JP5167719B2 - Thermoplastic elastomer composition and glazing gasket using the same - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition and a glazing gasket using the same.

A glazing gasket is generally disposed between the double glazing and the sash in the double glazing to which the sash is attached. The glazing gasket prevents water from entering the multilayer glass by physical adhesion between the glazing gasket and the glass.
Examples of the thermoplastic elastomer composition proposed for gaskets include Patent Document 1 and Patent Document 2.

Patent Document 1 discloses that “an oil containing 20 to 150 parts by weight of a mineral oil softener per 100 parts by weight of an olefin copolymer rubber having a Mooney viscosity of 100 ° C. (ML _{1 + 4} 100 ° C.) of 120 to 350”. Expanded olefin copolymer rubber (A) selected from 40 to 95% by weight, propylene polymer resin (B) having reduced viscosity of 1.7 dl / g or more and 5 to 60% by weight, and polybutene, polyisobutylene and butyl rubber "A thermoplastic elastomer composition characterized in that it is obtained by dynamically heat-treating a mixture of 0 to 50% by weight of at least one polymer (C) and partially cross-linking."

  Patent Document 2 states that “(a) an ethylene / α-olefin random copolymer, (b) an olefin resin, and (e) a softener-containing mixture in the presence of (f) an organic peroxide. In the dynamic heat treatment, the (to) maleimide compound is added in an amount of 0.1 parts by weight with respect to 100 parts by weight of the total amount of (i) an ethylene / α-olefin random copolymer, (b) an olefin resin, and (e) a softener. 3-10 parts by weight is added and obtained by dynamically heat-treating the thermoplastic elastomer composition for heat fusion.

  Further, in Patent Document 3, for a rubber roller, “a hydrogenated styrene thermoplastic elastomer and an olefin resin are combined in an amount of 20 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the rubber. A rubber composition that has been dynamically vulcanized with a vulcanizing agent and dispersed in a mixture of the above hydrogenated styrene thermoplastic elastomer and olefin resin has been proposed.

JP-A-6-316657 JP 2003-171511 A Japanese Patent Laid-Open No. 11-236465

  However, when a glazing gasket is prepared using the composition described in Patent Documents 1 to 3, and the obtained glazing gasket and a multilayer glass are bonded with a hot melt adhesive, a hot melt system is used. It was revealed that the adhesive strength between the adhesive and the glazing gasket was lowered, and as a result, the long-term durability of the double-glazed glass with the glazing gasket was deteriorated.

The present inventor has found that the decrease in the adhesive strength between the hot-melt adhesive and the glazing gasket is a paraffin oil blended as a softener in the rubber described in Patent Documents 1 to 3. Has been found to occur due to the transition of oils and / or plasticizers to hot melt adhesives.
In addition, the present inventor simply reduced the oil and / or plasticizer content in the thermoplastic elastomer composition, or replaced a part thereof with a liquid polymer, and the viscosity of the thermoplastic elastomer composition became extremely high. It was found that the fluidity may be increased due to an increase.

  Therefore, the present invention provides a thermoplastic elastomer composition excellent in fluidity, a glazing gasket excellent in adhesion to a hot melt adhesive, and a multilayer glass with a glazing gasket excellent in long-term durability. Is an issue.

As a result of intensive studies to solve the above problems, the present inventor has found that a crystalline polyolefin having a predetermined viscosity, a styrene thermoplastic elastomer having a predetermined viscosity and hardness, and an ethylene-propylene rubber having a predetermined viscosity. It has been found that a thermoplastic elastomer composition obtained from a mixture containing a compound and a crosslinking agent is excellent in fluidity.
Further, the present inventor has found that a laminate having a hot-melt adhesive between such a thermoplastic elastomer composition and glass is excellent in adhesiveness between the thermoplastic elastomer composition and the hot-melt adhesive. I found.
Furthermore, the present inventor has found that a glazing gasket obtained from such a thermoplastic elastomer composition has excellent adhesion to a hot melt adhesive, and between such a glazing gasket and a multilayer glass. It was found that a double-glazed glass with a glazing gasket having a hot melt adhesive is excellent in long-term durability.

The present inventor has completed the present invention based on these findings. That is, the present invention provides the following (1) to ( 16 ).

