JP2019143003A - Resin composition and water stop material - Google Patents

Abstract

To provide a resin composition and a water stop material, which can sufficiently follow and come into intimate contact with an irregular surface such as the outer wall of a house under pressure (in the state of being pressed against the irregular surface) even when being applied to the irregular surface, can continue to express a following intimate contact property under the pressure for a long period, and can persistently secure excellent water-stop performance for a long period.SOLUTION: The resin composition satisfies the following (A) and (B): (A) a 25% compression modulus of 300 kPa or less; and (B) a relaxation modulus of 9.0 kPa or more after a lapse of 125 days at 30°C. The water stop material uses the resin composition described above. The water stop material includes the resin composition containing a thermoplastic elastomer, an acid-modified resin, and 80 to 310 pts.mass of a metal hydroxide and 160 to 460 pts.mass of a softening agent with respect to 100 pts.mass in total of the thermoplastic elastomer and the acid-modified resin.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a waterstop material.

The outer wall of the detached house is provided with a through hole for providing a ventilation opening, a water supply / distribution pipe, an air conditioner pipe, and a wiring. A penetration pipe is usually installed in the penetration portion, and a sealing material or the like is disposed in a gap between the outer wall and the penetration pipe, and the gap is sealed to prevent intrusion of rainwater or the like.
Further, in Patent Document 1, a flange member (head portion) having an elastic member is provided on a pipe installed in the outer wall penetrating portion, and this flange member is pressed against the outer wall with a screw to prevent water stoppage between the pipe and the wall surface. Techniques to ensure are disclosed.

Japanese Patent No. 5830455

Residential exterior walls are usually designed with siding or mortar. Therefore, even when applying the technique described in Patent Document 1, in order to increase the adhesion between the elastic member and the wall surface and ensure sufficient water stopping, the uneven design of the outer wall is dropped and a flat surface is provided. It was necessary to install a through pipe. Moreover, since a house generally resides for a long period of several decades, it is necessary to ensure the water-stopping between the through pipe and the outer wall for a long period of time.
Therefore, the present invention closely follows the unevenness under pressure (in a state where it is pressed against the uneven surface) even when the uneven surface is applied as it is to the uneven surface of a housing outer wall or the like without being processed. Resin composition and water stop which can be developed and can continue to express the follow-up adhesion under this pressure over a long period of time, and as a result, can exhibit excellent water stoppage for a long period of time The problem is to provide materials.

  In view of the above problems, the present inventors have prepared various resin compositions having elasticity and physical properties, and studied their water stopping performance. As a result, a resin composition that exhibits excellent followability to an uneven surface under pressure and can maintain this follow-up contact state for a long period of time has been prepared. As a result of studying the relationship between the physical properties of the resin composition and the water-stopping performance, the 25% compression modulus is small and has a certain degree of softness, while suppressing stress relaxation over time in a pressure-deformed state. It has been found that the above problems can be solved by the resin composition having the physical properties. The present invention has been further studied based on these findings and has been completed.

That is, the said subject was solved by the following invention.
[1]
Resin composition satisfying the following (A) and (B):
(A) 25% compression modulus is 300 kPa or less,
(B) The relaxation elastic modulus after 125 days at 30 ° C. is 9.0 kPa or more.
[2]
The resin composition according to [1], wherein the resin component constituting the resin composition includes a thermoplastic elastomer.
[3]
[2] The resin composition according to [2], wherein the thermoplastic elastomer includes a styrene-based thermoplastic elastomer.
[4]
The resin composition according to any one of [1] to [3], wherein the resin composition contains a softening agent.
[5]
[1] to [4], wherein the resin composition contains a metal hydroxide, and the resin component constituting the resin composition includes an acid-modified styrene-based thermoplastic elastomer and an acid-modified resin. Any resin composition.
[6]
The ratio of the acid-modified resin in the resin component constituting the resin composition is 10 to 40% by mass, and the metal hydroxide has a total content of 100 parts by mass of the resin component constituting the resin composition. The resin composition according to [5], wherein the content is 80 to 310 parts by mass.
[7]
The resin composition according to any one of [1] to [6], which is formed into a donut shape.
[8]
The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the outer diameter of the cylindrical pipe having a hole diameter of 37.1 mm at the end of the cylindrical axis is provided. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. When the water is put into a screwed state and water of 25 ° C. is put into the pipe up to a height of 10 cm, water leakage does not occur at 30 ° C. for 30 minutes or more, [1] to [7] of Fat composition.
[9]
The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the outer diameter of the cylindrical pipe having a hole diameter of 37.1 mm at the end of the cylindrical axis is provided. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged so that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate are placed until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. When the water is allowed to stand at 30 ° C. for 125 hours, and then 25 ° C. water up to a height of 10 cm is put into the pipe, no water leaks at 30 ° C. for 30 minutes or more. [1] Resin composition according to any one of to [8].
[10]
The resin composition according to any one of [1] to [9], which is used as a waterstop material.
[11]
Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of a softening agent for a total of 100 parts by mass of the thermoplastic elastomer, the acid-modified resin, the thermoplastic elastomer and the acid-modified resin. A waterstop material comprising a resin composition.
[12]
The waterstop material according to [11], wherein the thermoplastic elastomer includes a styrene-based thermoplastic elastomer.
[13]
The waterstop material according to [11] or [12], wherein a 25% compression modulus of the resin composition is 300 kPa or less.
[14]
The water blocking material is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the cylindrical pipe having a hole diameter of 37.1 mm has an outer diameter that the cylindrical pipe has at the cylindrical axial end. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. And [11] to [13], in which water is not leaked at 30 ° C. for 30 minutes or more when water of 25 ° C. is put into the pipe up to a height of 10 cm. of Water material.
[15]
The water blocking material is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the cylindrical pipe having a hole diameter of 37.1 mm has an outer diameter that the cylindrical pipe has at the cylindrical axial end. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. And when the water is allowed to stand at 30 ° C. for 125 hours and then water of 25 ° C. is added to the height of 10 cm in the pipe, no water leaks at 30 ° C. for 30 minutes or more. 11] ~ water stopping material according to any one of [14].

