lined pipe.
Method, using a solvent-type adhesive as the adhesive
May cause the working environment to be contaminated by organic solvents or
Requires a lot of work space and processes
There was also a problem. An object of the present invention is to provide a conventional synthetic resin lining.
To solve the problems of the manufacturing method of plastic pipes,
Of synthetic resin-lined pipe that can improve durable adhesion with steel
It is to provide a method. [0008] SUMMARY OF THE INVENTION The present invention provides a metal tube and a metal tube.
With an adhesive between the metal tube and the synthetic resin tube
In the state where it is present, expand the synthetic resin tube or use a metal tube.
In the method of manufacturing a synthetic resin lining tube for reducing the diameter of
Hot melt adhesive based on saturated polyester
(Y) is interposed on the outer peripheral surface side of the synthetic resin pipe, and the general formula A-
BA or AB (where A is substantially a monovinyl residue)
B represents a block composed of a substituted aromatic compound polymer,
A block qualitatively composed of an olefin polymer is shown. )so
Wherein the monovinyl-substituted aromatic compound polymer content is 1
0-70% by weight, weight average molecular weight 5,000-10
000 block copolymer or hydrogenated product thereofIn
Carboxylic acid group, acid anhydride group or epoxy group
What you have in your child(Less than,As appropriate, Block copolymer
U) with the main componentRubber compatible with a softening point of 70 to 150 ° C
Terpene with a tackifying resin and a softening point of 120 to 160 ° C
Contains phenolic resinHot melt adhesive (X) with gold
Manufacture of synthetic resin-lined pipe interposed on the inner peripheral surface side of the pipe
Manufacturing method. In the present invention, the metal tube is, for example,
Examples include a steel pipe and an aluminum pipe. The synthetic resin pipe used in the present invention includes:
PVC pipe, chlorinated PVC pipe, polyethylene
Resin tubes, polypropylene resin tubes, and the like can be given. Again
Some synthetic resin tubes have a foam layer on the outer periphery.
You. As a synthetic resin tube with a foam layer on the outer periphery, foam
Extrusion using a synthetic resin composition and a synthetic resin
It is manufactured by extrusion molding by a molding method or the like. Departure
As the foam layer, for example, polyethylene, polypropylene
Olefin resin foam, vinyl chloride resin foam, etc.
Body, polystyrene foam, polyurethane foam, etc.
Can be As the foam structure of the foam, the closed cell structure
Has better heat insulation and sound insulation than the open-cell structure.
Have been. In the present invention, the hot melt adhesive
The saturated polyester resin in (Y) is a saturated dicarboxylic acid
Component and glycol component by esterification.
Can be As the saturated dicarboxylic acid component, terephthalic
Acid, isophthalic acid, phthalic acid, 1,4-naphthalic acid,
Aromatic dicarboxylic acids such as 1,5-naphthalic acid, tet
Lahydrophthalic anhydride, 2,5-norbornanedicarbo
Acid, hetonic acid, oxalic acid, malonic acid, dimethylmalon
Acid, succinic acid, glutaric acid, adipic acid, pimerin
Acid, suberic acid, azelaic acid, sebacic acid, etc.
Aromatic dicarboxylic acids and the like can be mentioned. As the glycol component, ethylene glycol
, Diethylene glycol, triethylene glycol
, Polyethylene glycol, 1,2- or 1,3-p
Propylene glycol, polypropylene glycol, neo
Pentyl glycol, 1,3-, 1,4- or 2,3-
Butylene glycol, 1,5-pentanediol, 1,
6-hexanediol, 2-ethyl-1,3-hexane
Diol, 2,2,4-trimethyl-1,3-pentane
Diol, 1,4-cyclohexanedimethanol, poly
Examples include tetramethylene glycol and bisphenol A.
I can do it. The above-mentioned components are usually used in a saturated polyester resin.
150 ° C to 250 ° C under an inert gas atmosphere according to the method
About 220 to 280 ° C under reduced pressure
To produce a polycondensation. [0014] The saturated polyester resin targeted in the present invention
Has a molecular weight of 10,000 to 50,000 and an acid value of 0.5
~ 6 KOHmg / g. In the present invention, the hot melt adhesive
As the block copolymer in (X), for example, pig
Both ends of the diene polymer block (component B)
A structure having a structure in which a limmer block (A component) is bonded.