(1) a crystalline polyolefin having a viscosity of 500 Pa · s or less at a shear rate of 100 s ⁻¹ at 180 ° C .;
A styrenic thermoplastic elastomer having a viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. of 2000 Pa · s or less and a Shore A hardness of 50 or less;
An ethylene-propylene rubber compound having a Mooney viscosity of 35 or less at 100 ° C;
The mixture containing the crosslinking agent, Ru obtained by dynamic crosslinking,
A thermoplastic elastomer composition in which the ethylene-propylene rubber compound contains 25% by mass or more of a liquid polymer having a kinematic viscosity at 40 ° C. of 5000 to 350,000 mm ² / s .

  (2) The thermoplastic elastomer composition according to (1), wherein the total content of the ethylene-propylene rubber compound and the crosslinking agent in the mixture is 75% by mass or more.

  (3) The crystalline polyolefin is polyethylene, polypropylene, ethylene propylene copolymer, ethylene α-olefin copolymer, propylene α-olefin copolymer, ethylene propylene α-olefin copolymer, ethylene butene copolymer, The thermoplastic elastomer composition according to the above (1) or (2), which is at least one selected from the group consisting of a propylene butene copolymer and an ethylene propylene butene copolymer.

  (4) The above (Styrenic thermoplastic elastomer is at least one selected from the group consisting of a hydrogenated styrene butadiene random copolymer, a hydrogenated styrene butadiene block copolymer, and a hydrogenated styrene isoprene block copolymer) The thermoplastic elastomer composition according to any one of 1) to (3).

  (5) The hydrogenated styrene butadiene random copolymer and the hydrogenated styrene butadiene block copolymer have a butylene component content of the hydrogenated styrene butadiene random copolymer and the hydrogenated styrene butadiene block copolymer. The thermoplastic elastomer composition according to the above (4), which is 50 to 90% by mass of the total amount of the ethylene component and the butylene component therein.

  (6) The content of the propylene component in the hydrogenated styrene isoprene block copolymer is 50 to 90% by mass of the total amount of the ethylene component and the propylene component in the hydrogenated styrene isoprene block copolymer. The thermoplastic elastomer composition according to (4) above.

( 7 ) The liquid polymer is liquid polybutene, liquid polyisobutene, liquid polyisoprene, liquid polybutadiene, liquid poly α-olefin, liquid ethylene α-olefin copolymer, liquid ethylene propylene copolymer, and liquid ethylene butylene copolymer. The thermoplastic elastomer composition according to any one of the above ( 1 ) to (6), which is at least one selected from the group consisting of:

( 8 ) The thermoplastic elastomer composition according to any one of ( 1 ) to ( 7 ) , wherein the liquid polymer has a ratio (η40 / η100) of kinematic viscosity at 40 ° C to kinematic viscosity at 100 ° C of 30 or more. object.

( 9 ) The thermoplastic elastomer composition according to any one of (1) to ( 8 ), which contains 15% by mass or less of oil and / or plasticizer.

( 10 ) By dynamically crosslinking the mixture, at least a part of the ethylene-propylene rubber compound becomes a crosslinked rubber, and the ethylene-propylene rubber compound becomes particles in the crystalline polyolefin and the styrene thermoplastic elastomer. The thermoplastic elastomer composition according to any one of (1) to ( 9 ), wherein the thermoplastic elastomer composition is dispersed in a shape.

( 11 ) Shore A hardness is 65 or less, compression set is 50% or less, tensile strength is 4.5 MPa or more, and viscosity under conditions of 180 ° C. and shear rate of 100 s ⁻¹ is 2000 Pa · s or less. The thermoplastic elastomer composition according to any one of (1) to ( 10 ) above.

( 12 ) The dynamic crosslinking is performed using a twin-screw kneading extruder,
The biaxial kneading extruder has two screws having a screw length (La) / screw diameter (D) of 40 or more from the center position of the material inlet,
The screw has a first kneading region in a range where the screw length (La) / screw diameter (D) from the center position of the material inlet is 5 to 15,
In the first kneading region, at least four kneading segments having a screw length (Lb) / screw diameter (D) of 1 or less,
The thermoplastic elastomer composition according to any one of (1) to ( 11 ), wherein the temperature in the first kneading region is a temperature not higher than the melting point of the crystalline polyolefin.