  Even when the resin composition and the water-stopping material of the present invention are applied to an uneven surface such as an outer wall of a house, they can closely follow the unevenness under pressure and can adhere to the uneven surface. Adhesion can continue to be developed over a long period of time, and thus excellent waterstop can be developed over a long period of time.

It is a front view which shows typically the state by which the test tool used for the water-stop test as described in an Example was assembled.

[Resin composition]
The resin composition of the present invention has specific properties such that the 25% compression modulus is 300 kPa or less and the relaxation modulus after 125 days at 30 ° C. is 9.0 kPa or more. When the 25% compression modulus is 300 kPa or less, a certain high unevenness followability is imparted to the resin composition. That is, it is possible to sufficiently enhance the follow-up adhesion to the uneven surface under pressure.
Moreover, when the relaxation elastic modulus after 125 days at 30 ° C. is 9.0 kPa or more, the stress relaxation with time in the pressure deformation state is suppressed, and a constant high stress can be expressed over a long period of time. Therefore, a resin composition that follows and adheres closely to the uneven surface by applying pressure can stably maintain the following contact state for a long period of time.
That is, the resin composition of the present invention realizes both of the contradictory properties (deformability) and elasticity, which are mutually contradictory properties, at an unprecedented high level. It has unique physical properties suitable as a water material.
The form of the resin composition of the present invention may be composed of a solid content without containing a solvent. Further, a form in which a resin component or the like is dissolved in a solvent and the solvent is volatilized during molding or the like may be used. In addition, even if the resin composition of this invention is a form containing a solvent, the value of the compression modulus and relaxation elastic modulus prescribed | regulated by this invention are the physical properties of the resin composition in the state except the solvent.

<25% compression modulus>
As described above, the resin composition of the present invention has a 25% compression modulus of 300 kPa or less. That is, it has a certain soft physical property and is excellent in the followability to the uneven surface under pressure.
In the resin composition of the present invention, the 25% compression modulus is preferably 270 kPa or less, more preferably 250 kPa or less, and further preferably 230 kPa or less. The 25% compression modulus is usually 30 kPa or more, and 40 kPa or more is practical.
The 25% compression modulus of the resin composition is measured according to JIS K 6254 method C. More specifically, it can be determined by the method described in Examples described later.

<Relaxation modulus after 125 days at 30 ° C.>
As described above, the resin composition of the present invention has a relaxation elastic modulus of not less than 9.0 kPa after 125 days at 30 ° C. That is, in the pressure deformation state, the stress relaxation over time can be suppressed and a certain elasticity can be maintained. As a result, the resin composition that has been applied to the uneven surface by applying pressure can be maintained in the following adhesion state for a long period of time.
The resin composition of the present invention preferably has a relaxation elastic modulus of 9.2 kPa or more after 125 days at 30 ° C. The relaxation elastic modulus is usually 100 kPa or less, practically 90 kPa or less, and preferably 80 kPa or less.
The relaxation modulus after 125 days at 30 ° C. can be measured according to the method described in paragraphs [0023] to [0025] of JP2013-134477A. More specifically, it can be determined by the method described in Examples described later.

<Ingredients of resin composition>
If the resin composition of this invention has the said characteristic, there will be no restriction | limiting in particular in the component composition. For example, the resin composition of the present invention can be obtained by using a thermoplastic resin as a base resin and, if necessary, blending softeners, fillers and the like, and blending conventional additives and the like as necessary.
In addition, it is also preferable that at least a part of the resin component described below constituting the resin composition is in an acid-modified form as described later.

(Resin component)
The resin composition of the present invention usually contains a thermoplastic resin as the resin component (polymer component), and it is preferable that all of the resin components are thermoplastic resins. The kind of the thermoplastic resin is not particularly limited as long as the resin composition having physical properties or characteristics defined in the present invention can be realized.
Preferable examples of the thermoplastic resin include polystyrene resin, polyurethane resin, polyamide resin, polyester resin and the like. Especially, it is preferable that the thermoplastic resin used for this invention contains a thermoplastic elastomer. The proportion of the thermoplastic elastomer in the thermoplastic resin in the resin composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, More preferably, it is 90 mass% or more, and it is also preferable that all the thermoplastic resins in the resin composition of the present invention are thermoplastic elastomers.
Examples of the thermoplastic elastomer include styrene-based, polyurethane-based, polyamide-based, and polyester-based elastomers, and one or more of these can be used. Hereinafter, the preferable form of the thermoplastic elastomer used for this invention is demonstrated.

− Styrenic thermoplastic elastomer −
Examples of the styrene thermoplastic elastomer include styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB, styrene-ethylene / butylene block copolymer), and styrene-butadiene-styrene block. Copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS, styrene-ethylene / butylene-styrene block copolymer), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene Block copolymer (SEP, styrene-ethylene / propylene block copolymer), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS, styrene- Styrene / propylene - styrene block copolymer) and the like, can be used alone or in combination of two or more thereof.

− Polyurethane thermoplastic elastomer −
Examples of the polyurethane-based thermoplastic elastomer include elastomers containing structural units of a hard segment composed of low-molecular glycol and diisocyanate and a soft segment composed of a high molecular (long chain) diol and diisocyanate.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 or more and less than 10,000.
As the low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number average molecular weight of the short-chain diol is preferably 48 or more and less than 500.
The resin composition of this invention can use the 1 type (s) or 2 or more types of a polyurethane-type thermoplastic elastomer.

− Polyamide based thermoplastic elastomer −
Examples of the polyamide-based thermoplastic elastomer include a multi-block copolymer in which the hard segment is polyamide and the soft segment is polyether or polyester. Examples of the hard segment include polyamide 6, 66, 610, 11, 12, and the like. Polyethers in the soft segment include polyethylene glycol, diol poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, and the like. Polyesters include poly (ethylene adipate) glycol and poly (butylene-1,4-adipate) glycol. Etc.
The resin composition of this invention can use the 1 type (s) or 2 or more types of a polyamide-type thermoplastic elastomer.