Tylene-butadiene-styrene block copolymer (SB
S) and the butadiene polymer portion of this SBS (B component)
Hydrogenation) (SEBS)
Or at both ends of the isoprene polymer block (component B)
Styrene polymer block (component A) bonded structure
Styrene-isoprene-styrene block copolymer having
Coalescence (SIS) and isoprene polymer part of this SIS
Hydrogenated (SEP)
S) etc.A carboxylic acid group, an acid anhydride group, or an epoxy group
The main component is one having a xy group in the molecule (hereinafter referred to as
A softening point of 70 to 150 ° C.
Having a softening point of 120 to 160 ° C.
Containing terpene phenolic resinIs mentioned
You. This polymer is a hard block of a styrene phase.
(A component) and an elastic block such as a butadiene phase
(B component). Hard block
If the content of (A component) is low, the elastic modulus and cohesive force of the resin
Lowers adhesive strength and heat resistance when used in adhesives
A problem arises in sex. Also contains hard block (A component)
If the modulus is too high, the modulus will be too high to lose flexibility.
It becomes a so-called hard adhesive and has fluidity and peeling when heated.
Strength decreases. Therefore, the component A in the block copolymer
Is 10 to 70% by weight, preferably 15% by weight.
~ 35% by weight. Average molecular weight of block copolymer
(Weight average) is 5,000 to 100,000. As the block copolymer, carboxylic acid
Having a group, acid anhydride group or epoxy group in the molecule
UsedUsed. Carboxylic acid group, acid anhydride group, or epoxy
Block copolymers having a siloxane group in the molecule are
To the copolymer, unsaturated carboxylic acid, its acid anhydride, or
Epoxy group-containing unsaturated compound in molten or solution state
, With or without the use of radical initiators
It can be obtained by raft polymerization. Examples of the unsaturated carboxylic acid include male
Formic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid
Carboxylic acids such as carboxylic acid and crotonic acid;
Examples of the hydrate include acid anhydrides of the above carboxylic acids.
However, dicarboxylic anhydrides are preferably used, and
Maleic acid is preferably used. As examples of epoxy group-containing unsaturated compounds
Is glycidyl acrylate, glycidyl methacrylate,
Glycidyl itaconate, allyl glycidyl ether, etc.
But with unsaturated and epoxy groups in the molecule
All compounds can be used. Carboxylic acid group, acid anhydride group, or epoxy
Carboxylic Acids in Block Copolymers Having Groups in the Molecule
The content of the group, acid anhydride group, or epoxy group is usually
0.01 to 30% by weight is preferred, and 0.05 to 10% by weight
% Is more preferred. When the content is less than 0.01% by weight
Shows almost no improvement in adhesion due to grafting.
If the amount exceeds 30% by weight, the effect of the graft is
No further improvement. In the present invention, the hot melt adhesive
(X) contains a rubber-compatible adhesive having a softening point of 70 to 150 ° C.
Resin and a terpene pheno having a softening point of 120 to 160 ° C.
Containing resinYou. Adhesion of rubber compatible with a softening point of 70 to 150 ° C
The resin is an elastic block of a block copolymer (component B).
And has the effect of increasing its adhesiveness. softening
If the point is lower than 70 ° C., the hot melt adhesive (X) has
Thermal properties are apt to decrease, and conversely, if it is higher than 150 ° C,
Tackiness or adhesiveness is hardly developed. Adhesion of rubber compatible with a softening point of 70 to 150 ° C
Examples of the resin include, for example, an alicyclic petroleum resin and an aliphatic stone.
Oil resins, terpene resins and the like can be mentioned. Softening point 70-1
The addition amount of the rubber-compatible tackifying resin at 50 ° C.
5 to 50 parts by weight based on 100 parts by weight of the copolymer is preferred.