( 13 ) The thermoplastic resin according to ( 12 ), wherein the screw of the twin-screw kneading extruder further has a second kneading region in which the screw length (Lb) / screw diameter (D) is 10 or more. Elastomer composition.

( 14 ) A laminate having a hot melt adhesive between the thermoplastic elastomer composition according to any one of (1) to ( 13 ) and glass.

( 15 ) A glazing gasket obtained from the thermoplastic elastomer composition according to any one of (1) to ( 13 ).

( 16 ) A multilayer glass with a glazing gasket having a hot melt adhesive between the multilayer glass and the glazing gasket described in ( 15 ) above.

  As shown below, according to the present invention, a thermoplastic elastomer composition having excellent fluidity can be provided. Further, by using this thermoplastic elastomer composition, it is possible to provide a glazing gasket excellent in adhesion to a hot melt adhesive and a multi-layer glass with a glazing gasket excellent in long-term durability.

The present invention is described in detail below.
The thermoplastic elastomer composition of the present invention, the viscosity at a shear rate 100s ^-1 at 180 ° C. and the crystalline polyolefin is less than 500 Pa · s, a viscosity at a shear rate of 100s ^-1 at 180 ° C. or less 2000 Pa · s A mixture containing a styrene thermoplastic elastomer having a Shore A hardness of 50 or less, an ethylene-propylene rubber compound having a Mooney viscosity of 35 or less at 100 ° C., and a crosslinking agent; It is a thermoplastic elastomer composition that can be obtained.
Next, the crystalline polyolefin, the styrene thermoplastic elastomer, the ethylene-propylene rubber compound, and the crosslinking agent will be described in detail.

<Crystalline polyolefin>
The crystalline polyolefin refers to a polymer that exhibits a melting point and exhibits diffraction derived from a crystalline phase by X-ray diffraction among olefin polymers.

In the present invention, from the viewpoint of improving the fluidity of the thermoplastic elastomer composition of the present invention to be obtained, a crystalline polyolefin having a viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. of 500 Pa · s or less is used. .
Here, in the present invention, the viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. is a value measured using a capillary rheometer (Toyo Seiki Seisakusho).
Specifically, using a barrel with a diameter of 9.55 mm, a capillary with a diameter of 1 mm and a length of 10 mm, and at a piston speed of 5, 10, 20, and 50 mm / min at 180 ° C., each shear rate (61, 122, 243 , 608 s ⁻¹ ). A logarithmic plot of the shear rate and the viscosity was performed, and the viscosity at a shear rate of 100 s ⁻¹ was calculated from the linear approximation formula of the obtained flow curve.

Further, the molecular weight of the polyolefin of the crystalline polyolefin is preferably a weight average molecular weight of 100,000 to 10,000,000 because the heat resistance and mechanical strength of the thermoplastic elastomer composition of the present invention to be obtained become better. 1 to 6 million is more preferable.
Furthermore, the crystalline polyolefin preferably has a crystallinity of 25% or more as measured through X-ray diffraction.

  Specific examples of such crystalline polyolefin include polyethylene, polypropylene, ethylene propylene copolymer, ethylene α-olefin copolymer, propylene α-olefin copolymer, and ethylene propylene α-olefin copolymer. , Ethylene butene copolymer, propylene butene copolymer, ethylene propylene butene copolymer, and the like. These may be used alone or in combination of two or more.

  Among these, polypropylene and polyethylene are preferable because the thermoplastic elastomer composition of the present invention obtained has good heat resistance, mechanical strength, and chemical resistance.

<Styrenic thermoplastic elastomer>
Styrenic thermoplastic elastomer refers to a thermoplastic elastomer containing a styrene compound as a repeating unit.

In the present invention, from the viewpoint of improving the fluidity and flexibility of the thermoplastic elastomer composition of the present invention obtained, the viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. is 2000 Pa · s as a styrenic thermoplastic elastomer. The shore A hardness is 50 or less.
Here, the viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. is a value measured using a capillary rheometer, and the Shore A hardness is a “durometer hardness test (type A)” defined by JIS K6253-1997. It is the value measured by.

  Further, the styrene-based thermoplastic elastomer has a weight average molecular weight of 50, from the viewpoint that the fluidity of the thermoplastic elastomer composition of the present invention to be obtained becomes better, and an increase in hardness and an increase in compression set can be suppressed. It is preferably from 000 to 500,000, more preferably from 50,000 to 300,000, and even more preferably from 70,000 to 200,000.