− Polyester thermoplastic elastomer −
Examples of the polyester-based thermoplastic elastomer include a high melting point polyester segment (hard segment) described in JP-A No. 11-92636 and a low melting point polymer segment (soft segment) having a molecular weight of about 400 to 6,000. Block copolymers can be used. Examples of the high melting point polyester segment include polybutylene terephthalate (PBT). Examples of the low melting point polymer segment include amorphous polyether having a glass transition temperature of −70 ° C., such as polytetramethylene ether glycol (PTMG).
The resin composition of this invention can use the 1 type (s) or 2 or more types of a polyester-type thermoplastic elastomer.

  Especially, it is preferable that the resin composition of this invention contains a thermoplastic elastomer and the said thermoplastic elastomer contains a styrene-type thermoplastic elastomer. As for the resin component which comprises the resin composition of this invention, it is preferable that the 50 mass% or more is comprised with the styrene-type thermoplastic elastomer, More preferably, it is 60 of the resin component which comprises the resin composition of this invention. It is preferable that at least 90% by mass, more preferably at least 70% by mass, further preferably at least 80% by mass, particularly preferably 90% by mass is composed of a styrenic thermoplastic elastomer. All of the resin components constituting the resin composition of the present invention may be styrene-based thermoplastic elastomers.

When the resin composition of the present invention is a form containing a metal hydroxide as will be described later, the resin composition of the present invention preferably contains one or more acid-modified resins as a thermoplastic resin. . Details of the reason will be described later.
In the present invention, “acid-modified” means not only the form in which an acid group is introduced, but also the form in which an acid anhydride group is introduced. Further, when the acid-modified resin used as a raw material is in a form into which an acid anhydride group has been introduced, after preparing a resin composition through kneading or the like, at least one of the acid anhydride groups in the composition. The part is hydrolyzed by moisture in the air and opened to form an acid group.
The acid modification is performed by graft reaction of an acid compound (compound having an acid group or an acid anhydride group), or by copolymerizing the acid compound as a monomer. In addition to the acid-modified resin having an acid group or an acid anhydride group as a polar group, another polar group may be introduced.

The acid compound used for acid modification of the resin is preferably an organic acid compound or an acid anhydride compound, and more preferably a compound having a dicarboxylic acid anhydride structure.
Examples of the compound having a dicarboxylic acid anhydride structure include aromatic polyvalent carboxylic acids and aliphatic polyvalent carboxylic acid anhydrides. Among these, a compound having a structure in which a dicarboxylic anhydride structure forms a ring is preferable, and a compound having a structure in which two adjacent carboxy groups of an aromatic polyvalent carboxylic acid are dehydrated and condensed is more preferable. When the dicarboxylic acid anhydride structure forms a ring, this ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

  Preferable examples of the acid compound used for acid modification of the resin include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, phthalic anhydride, 4-methylphthalic anhydride, 4-chlorophthalic anhydride, 4-tert-butylphthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, tetrafluorophthalic anhydride, anhydrous Examples thereof include tetrabromophthalic acid, trimellitic anhydride, and pyromellitic anhydride. Among them, maleic anhydride, 4,4′-carbonyldiphthalic anhydride, 4,4′-oxydiphthalic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, and 4,4 ′ -Acid compounds selected from biphthalic anhydride are preferred.

  The resin serving as the base of the acid-modified resin (resin before being acid-modified) is not limited as long as the effects of the present invention are not impaired. For example, an elastomer resin having a high elastic modulus (for example, the above-described thermoplastic elastomer resin) can be suitably used. A polyolefin resin having a low elastic modulus can also be used.

Preferable examples of the acid-modified resin include acid-modified polyolefin resin. Specific examples of the acid-modified polyolefin resin include acid-modified polyethylene and acid-modified polypropylene.
Also suitable are acid-modified ethylene-propylene copolymers, acid-modified ethylene-α-olefin copolymers (ethylene-vinyl acetate copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, etc.). Can be used.
Another preferred example of the acid-modified resin is an acid-modified polystyrene resin. The acid-modified polystyrene resin is preferably an acid-modified styrene thermoplastic elastomer. Specific examples include acid-modified styrene-ethylene / butylene-styrene block copolymers (hereinafter referred to as acid-modified SEBS), acid-modified styrene-butadiene-styrene block copolymers (hereinafter referred to as acid-modified SBS), and the like. .
Of the acid-modified resins, acid-modified styrene thermoplastic elastomers such as acid-modified SEBS and acid-modified SBS are particularly preferable.
Acid-modified SEBS is obtained by modifying an ethylene / butylene block in a styrene-ethylene / butylene-styrene block copolymer with an acid compound. Acid-modified SBS is obtained by modifying a butadiene component in a styrene-butadiene-styrene block copolymer with an acid compound.
The acid-modified resin has a larger interaction with the metal hydroxide than the unmodified resin. Such an acid-modified resin can be synthesized by a conventional method, and a commercially available product can also be used. For example, Tuftec M1911 (trade name, manufactured by Asahi Kasei Chemicals) and the like are commercially available as acid-modified SEBS.

(Metal hydroxide)
The resin composition of the present invention can contain a metal hydroxide. By containing a metal hydroxide, it becomes possible to suppress stress relaxation of the resin composition. This stress relaxation inhibiting action by the metal hydroxide becomes more apparent when the resin composition contains an acid-modified resin. This is because the acid group of the acid-modified resin interacts with the hydroxyl group of the metal hydroxide (hydrogen bond interaction or ester bond formation), and the acid-modified resin is physically and chemically treated by the metal oxide. This is considered to be due to the fact that the molecular movement of the acid-modified resin is restricted. From this viewpoint, the metal constituting the metal hydroxide is preferably a polyvalent metal, more preferably a divalent or trivalent metal, and more preferably a divalent metal.
From the viewpoint of more effectively expressing such a stress relaxation suppressing action, the ratio of the acid-modified resin to the total of the resin components constituting the resin composition of the present invention is 10 to 40% by mass (preferably 15 to 35% by mass). %), And the content of the metal hydroxide is preferably 80 to 310 parts by mass with respect to 100 parts by mass in total of the content of the resin components constituting the resin composition of the present invention. By setting the amount of the metal hydroxide within the above range, it is easier to extend and the physical properties can be higher. The resin other than the acid-modified resin occupying the resin component constituting the resin composition of the present invention is preferably the thermoplastic resin described above (not acid-modified).