New As the softening point of terpene phenol resin
Is used having a softening point of 120 to 160 ° C. Soft
When the transition point is lower than 120 ° C., the hot melt adhesive (X)
Heat resistance tends to decrease, and conversely, it becomes higher than 160 ° C.
, It is difficult to develop tackiness or adhesiveness. Softening point
Is the amount of terpene phenol resin added at 120-160 ° C
Is 10 to 5 with respect to 100 parts by weight of the block copolymer.
0 parts by weight is preferred. In the present invention, the hot melt adhesive
In (X) and (Y), if necessary, calcium carbonate
, Barium phosphate, clay, talc or titanium oxide
Filler, naphthenic, aroma, paraffin oil, etc.
Fluidity modifiers such as dioctyl phthalate (DOP)
Plasticizers such as butyl phthalate (DBP), antioxidants, etc.
Can be contained. [0026] The method for producing a synthetic resin-lined pipe of the present invention comprises:
Hot melt adhesives based on saturated polyester
By interposing it on the outer peripheral surface side of the synthetic resin tube,
Of hot melt adhesive (Y) containing polyester
Durable adhesion such as cold shock resistance to synthetic resin pipes is improved, and
Hot-melt bonding mainly composed of block copolymer
By interposing the agent (X) on the inner peripheral side of the metal tube,
Heat resistance and hot water resistance of block copolymers to metal tubes
Since the durable adhesiveness is improved, the distance between the metal tube and the synthetic resin tube
For durable adhesive properties such as cold shock resistance, heat resistance and hot water resistance
An excellent synthetic resin lining tube can be obtained. [0027] EXAMPLES Examples and comparative examples of the present invention will be described below.
With this, the present invention is clarified.Examples 1 to 5, Comparative Examples 1 to 4 Table 1 shows the hot menus used in Examples 1 to 5 and Comparative Examples 1 to 4.
3 shows the composition of the base adhesives (X) and (Y). Table
1, the saturated poly in the hot melt adhesive (Y)
As the ester, Toyobo Co., Ltd., trade name "Byron G
M995 "[molecular weight: 25,000, melt viscosity: 6000 Ps
(200 ° C), melting point: 113 ° C, glass transition temperature: -2
0 ° C], and as a saturated polyester, Unitika
Product name "Unitika Elitel UE3800"
20,000, melt viscosity: 800 Ps (200 ° C), melt
Point: 133 ° C, glass transition temperature: -5 ° C]. Also, the hot melt adhesive shown in Table 1
2% by weight of the block copolymer in (X)
Water maleic acid-modified SEBS (trade name “Tough
Tech M1913, styrene content about 30% by weight, molecule
Amount: about 50,000), and as the block copolymer,
0.1 mmol / g epoxy-modified SEBS (Asahi Kasei Corporation)
Made, trade name "TUFTEC Z513", styrene content about
30%, molecular weight: about 50,000) using aliphatic saturated hydrocarbons
As the resin, “Arucon P-1” manufactured by Arakawa Chemical Co., Ltd.
00 "(softening point 100 ° C) using terpene phenol
As a resin, a product name “YS PO” manufactured by Yashara Chemical Co., Ltd.
Lister S-145 "(softening point 145 ° C) was used. E
Hot melt adhesive (X) hot melt kneading at 160 ° C for 10 minutes
Adjusted by [0029] [Table 1] The hot melt adhesives (A) and (B)
The following (1) small sample
Evaluation of specimen adhesion and (2) Lining tube test
The adhesion performance was evaluated by the test method. (1)Small specimen adhesion evaluation(90 ° peeling test
Experiment)   25mm x 125mm x thickness 1.6 as an adherend
mm JIS G3141 cold rolled steel plate and 25 mm x
Prepare a 125mm x 1.6mm thick canvas (No. 9)
Hot melt adhesive (X) (thickness: about 100
~ 150μm) and hot melt adhesive on top
(Y) (thickness: 50 to 100 μm) is applied, and
Attach the canvas and apply the temperature of 150 ℃ x 2kg / cm
^TwoUnder the conditions described below. Assessing them for initial normal adhesion,
And after immersion in hot water of 85 ° C for 3 days, 50 ° C x 6 hours
Dry under reduced pressure for 90 ° peel test (measuring temperature: 23 ° C, pull
(Stretching speed: 50mm / min)
The sex was evaluated. As an adherend, 25 mm × 100 mm
× 4mm thick chlorinated vinyl chloride resin plate and 25mm × 1
Prepare a 25mm × 1.6mm thick canvas (No. 9),
Hot melt adhesive on the chlorinated vinyl chloride resin plate surface
(Y) (thickness: 50 to 100 μm) is applied, and
Hot melt adhesive (X) (thickness: about 100-150μ)
m), and a canvas is stuck thereon, and the temperature is 150
℃ x pressurized 2kg / cm ^TwoUnder the conditions described below. Those
Initial normal adhesion evaluation (temperature at the time of measurement: 23 ° C.), and 8
After immersion in hot water at 5 ° C for 3 days, dry under reduced pressure at 50 ° C for 6 hours.