Furthermore, it is preferable that the styrene-based thermoplastic elastomer has a styrene content of 40% by mass or less because the hard segment portion (styrene block) is small and the temperature dependency of rigidity can be reduced.
Here, the styrene content (bound styrene content) of the styrene-based thermoplastic elastomer can be determined according to the test method described in JIS K6383: 2001 (Test Method for Synthetic Rubber SBR).

  Examples of such styrenic thermoplastic elastomers include random copolymers of one or more dienes selected from the group consisting of isoprene, butadiene and isobutylene and styrene, hydrogenated products thereof; polyisoprene, hydrogenated Polyisoprene, polybutadiene (1,2-polybutadiene, 1,4-polybutadiene), hydrogenated polybutadiene (hydrogenated, 1,2-polybutadiene, 1,4-polybutadiene), polyisobutylene, polyethylene, polypropylene And a copolymer of at least one block selected from the group consisting of polyvinyl and a polystyrene block, a hydrogenated product thereof; a mixture of these copolymers; and the like.

  Specifically, hydrogenated styrene butadiene random copolymer (h-SBR), polystyrene-polyisoprene-polystyrene block copolymer (SIS), polystyrene-polybutadiene-polystyrene block copolymer (SBS), hydrogenated styrene butadiene. Block copolymer [polystyrene-hydrogenated-1,2-polybutadiene / hydrogenated-1,4-polybutadiene-polystyrene block copolymer (SEBS)], hydrogenated styrene isoprene block copolymer [polystyrene-hydrogenated polyisoprene -Polystyrene block copolymer (SEPS)], polystyrene-vinyl-polyisoprene-polystyrene block copolymer (SHIVS), polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene block copolymer, Examples include a restyrene-polyisobutylene block copolymer, a polystyrene-polyisobutylene-polystyrene block copolymer (SIBS), a polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene copolymer, and the like. In addition, two or more kinds may be used in combination.

Among these, the fluidity and flexibility of the thermoplastic elastomer composition of the present invention are further improved, and the thermal stability is also improved, so that hydrogenated styrene butadiene random copolymer (h-SBR), polystyrene- Polybutadiene-polystyrene block copolymer (SBS), hydrogenated styrene butadiene block copolymer (SEBS), and hydrogenated styrene isoprene block copolymer (SEPS) are preferred.
Further, the flowability of the thermoplastic elastomer composition of the present invention is further improved, the thermal stability is also improved, the increase in hardness and the increase in compression set are suppressed, and h-SBR is excellent because of its excellent tensile strength. , SBS, SEBS, and SEPS are preferable, and h-SBR, SEBS, and SEPS are more preferable.

Here, the content of the butylene component in the hydrogenated styrene butadiene random copolymer (h-SBR) and the hydrogenated styrene butadiene block copolymer (SEBS) is such that the ethylene component and the butylene component in h-SBR and SEBS are The total amount is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, and even more preferably 70 to 80% by mass.
Moreover, it is preferable that content of the propylene component in hydrogenated styrene isoprene block copolymer (SEPS) is 50 to 90 mass% of the total amount of the ethylene component and propylene component in SEPS, and 60 to 80 mass. % Is more preferable, and 60 to 70% by mass is even more preferable.

In the present invention, by using the above-mentioned crystalline polyolefin and styrene-based thermoplastic elastomer, the resulting thermoplastic elastomer composition of the present invention has good fluidity, and suppresses an increase in hardness and an increase in compression set. be able to.
This is because the fluidity of the matrix (continuous phase) can be increased by using a low-viscosity crystalline polyolefin and a styrene-based thermoplastic elastomer. It is thought that it will be improved.
In addition, by using a styrenic thermoplastic elastomer that is compatible with the crystalline polyolefin, the styrenic thermoplastic elastomer is finely dispersed in the crystalline polyolefin, thereby suppressing a significant decrease in the mechanical strength of the crystalline polyolefin. However, since it becomes possible to obtain the effect of softening by the styrene-based thermoplastic elastomer, it is considered that an increase in hardness and an increase in compression set of the obtained thermoplastic elastomer composition of the present invention can be suppressed.