  Examples of the gold hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, manganese hydroxide, zinc hydroxide, copper hydroxide (II), iron hydroxide (II), iron hydroxide (III) and the like. 1 type, or 2 or more types of these can be used.

(Softener)
The resin composition of the present invention preferably contains a softening agent. By containing a softening agent, the uneven | corrugated followable | trackability of the resin composition of this invention can be improved more. In particular, when the resin composition is in a form containing an acid-modified resin and a metal hydroxide, the softening agent moderately suppresses the increased elastic modulus by suppressing stress relaxation, and both elasticity and flexibility. A resin composition having physical properties having higher characteristics can be obtained.
There is no restriction | limiting in particular in the softener which can be used for this invention. For example, those used as general softeners for rubbers and elastomers can be widely used. A preferred example of the softening agent is oil. This oil is a component that is compatible with chloroform and also compatible with ethanol, as described in the examples described later. In the present invention, “showing compatibility with X (solvent)” means that the solubility in X is “50 g / 100 g-X” or more at 25 ° C.
Examples of the oil include paraffinic oil, naphthenic oil, aromatic oil, silicone oil, polybutene oil, and plant-derived oil, and one or more of these can be used. Among these, from the viewpoint of compatibility with the resin component, paraffinic oil, naphthenic oil, aromatic oil, polybutene oil, or plant-derived oil (especially terpene oil) is preferable, particularly paraffinic oil, Those selected from polybutene oils and terpene oils are preferred. These may be used individually by 1 type and may use 2 or more types together.
In the resin composition of the present invention, the content of the softening agent is preferably 150 to 500 parts by mass with respect to 100 parts by mass of the total content of the resin components constituting the resin composition of the present invention, more preferably. It is 160-460 mass parts, More preferably, it is 190-400 mass parts, More preferably, it is 200-350 mass parts.

<Shape of resin composition>
If the resin composition of this invention is a form which contains each component homogeneously, there will be no restriction | limiting in particular in the shape. For example, it may be in the form of a kneaded product obtained by kneading the components, in the form of pellets, or in the form of a molded product. Further, the resin composition of the present invention may contain a solvent, and a resin component or the like may be dissolved in the solvent.
When the resin composition of this invention is a form of a molded article, the form shape | molded by the donut shape is mentioned as an example of preferable shape. This donut-shaped molded product can be suitably used as a water-stopping material used for, for example, a penetration pipe installed in a penetration portion such as a housing outer wall. The doughnut-shaped molded body may be circular, polygonal, or elliptical. That is, in the present invention, the donut shape is not particularly limited as long as it has a hole (through hole) at the center. What is necessary is just to adjust the size of a doughnut-shaped molded article suitably considering the magnitude | sizes of the through-hole etc. to apply. The donut-shaped molded product is preferably a flat plate having a hole in the center, and the thickness is usually 3 to 15 mm, preferably 5.5 to 10.0 mm.

<Water-stop performance of resin composition>
The resin composition of the present invention preferably exhibits a desired water stopping performance. More specifically, in the water-stopping test performed under the following conditions (I) and / or (II), it is preferable that no water leakage occurs at 30 ° C. for 30 minutes or more.

(Condition (I))
The resin composition was molded into a donut shape with a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the doughnut-shaped molded product was formed into a cylindrical pipe having a hole diameter of 37.1 mm at the outer end in the cylindrical axial direction of 105 mm. On the surface of the stainless steel flange so that the hole of the cylindrical pipe is located in the center of the hole of the donut-shaped test piece, and the siding plate on the side opposite to the flange side of the donut-shaped molded product Is arranged so that the concave-convex surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the concave-convex surface of the siding plate and the flange surface is 2.0 mm The condition in which 25 ° C. water is put into the pipe up to a height of 10 cm.

(Condition (II))
The resin composition was molded into a donut shape with a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the doughnut-shaped molded product was formed into a cylindrical pipe having a hole diameter of 37.1 mm at the outer end in the cylindrical axial direction of 105 mm. On the surface of the stainless steel flange so that the hole of the cylindrical pipe is located in the center of the hole of the donut-shaped test piece, and the siding plate on the side opposite to the flange side of the donut-shaped molded product Is arranged so that the concave-convex surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the concave-convex surface of the siding plate and the flange surface is 2.0 mm Was screwed and allowed to stand at 30 ° C. for 125 hours, and then 25 ° C. water was added to the height of 10 cm in the pipe.

<Application>
The resin composition of the present invention is suitable as a waterstop material. In the present invention, the “water-stopping material” is used to mean a joint material.
The resin composition of the present invention can be preferably applied, for example, as a waterproofing material for a housing penetration member, as a waterproofing material around an aluminum sash, as a jointing material around a kitchen, and as a jointing material for an outer wall siding ring. it can.

  Then, the water stop material of this invention is demonstrated.

[Waterproof material]
The waterstop material of the present invention comprises a resin composition containing a thermoplastic elastomer, an acid-modified resin, a metal oxide, and a softening agent. In the resin composition constituting the waterstop material, the metal oxide content is 80 to 310 parts by mass and the softener content is 160 to 460 parts by mass with respect to 100 parts by mass in total of the thermoplastic elastomer and the acid-modified resin. Part. Preferred forms of the thermoplastic elastomer, acid-modified resin, metal oxide, and softener contained in the resin composition constituting the water-stopping material of the present invention are the thermoplastic elastomer described in the above-described resin composition of the present invention, It is synonymous with the preferable form of an acid-modified resin, a metal oxide, and a softening agent, The preferable content in these water stop materials (in resin composition) is also in the resin composition demonstrated in the resin composition of this invention. It is synonymous with preferable content of. In the waterstop material of the present invention, when it is simply referred to as “thermoplastic elastomer”, it means a thermoplastic elastomer which is not acid-modified unless otherwise specified.