Dry and repeat 90 ° peel test (measuring temperature: 23 ° C tensile
(Velocity: 50 mm / min) to evaluate the adhesiveness after immersion in hot water
Valued. Table 2 shows the results. [0033] [Table 2] (2)Lining tube test(La by diameter reduction method
Production method of inning tube and its evaluation) On the outer peripheral surface of a chlorinated vinyl chloride resin tube (outer diameter: 52 mm)
Hot melt adhesive (Y) (thickness: 50-100 μm)
And hot-melt adhesive (X) (thickness:
(Approximately 100 to 150 μm), and apply
After reducing the diameter of the steel pipe with a roll,
Cured for 2 hours to produce a lining steel pipe. About the obtained lining steel pipe,
The evaluation of the adhesion was evaluated by the percussion method. That is, the obtained length
Leave 1m lining steel pipe in 0 ° C atmosphere for more than 5 hours
After that, let it fall freely on the concrete surface from the height of 1m,
Evaluation of adhesion between plastic tube and metal tube by percussion method
Was. In addition, 30 cm of the obtained lining steel pipe was
One cycle of 5 minutes of cold water immersion at 5 ° C and 5 minutes of hot water immersion at 85 ° C
And the adhesive state after 500 cycles is cooled by percussion.
The hot water immersion cycle durability was evaluated. These results
It is shown in Table 3. In Table 3, the mark “○” indicates that there was no peeling at the bonded portion.
Indicates that the adhesive part was partially peeled off.
Indicates that almost all of the bonded part is peeled off.
You. [0037] [Table 3] As is clear from Tables 2 and 3, the present invention
In the case of Examples 1 to 5, all of them were subjected to the 90 ° peel test.
Initial adhesion to metal and synthetic resin, durable adhesion
(85 ° C x 3 days later)
Initial adhesion and cold shock resistance or
Has excellent durability such as hot water resistance,
In the case of Comparative Examples 1-4, at least one of them was inferior.
I have. [0039] The method of manufacturing the synthetic resin-lined pipe of the present invention.
Since the method is configured as described above,
Cold shock resistance, heat resistance, hot water resistance, etc.
It is possible to obtain a synthetic resin lining tube with excellent durability
it can.

Claims (1)

(57) [Claims 1] In a state where an adhesive is interposed between a metal pipe and a synthetic resin pipe inserted into the metal pipe, whether or not the synthetic resin pipe is expanded in diameter. Alternatively, in a method for manufacturing a synthetic resin-lined pipe for reducing the diameter of a metal pipe, a hot melt adhesive (Y) containing a saturated polyester as a main component is interposed on the outer peripheral surface side of the synthetic resin pipe, and the general formula ABA or AB (where A
Represents a block substantially composed of a monovinyl-substituted aromatic compound polymer, and B represents a block substantially composed of an olefin polymer. A) 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 100,000 or a hydrogenated product thereof, , Acid anhydride
And those having an epoxy group in the molecule
And a rubber compatible tackifying resin having a softening point of 70 to 150 ° C.
With a terpene phenol resin having a softening point of 120 to 160 ° C
A method for producing a synthetic resin-lined pipe, characterized in that a hot melt adhesive (X) to be contained is interposed on the inner peripheral surface side of a metal pipe.