  Here, examples of the combination of the crystalline polyolefin and the styrene-based thermoplastic elastomer include the various exemplary combinations described above, but the fluidity of the resulting thermoplastic elastomer composition of the present invention becomes better, and the hardness is improved. At least one selected from the group consisting of crystalline polyethylene and crystalline polypropylene, a hydrogenated styrene butadiene random copolymer (h-SBR), and a hydrogenated styrene butadiene for the reason that the increase in increase and compression set can be further suppressed. A combination with at least one selected from the group consisting of a block copolymer (SEBS) and a hydrogenated styrene isoprene block copolymer (SEPS) is preferably exemplified.

  In the present invention, the content of the above-described crystalline polyolefin and the styrene-based thermoplastic elastomer is more compatible, and the resulting thermoplastic elastomer composition of the present invention has better fluidity and hardness. From the reason that the increase in the rise and compression set can be further suppressed, the styrene-based thermoplastic elastomer is preferably 20 to 200 parts by mass, and 50 to 100 parts by mass with respect to 100 parts by mass of the crystalline polyolefin. Is more preferable.

Furthermore, in the present invention, the total content of the above-described crystalline polyolefin and styrene-based thermoplastic elastomer is the amount before the dynamic crosslinking including the ethylene-propylene-based rubber compound and the crosslinking agent described later and other various additives. It is preferable that it is 10-35 mass% with respect to the mass of the whole mixture.
When the content is within this range, the above-described crystalline polyolefin and styrene thermoplastic elastomer become a matrix (continuous phase), an ethylene-propylene rubber compound described later becomes a domain (dispersed phase), and is flexible and excellent. A thermoplastic elastomer composition exhibiting rubber-like elasticity can be obtained.

  The total content of the crystalline polyolefin and the styrenic thermoplastic elastomer described above is such that the resulting thermoplastic elastomer composition of the present invention exhibits low hardness, low compression set, and excellent mechanical strength. For the reason, the content is more preferably 20 to 30% by mass with respect to the mass of the whole mixture before dynamic crosslinking including the later-described ethylene-propylene rubber compound and crosslinking agent and other various additives.

<Ethylene-propylene rubber compound>
The ethylene-propylene rubber compound is an uncrosslinked ethylene propylene copolymer (EPR) and / or an ethylene propylene diene terpolymer (EPDM) copolymerized by adding a small amount of non-conjugated diene to ethylene and propylene. This is a rubber compound contained as a rubber.

In the present invention, an ethylene-propylene rubber compound having a Mooney viscosity of 35 or less at 100 ° C. is used.
By using such an ethylene-propylene rubber compound, an extreme increase in the viscosity of the resulting thermoplastic elastomer composition of the present invention can be prevented, the fluidity can be improved, and the oil and / or plasticizer described below can be used. It is difficult to shift to a hot melt adhesive, and the adhesiveness with the hot melt adhesive is also good.
This is because whether or not the ethylene-propylene rubber compound becomes a dispersed phase at a predetermined volume fraction during dynamic cross-linking described later depends on the viscosity ratio between the continuous phase and the dispersed phase at the shear rate during kneading. Since it is thought that it depends greatly, reducing the viscosity of the ethylene-propylene rubber compound that becomes the dispersed phase while keeping the viscosity ratio constant is the viscosity of the crystalline polyolefin and the styrene thermoplastic elastomer that are relatively continuous phases. Will be lowered. And when the viscosity of a continuous phase reduces, the viscosity of the thermoplastic-elastomer composition of this invention obtained will reduce, and it will be thought that fluidity | liquidity etc. become favorable.
Here, the Mooney viscosity at 100 ° C. is “Mooney viscosity test” described in JIS K6300-1: 2001 using a Mooney viscometer (L-shaped rotor) under the conditions of a preheating time of 1 minute and a test temperature of 100 ° C. It is the value measured by.

Moreover, in this invention, the aspect in which the said ethylene-propylene type rubber compound contains 25 mass% or more of liquid polymers whose kinematic viscosity in 40 degreeC is 5000-350,000 mm < ² > / s is preferable.
By containing such a liquid polymer, the oil and / or plasticizer, which will be described later, are less likely to migrate to the hot melt adhesive, and the adhesiveness with the hot melt adhesive is also improved.