  The resin composition constituting the water-stopping material of the present invention preferably has a 25% compression modulus of 300 kPa or less. If it is a composition of the resin composition which comprises the water-stopping material of this invention, even if it makes the said resin composition a physical property whose 25% compression modulus is 300 kPa or less, about a relaxation elastic modulus, it can be made into a sufficiently high state. . That is, a resin composition having physical properties in which the 25% compression modulus is small and has a certain softness, and the stress relaxation with time in a pressure deformation state is suppressed, and more suitable physical properties as a waterstop material. It can be. The resin composition constituting the water-stopping material of the present invention has a 25% compression modulus of preferably 270 kPa or less, more preferably 250 kPa or less, and further preferably 230 kPa or less. The 25% compression modulus is usually 30 kPa or more, and 40 kPa or more is practical.

  Moreover, it is preferable that the water stop material of this invention shows desired water stop performance. More specifically, in the water-stopping test performed under the above-described conditions (I) and / or (II), it is preferable that no water leakage occurs at 30 ° C. for 30 minutes or more.

  The shape of the water stop material of the present invention is not particularly limited. For example, it may be in the form of a kneaded product obtained by kneading the components, in the form of pellets, or in the form of a molded product. Moreover, the water stop material of the present invention may contain a solvent, and a resin component or the like may be dissolved in the solvent. The waterstop material of the present invention is also preferably in the form formed in the above-mentioned donut shape.

  The water-stop material of the present invention is preferably applied, for example, as a water-stop material for a housing penetration member, as a water-stop material around an aluminum sash, as a joint material around a kitchen, and as a joint material for an outer wall siding ring. it can.

  The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[material]
<Base resin formulation>
(Non-acid-modified resin)
・ Styrenic thermoplastic elastomer formulation (Aron Kasei Co., Ltd., trade name: AR-SC-0 (SEBS)
Styrenic thermoplastic elastomer preparation (manufactured by Riken Technos, trade name: TPE LQR7466N, hydrogenated styrene-ethylene-α-olefin copolymer)
(Acid-modified resin)
-Maleic anhydride-modified SEBS preparation (manufactured by Asahi Kasei Chemicals Corporation, trade name: Tuftec M1911)

<Softener>
・ Paraffin oil (manufactured by Sun Japan Oil Company, trade name: SUNPAR2280)
・ Polybutene oil (manufactured by JXTG Energy, trade name: LV-50)

<Filler>
・ Magnesium hydroxide (Kamishima Chemical Industries, trade name: Magsees N6)
・ Calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Shiraka Hana CC)

[Preparation Example]
<Preparation of resin composition>
The base resin formulation, softener and filler were mixed (total amount 700 g) and kneaded so as to have the component composition (unit: parts by mass) shown in the table below, and each of Examples 1 to 7 and Comparative Examples 1 to 5 A resin composition was obtained. This kneading was performed using a 1 L kneader (manufactured by Moriyama, MS type small pressure kneader (capacity 1 L)) set at 150 ° C. for 10 to 15 minutes until each component became uniform. Preparation of the resin composition of each Example and a comparative example is demonstrated in detail.

(Example 1)
10.0 parts by mass of acid-modified SEBS formulation (trade name: Tuftec M1911, manufactured by Asahi Kasei Chemicals Co., Ltd.) with respect to 90.0 parts by mass of styrene-based thermoplastic elastomer formulation (manufactured by Riken Technos, trade name: TPE LQR7466N), polybutene 40.0 parts by mass of oil (manufactured by JXTG Energy, trade name: LV-50) and 50.0 parts by weight of magnesium hydroxide (manufactured by Kamishima Chemical Industry, trade name: Magsees N6) are blended and kneaded as described above. The resin composition of Example 1 was obtained. The component content in the obtained resin composition was determined as follows (component content was similarly determined also about the resin composition of Examples 2-7 and Comparative Examples 1-5).

− Method for determining component content −
-Content of softener component--
2.727 g of the resin composition was immersed in 20 mL of chloroform and allowed to stand until the chloroform-soluble components (components other than the filler) were completely dissolved. Thereafter, this chloroform solution was dropped into a sufficient amount (1.0 L or more) of ethanol to coagulate and precipitate the resin component and the filler component. The precipitate was separated by filtration under reduced pressure using a filter paper, and then the precipitate was washed by pouring ethanol into the precipitate. Then, it dried and removed ethanol, and when the mass of the deposit was measured, it was 1.380g.
Since the amount of the resin composition at the starting point is 2.727 g as described above, [2.727 g] − [1.380 g] = [1.347 g] is the amount of the softening agent (oil).

--- Resin component content ---
1.380 g of the precipitate was again immersed in chloroform to completely dissolve the chloroform-soluble component, and then the filler component was removed by a syringe filter (pore size 0.80 μm → pore size 0.45 μm, filtered once each). When the obtained filtrate was dried to remove chloroform, the component that remained without volatilization was 0.660 g. This residual component 0.660 g is the amount of the resin component.

-Content of filler component ---
The amount of the filler component is 0.720 g obtained by subtracting 1.347 g of the softening material component and 0.660 g of the resin component from 2.727 g of the resin composition at the starting time.

-Ratio of acid-modified resin and non-acid-modified resin in the resin component-
In Example 1, the amounts of the styrenic thermoplastic elastomer resin and the acid-modified SEBS in the resin component were determined as follows.
3.498 g of a styrene-based thermoplastic elastomer preparation (trade name: TPE LQR7466N, manufactured by Riken Technos Co., Ltd.) was completely dissolved in chloroform and then dropped into a sufficient amount of ethanol to obtain a precipitate. The precipitate was separated by filtration under reduced pressure using a filter paper, and then the precipitate was washed by pouring ethanol into the precipitate. Then, it dried and removed ethanol, and when the mass of the deposit was measured, it was 1.404g. Therefore, the softener component is [3.498 g]-[1.404 g] = [2.094 g] (styrene-based thermoplastic elastomer resin: softening agent = 2: 3 (mass ratio)).
Here, in the resin composition of Example 1, 10 parts by mass of maleic anhydride-modified SEBS preparation is blended with 90 parts by mass of the styrene-based thermoplastic elastomer preparation.
As described above, since the styrene-based thermoplastic elastomer formulation is styrene-based thermoplastic elastomer resin: softening agent = 2: 3 (mass ratio), 36 parts by mass out of 90 parts by mass of the styrene-based thermoplastic elastomer formulation It becomes a styrene-based thermoplastic elastomer which is an acid-modified resin, and the remaining 54 parts by mass becomes a softener component. On the other hand, the maleic anhydride-modified SEBS preparation blended in the resin composition does not contain a softening agent.
Therefore, if it converts so that it may become 100 mass parts in the whole resin component (36 mass parts +10 mass parts), non-acid modification resin will be calculated with 78.3 mass parts, and acid modification resin will be 21.7 mass parts.

(Example 2)
To 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil Example 1 except that 28.8 parts by mass (trade name: LV-50, manufactured by JXTG Energy Co., Ltd.) and 36.8 parts by mass of magnesium hydroxide (trade name: Magsees N6, manufactured by Kamishima Chemical Industry Co., Ltd.) were blended. In the same manner as described above, the resin composition of Example 2 was prepared.

(Example 3)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals, brand name: Tuftec M1911) with respect to 90.0 parts by mass of styrene-based thermoplastic elastomer preparation (Aron Kasei Co., Ltd., trade name: AR-SC-0) In addition, 78.8 parts by mass of paraffinic oil (manufactured by Sun Oil Co., Ltd., trade name: SUNPAR2280) and 100.8 parts by mass of magnesium hydroxide (trade name: Mag Seeds N6, manufactured by Kamishima Chemical Co., Ltd.) The resin composition of Example 3 was prepared in the same manner as Example 1.

Example 4
90.0 parts by mass of a styrene-based thermoplastic elastomer formulation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil Example 1 except that 38.0 parts by mass (trade name: LV-50, manufactured by JXTG Energy Co., Ltd.) and 92.0 parts by mass of magnesium hydroxide (trade name: Magsees N6, manufactured by Kamishima Chemical Industry Co., Ltd.) were blended. The resin composition of Example 4 was prepared in the same manner as described above.

(Example 5)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals, brand name: Tuftec M1911) with respect to 90.0 parts by mass of styrene-based thermoplastic elastomer preparation (Aron Kasei Co., Ltd., trade name: AR-SC-0) In addition, 33.3 parts by weight of paraffinic oil (Nihon Sun Oil Co., Ltd., trade name: SUNPAR2280) and 97.5 parts by weight of magnesium hydroxide (Kamishima Chemical Industries, trade name: Magsees N6) were blended. The resin composition of Example 5 was prepared in the same manner as Example 1.

(Example 6)
To 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil Example 1 except that 61.0 parts by mass (trade name: LV-50, manufactured by JXTG Energy Co., Ltd.) and 36.8 parts by mass of magnesium hydroxide (trade name: Magsees N6, manufactured by Kamishima Chemical Industry Co., Ltd.) were blended. In the same manner as described above, the resin composition of Example 5 was prepared.

(Example 7)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals, brand name: Tuftec M1911) with respect to 90.0 parts by mass of styrene-based thermoplastic elastomer preparation (Aron Kasei Co., Ltd., trade name: AR-SC-0) In addition, 78.8 parts by mass of paraffinic oil (manufactured by Sun Japan Oil Co., Ltd., trade name: SUNPAR2280), 81.3 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Co., Ltd., trade name: Magseeds N6) The resin composition of Example 5 was prepared in the same manner as Example 1.

(Comparative Example 1)
To 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil Example 1 except that 15.0 parts by mass (trade name: LV-50, manufactured by JXTG Energy Co., Ltd.) and 50.6 parts by mass of magnesium hydroxide (trade name: Magsees N6, manufactured by Kamishima Chemical Industry Co., Ltd.) were blended. In the same manner, a resin composition of Comparative Example 1 was prepared.

(Comparative Example 2)
To 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil Example 1 except that 28.8 parts by mass (trade name: LV-50, manufactured by JXTG Energy Co., Ltd.) and 23.0 parts by mass of magnesium hydroxide (trade name: Magsees N6, manufactured by Kamishima Chemical Industry Co., Ltd.) were blended. In the same manner, a resin composition of Comparative Example 2 was prepared.

(Comparative Example 3)
120.0 parts by mass of polybutene oil (manufactured by JXTG Energy, trade name: LV-50), 100 parts by weight of magnesium styrene (100% by weight, manufactured by Riken Technos, trade name: TPE LQR7466N) A resin composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that 32.0 parts by mass of Kamishima Chemical Industries, trade name: Magsees N6) was blended.

(Comparative Example 4)
10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals, brand name: Tuftec M1911) with respect to 90.0 parts by mass of styrene-based thermoplastic elastomer preparation (Aron Kasei Co., Ltd., trade name: AR-SC-0) , Except that 88.5 parts by mass of paraffinic oil (manufactured by Sun Japan Oil Company, trade name: SUNPAR2280), 100.8 parts by mass of magnesium hydroxide (manufactured by Kamishima Chemical Co., Ltd., trade name: Magsees N6) A resin composition of Comparative Example 4 was prepared in the same manner as Example 1.

(Comparative Example 5)
To 90.0 parts by mass of a styrene-based thermoplastic elastomer preparation (manufactured by Riken Technos Co., Ltd., trade name: TPE LQR7466N), 10.0 parts by mass of acid-modified SEBS (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec M1911), polybutene oil (JXTG Energy Co., Ltd., trade name: LV-50) 40.0 parts by mass, calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Shiraka Hana CC) 50.0 parts by mass, except that the same as Example 1, Thus, a resin composition of Comparative Example 6 was prepared.