Regarding the kinematic viscosity of the above liquid polymer, the fluidity of the resulting thermoplastic elastomer composition of the present invention is further improved, and the content of oil and / or plasticizer described later is further reduced to provide a hot melt adhesive. prevent migration, the reason that adhesion between the hot-melt adhesive is further improved, is preferably from 5000~200000mm ² / s, and more preferably 10000~100000mm ² / s.

  Examples of such liquid polymers include liquid polybutene; liquid polyisobutene; liquid polyisoprene; liquid polybutadiene; liquid polyα-olefin; liquid ethylene α-olefin copolymer; liquid ethylene propylene copolymer; Polymers, liquid acrylonitrile butadiene copolymers, hydroxy group-terminated polybutadienes and their hydrogenated products, hydroxy group-modified polymers such as hydroxy group-terminated polyisoprenes and their hydrogenated products; epoxy group-modified polymers such as epoxy-modified polybutadienes; (Meth) acrylic group-modified polymers such as acrylic-terminated polybutadiene; hydrolyzable silicon group-containing polyolefins such as silane-grafted polyolefin and silane-terminated polyolefin; maleic anhydride-modified poly Acid anhydride group modified polymers such as isoprene, maleic anhydride modified polybutadiene, maleic anhydride modified polybutene, maleic anhydride modified ethylene propylene copolymer, maleic anhydride modified ethylene alpha olefin copolymer; carboxy modified polybutadiene, carboxy modified Polyisoprene, carboxy group-modified polymer such as carboxy group-terminated acrylonitrile butadiene copolymer (CTBN); amino group-modified polymer such as amino group-terminated acrylonitrile butadiene copolymer (ATBN); You may use independently and may use 2 or more types together.

Among these, the fluidity of the resulting thermoplastic elastomer composition of the present invention is particularly good, and the liquid and the polyisobutene, which will be described later, are difficult to migrate to the hot-melt adhesive because the oil and / or plasticizer described later is particularly difficult to migrate. It is preferably at least one selected from the group consisting of liquid polyisoprene, liquid polybutadiene, liquid poly α-olefin, liquid ethylene α-olefin copolymer, liquid ethylene propylene copolymer and liquid ethylene butylene copolymer. .
Especially, it is especially preferable that ratio ((eta) 40 / (eta) 100) of kinematic viscosity in 40 degreeC and kinematic viscosity in 100 degreeC is 30 or more.
By containing such a liquid polymer, an extreme increase in the viscosity of the resulting thermoplastic elastomer composition of the present invention is prevented, and the fluidity becomes better. This is because the temperature dependence of the kinematic viscosity of the ethylene-propylene rubber compound is increased, so that the viscosity at the time of dynamic cross-linking (at high temperature) described later can be lowered, and the ethylene-propylene rubber compound has the above-described crystal. This is presumably because it can be finely dispersed in a matrix component having a low viscosity, such as a functional polyolefin and a styrene thermoplastic elastomer. In addition, when used as a glazing gasket (at low temperatures), the fluidity of the liquid polymer is reduced, so that it does not migrate to a hot melt adhesive as in the case of oils and / or plasticizers to be described later. It is thought that it does not cause sex decline.

Here, the kinematic viscosity at 40 ° C. (η40) and the kinematic viscosity at 100 ° C. (η100) are values measured according to the “kinematic viscosity test method” described in JIS K2283-1993, respectively.
Further, the lower limit of the kinematic viscosity (η40) and 5000 mm ² / s or more, the upper limit was set to less than 350000mm ² / s is significant to ensure the adhesion of the thermoplastic elastomer composition obtained.
Furthermore, the ratio of the kinematic viscosity at 40 ° C. to the kinematic viscosity at 100 ° C. (η40 / η100) was set to 30 or more from the viewpoint of the temperature dependence of the kinematic viscosity of the liquid polymer. Significant to ensure liquidity.

  The content in the case of containing the liquid polymer is 25% by mass or more of the ethylene-propylene rubber compound, but the fluidity of the resulting thermoplastic elastomer composition of the present invention becomes better, and the oil and It is preferable that the content of the plasticizer is 25 to 35% by mass because the plasticizer is less likely to migrate to the hot melt adhesive and is more excellent in adhesion between the hot melt adhesive and the thermoplastic elastomer composition of the present invention. .