[Measurement of physical properties of resin composition]
The obtained resin compositions of Examples and Comparative Examples were obtained in a length of 160 × width of 200 × height of 2 mm (for relaxation modulus measurement), length of 160 × width of 200 × height of 7 mm (for water-stopping test), and length Each mold of 160 × width 200 × height 13 mm (for measuring 25% compression modulus) was put into a press machine in which the press plate temperature was previously set at 160 ° C. and pressed at a pressure of 5 MPa for 5 minutes. In the pressed state, it is cooled to 30 ° C. or less as it is, and the resin compositions of each Example and Comparative Example are 1.9 mm in thickness (for relaxation modulus measurement), 6.7 mm (for water-stop test), 12.5 mm ( A test sheet (for measuring 25% compression modulus) was prepared.

<Measurement of 25% compression modulus>
Based on JIS K 6254 method C, 25% compressive stress was measured. A disk made by attaching a metal compression jig to a universal tensile testing machine (manufactured by Shimadzu Tester Co., Ltd., Autograph AGS-1kNX) and punching a test sheet with a thickness of 12.5 mm to a diameter of 30 mm (measured diameter: 29.8 mm) A sample was placed in the center of the jig. The operation of compressing to a strain amount of 25% at a speed of 10 mm / min and immediately removing the load at 10 mm / min was repeated three times, and the stress in the state compressed to 25% was measured. The average value of the three measurements obtained was taken as the 25% compression modulus of the resin composition.
The results are shown in the table below.

<Measurement of relaxation modulus>
The test piece was fixed to a flat plate jig, and the storage elastic modulus (G ′), loss elastic modulus (G ″), and loss tangent value (tan δ) were measured under the following dynamic viscoelasticity test conditions.
The measurement conditions are a temperature range of 30 ° C. to 220 ° C., a 10 ° C. step, five types of frequencies (0.5 to 20 Hz), and a strain amount of 0.5%. Using a test piece having a diameter of 25 mm × thickness of 1.9 mm punched with a punch having a diameter of 25 mm, the response to strain during a continuous temperature rising process was measured. When the frequency and strain amount are too large, the test piece is twisted and the data becomes unstable. Therefore, the storage elastic modulus (G ′) was measured under the above conditions.
The following operations were performed on the storage modulus data at each temperature.
First, according to the time-temperature conversion rule (Time-Temperature-Superposition [TTS] = experimental rule that time and temperature can be handled equivalently), the following W.P. L. Referring to Formula F (Williams, Landel, Ferry Formula), the shift factor Logo _T (the amount by which the data of each temperature is moved horizontally along the frequency axis) when the reference temperature is 30 ° C. is defined by the following procedure: .
On the log-log graph with the horizontal axis representing the frequency and the vertical axis representing the modulus of elasticity, the viscoelasticity data (storage modulus) measured by changing the frequency at a measurement temperature of 30 ° C was fixed, and this data curve and 40 ° C The 40 ° C. data curve is shifted along the frequency side so that the same data curve measured in step 1 is smoothly connected. The same operation was performed on the data curve from 50 ° C. to 220 ° C., and finally synthesized as a single curve. From the amount of horizontal movement at each temperature, a _T (shift factor) and C1 and C2 were obtained recursively, and the resultant curve determined by these was used as the master curve. Furthermore, what takes the reciprocal of the horizontal axis (frequency) and converts the horizontal axis into time units is defined as a relaxation elastic modulus curve in the present invention.
On this curve, the value after 125 days (3000 hours) at 30 ° C. was read and taken as the elastic modulus after relaxation.
For the measurement, a dynamic viscoelasticity test apparatus (product name: ARES-G2 manufactured by TA Instruments) was used. The series of operations (procedures) were automatically performed using software (product name: TRIOS, manufactured by TA Instruments). At that time, the storage elastic modulus was selected as a parameter to be shifted, setting was made so as to allow only horizontal movement in the X-axis direction (frequency axis), and the master curve was determined.
The results are shown in the table below.

[Waterproof test]
<Prepared test equipment>
・ Siding board (Nichiha Co., Ltd., trade name: Moen Xcellade 16 New Grandle Series I EPB311N, maximum difference in height from the bottom of the concave part to the top of the convex part is 4.2 mm)
-Both-end welded vacuum tube NW flange x VF flange (made by MISUMI, model number: FNRFRR40, material: SUS304, height 50 mm, tube inner diameter 37.1 mm)
NW / KF standard long flange (manufactured by Cosmo Tech, model number: NW40LF70L, material: SUS304, height 70 mm, pipe inner diameter 37.1 mm)
・ MPC vacuum piping KF center ring (Mirapro, model number: MCK-2040)
・ NW clamp (ISO-KF flange type, manufactured by Mirapro, model number: MCK-1040)
・ M10 bolt and nut 4 sets (used to fix siding and VF flange)

<Processing of test equipment>
In accordance with the bolt hole of the VF flange of the double-sided welded vacuum tube (FRNRFR40), a hole was also drilled on the siding side so that the VF flange of the double-sided welded vacuum tube (FRRNFR40) could be fixed to the siding plate with M10 bolts. The attachment position of the VF flange is an arbitrary position with respect to the handle (unevenness) present on the siding plate.
A circular sheet having a diameter of 60 mm was cut out from a test sheet having a thickness of 6.7 mm, and a donut-shaped test piece having a hole having a diameter of 40 mm in the center of the obtained disk-shaped sheet was produced.

<Assembly of test tool and test piece>
As shown in FIG. 1, the siding plate 1, donut-shaped test piece 7, double-sided welded vacuum tube 2 (FRNRFR40), KF center ring 3 (MCK-2040), and long flange 4 (NW40LF70L) were stacked in this order from the bottom. At this time, the hole (diameter: 37.1 mm) of the double-sided welded vacuum tube 2 (FRNRFR40) was positioned in the center of the hole (diameter 40 mm) of the doughnut-shaped test piece 7.
NW clamp (ISO-KF flange type, manufactured by Mirapro, model number: MCK-1040) with both-end welded vacuum tube 2 (FRNRFR40) and long flange 4 (NW40LF70L) sandwiched between KF center ring 3 (MCK-2040) C).
Further, until the distance between the highest convex portion on the surface of the siding plate 1 and the lowermost end (VF flange outermost surface) of the double-sided welded vacuum tube 2 (FRNRFR40) facing the siding plate surface becomes 2.0 mm (doughnut shape) The bolts were tightened (until the minimum thickness of the test piece 7 was 2 mm). At this time, a 2.0 mm spacer was used so that the clearance between the siding plate 1 and the outermost surface of the VF flange was not changed.

<Water-stop test method>
Condition (I):
Water (25 ° C.) was poured into the pipe from the upper part of the long flange 4 (NW40LF70L), and the pipe was filled with water from the lower end of the VF flange of the both-end welded vacuum pipe 2 (FRNRFR40) to a position 10 cm in height. After 30 minutes at 30 ° C., the presence or absence of water leakage was examined visually. The case where there was no water leakage was marked with ◯, and the case where water leakage occurred was marked with ×.
Condition (II):
With the test tool or test piece assembled, the test tool or test piece was left in a thermostatic bath at 30 ° C. for 125 days. Thereafter, water (25 ° C.) was poured into the tube up to a height of 10 cm in the same manner as in the above condition (I), and after 30 minutes at 30 ° C., the presence or absence of water leakage was examined visually. The case where there was no water leakage was marked with ◯, and the case where water leakage occurred was marked with ×.

As shown in the above table, when the 25% compression modulus of the resin composition is larger than that of the present invention, the followability to the uneven surface is not sufficient, resulting in poor water stop performance (comparison). Example 1).
Even if the 25% compression modulus of the resin composition is within the range of the present invention, if the relaxation modulus after 125 days at 30 ° C. is smaller than the range of the present invention, the uneven tracking state is maintained for a long time under pressure. (Comparative Examples 2 to 5).
In contrast, when both the 25% compression modulus of the resin composition and the relaxation elastic modulus after 125 days at 30 ° C. satisfy the provisions of the present invention, the followability to the uneven surface is excellent. It was found that the state can be maintained for a long period of time, and as a result, excellent water stoppage can be maintained for a long period of time (Examples 1 to 7).

DESCRIPTION OF SYMBOLS 1 Siding board 2 Both-ends welded vacuum tube 3 Center ring 4 Long flange 5 Bolt 6 Nut 7 Resin composition (waterproof material)

Claims (15)

Resin composition satisfying the following (A) and (B):
(A) 25% compression modulus is 300 kPa or less,
(B) The relaxation elastic modulus after 125 days at 30 ° C. is 9.0 kPa or more.   The resin composition of Claim 1 in which the resin component which comprises the said resin composition contains a thermoplastic elastomer.   The resin composition according to claim 2, wherein the thermoplastic elastomer includes a styrenic thermoplastic elastomer.   The resin composition according to claim 1, wherein the resin composition contains a softening agent.   5. The resin composition according to claim 1, wherein the resin composition contains a metal hydroxide, and the resin component constituting the resin composition includes a styrenic thermoplastic elastomer that is not acid-modified and an acid-modified resin. Item 1. The resin composition according to item 1.   The ratio of the acid-modified resin in the resin component constituting the resin composition is 10 to 40% by mass, and the metal hydroxide has a total content of 100 parts by mass of the resin component constituting the resin composition. The resin composition according to claim 5, wherein the content is 80 to 310 parts by mass.   The resin composition according to any one of claims 1 to 6, which is formed into a donut shape.   The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the outer diameter of the cylindrical pipe having a hole diameter of 37.1 mm at the end of the cylindrical axis is provided. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. When the water is put into a screwed state and water of 25 ° C. is put into the pipe up to a height of 10 cm, water leakage does not occur at 30 ° C. for 30 minutes or more. Resin composition.   The resin composition is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the outer diameter of the cylindrical pipe having a hole diameter of 37.1 mm at the end of the cylindrical axis is provided. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. And then let stand at 30 ° C. for 125 hours, and then put water of 25 ° C. up to a height of 10 cm in the pipe at 30 ° C. for 30 minutes or more without water leakage. , Any one resin composition as claimed in claims 1-8.   The resin composition of any one of Claims 1-9 used as a water stop material.   Contains 80 to 310 parts by mass of metal hydroxide and 160 to 460 parts by mass of a softening agent for a total of 100 parts by mass of the thermoplastic elastomer, the acid-modified resin, the thermoplastic elastomer and the acid-modified resin. A waterstop material comprising a resin composition.   The waterstop material according to claim 11, wherein the thermoplastic elastomer includes a styrenic thermoplastic elastomer.   The waterstop material according to claim 11 or 12, wherein a 25% compression modulus of the resin composition is 300 kPa or less.   The water blocking material is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the cylindrical pipe having a hole diameter of 37.1 mm has an outer diameter that the cylindrical pipe has at the cylindrical axial end. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. 14 is a state in which the screw is tightened and water of 25 ° C. is put into the pipe up to a height of 10 cm, the water does not leak at 30 ° C. for 30 minutes or more. The water stopping material.   The water blocking material is molded into a donut shape having a hole diameter of 40 mm, an outer diameter of 60 mm, and a thickness of 6.7 mm, and the cylindrical pipe having a hole diameter of 37.1 mm has an outer diameter that the cylindrical pipe has at the cylindrical axial end. Placed on the surface of 105 mm stainless steel flange so that the hole of the cylindrical pipe is located at the center of the hole of the donut-shaped test piece, and the side opposite to the flange side of the donut-shaped molded product is siding A plate is arranged such that the uneven surface of the siding plate is on the donut-shaped molded product side, and the flange and the siding plate until the shortest distance between the uneven surface of the siding plate and the flange surface is 2.0 mm. And when the water is allowed to stand at 30 ° C. for 125 hours and then water of 25 ° C. is added to the height of 10 cm in the pipe, no water leaks at 30 ° C. for 30 minutes or more. Water stopping material according to any one of Motomeko 11-14.

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