  The combination of the crystalline polyolefin and the styrenic thermoplastic elastomer and the liquid polymer is not particularly limited. For example, as the crystalline polyolefin, at least one selected from the group consisting of crystalline polyethylene and crystalline polypropylene is used. At least one selected from the group consisting of hydrogenated styrene butadiene random copolymer (h-SBR), hydrogenated styrene butadiene block copolymer (SEBS) and hydrogenated styrene isoprene block copolymer (SEPS) as the thermoplastic elastomer. When is used, a combination with a liquid polybutene and / or a liquid ethylene α-olefin copolymer is preferable.

In the present invention, one of the preferred embodiments is that the ethylene propylene copolymer (EPR) and / or the ethylene propylene diene terpolymer (EPDM) contained as uncrosslinked rubber is oil-extended. As mentioned.
Here, the oil-extended uncrosslinked rubber contains uncrosslinked rubber and oil and / or a plasticizer, but considering the transition to a hot melt adhesive, the entire thermoplastic elastomer composition of the present invention The amount of oil and / or plasticizer is preferably 15% by mass or less based on the mass of.
The oil-extended uncrosslinked rubber is not particularly limited with respect to its production method. For example, a conventionally well-known thing is mentioned.

The oil and / or plasticizer is not particularly limited as long as it is a rubber softener. As the oil or plasticizer, it is preferable that the kinematic viscosity at 40 ° C. is less than 1000 mm ² / s.

  Specific examples of the oil include vegetable oils such as palm oil; mineral oil hydrocarbons such as paraffinic oil, naphthenic oil, and aromatic oil, and hydrogenated products thereof.

  Specific examples of the plasticizer include phthalate plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP); epoxidized soybean oil, Epoxy plasticizers such as epoxidized fatty acid esters; chlorinated plasticizers such as chlorinated fatty acid esters and chlorinated paraffins; tricresyl phosphate (TCP), tri-β-chloroethyl phosphate (TCEP), etc. Phosphoric acid plasticizers; adipic acid plasticizers such as dioctyl adipate (DOA) and didecyl adipate (DDA); sebacic acid plasticizers such as dibutyl sebacate (DBS); Azelaic acid plasticizer; triethyl citrate (T Citrate-based plasticizers such as C); polyester-based plasticizers such as polypropylene adipate (PPA); and the like.

Of these, mineral oil-based hydrocarbons are preferred and paraffin-based oils are more preferred because the fluidity of the thermoplastic elastomer composition of the present invention is better.
The paraffinic oil is not particularly limited. For example, a mixture of an aromatic ring, a naphthene ring, and a paraffin chain, in which the carbon number of the paraffin chain is 50% or more of the total carbon number can be mentioned.
Oils and / or plasticizers can be used alone or in combination of two or more.

  In the thermoplastic elastomer composition of the present invention, an ethylene-propylene system is obtained by dynamically crosslinking a mixture containing the above-described crystalline polyolefin, styrene-based thermoplastic elastomer, ethylene-propylene rubber compound, and a crosslinking agent described later. At least a part of the rubber compound becomes a crosslinked rubber, and a thermoplastic elastomer composition in which the ethylene-propylene rubber compound is dispersed in the form of particles in the crystalline polyolefin and the styrene thermoplastic elastomer can be obtained.

<Crosslinking agent>
The cross-linking agent is not particularly limited as long as it can cross-link ethylene propylene copolymer (EPR) and / or ethylene propylene diene terpolymer (EPDM) as uncrosslinked rubber. Examples thereof include sulfur-based, organic peroxide-based, and phenol resin-based rubber vulcanizing agents.

Specific examples of the sulfur vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like.
It is preferable that the usage-amount of a sulfur type vulcanizing agent is 0.5-4 mass parts with respect to 100 mass parts of uncrosslinked rubber, for example.

Specific examples of the organic peroxide vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like.
It is preferable that the usage-amount of an organic peroxide type | system | group vulcanizing agent is 1-15 mass parts with respect to 100 mass parts of uncrosslinked rubbers, for example.

Specific examples of the phenol resin-based vulcanizing agent include brominated phenol resins and mixed crosslinking systems containing halogen donors such as tin chloride and chloroprene and alkylphenol resins.
It is preferable that the usage-amount of a phenol resin type vulcanizing agent is 1-20 mass parts with respect to 100 mass parts of uncrosslinked rubbers, for example.

  As other vulcanizing agents, specifically, for example, magnesium oxide (about 4 parts by mass with respect to 100 parts by mass of uncrosslinked rubber), resurge (10 to 20 parts by mass with respect to 100 parts by mass of uncrosslinked rubber) Degree), p-quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene (about 2 to 10 parts by mass with respect to 100 parts by mass of uncrosslinked rubber), Methylindianiline (about 0.2 to 10 parts by mass with respect to 100 parts by mass of uncrosslinked rubber).

  In the present invention, the total content of the above-described ethylene-propylene rubber compound and the crosslinking agent is because the hardness, compression set and tensile strength of the resulting thermoplastic elastomer composition of the present invention are good. It is preferable that it is 75 mass% or more with respect to the mass of the whole mixture before dynamic crosslinking including the crystalline polyolefin mentioned above, a styrene-type thermoplastic elastomer, and other various additives, It is 75-85 mass%. Is more preferable.

The thermoplastic elastomer composition of the present invention can further contain a filler as necessary as another additive.
The filler is not particularly limited as long as it can contain the thermoplastic elastomer composition of the present invention, and specific examples thereof include talc, calcium carbonate, mica, carbon black and the like.

From the viewpoint that the content of the filler does not hinder the flexibility of the thermoplastic elastomer composition of the present invention, 50 to 100 parts by mass with respect to 100 parts by mass in total of the crystalline polyolefin and the styrene-based thermoplastic elastomer described above. It is preferable that it is 60-80 mass parts.
The filler content is based on the total mass of the mixture before dynamic crosslinking, including the above-mentioned crystalline polyolefin, styrene thermoplastic elastomer, ethylene-propylene rubber compound, crosslinking agent, and other various additives. The content is preferably 5 to 25% by mass, and more preferably 10 to 20% by mass.

Moreover, the thermoplastic elastomer composition of this invention can contain a crosslinking adjuvant as other additives as needed.
Specific examples of the crosslinking aid include zinc oxide; stearic acid, oleic acid, and Zn salts thereof.

In addition, the thermoplastic elastomer composition of the present invention can further contain a vulcanization accelerator as necessary as another additive.
Examples of the vulcanization accelerator include aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea vulcanization accelerators.

Specific examples of the aldehyde / ammonia vulcanization accelerator include hexamethylenetetramine.
Specific examples of the guanidine vulcanization accelerator include diphenyl guanidine.
Specific examples of the thiazole vulcanization accelerator include dibenzothiazyl disulfide (DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt, and the like.
Specific examples of the sulfenamide vulcanization accelerator include cyclohexylbenzothiazylsulfenamide (CBS), N-oxydiethylenebenzothiazyl-2-sulfenamide, and Nt-butyl-2. -Benzothiazole sulfenamide, 2- (thymolpolynyldithio) benzothiazole, etc. are mentioned.

Specific examples of the thiuram vulcanization accelerator include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide (TMTM), dibentamethylene thiuram tetrasulfide, and the like.
Specific examples of the dithioate vulcanization accelerator include Zn-dimethyldithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, and Tc-diethyl. Examples thereof include dithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoline pipecolyl dithiocarbamate, and the like.
Specific examples of the thiourea vulcanization accelerator include ethylene thiourea and diethyl thiourea.

  For example, the content of the vulcanization accelerator is about 0.5 to 2 parts by mass with respect to 100 parts by mass of the uncrosslinked rubber in the above-described ethylene-propylene rubber compound. It is done.

  Furthermore, the thermoplastic elastomer composition of the present invention is, for example, a tackifier such as rosin ester and coumarone resin, an anti-aging agent, a heat stabilizer, an antioxidant, a processing aid, as long as the object of the present invention is not impaired. Additives such as adhesives, hygroscopic agents, adhesive resins, heat stabilizers, light stabilizers, fluorescent brighteners, antistatic agents, lubricants, anti-adhesive agents, nucleating agents, dyes, pigments, flame retardants, barrier resins, and reinforcing materials An agent can be contained.

In the thermoplastic elastomer composition of the present invention, if the compatibility between the crystalline polyolefin and the styrene thermoplastic elastomer described above and the ethylene-propylene rubber compound is poor, a compatibilizer may be added as another additive. it can.
By adding a compatibilizing agent, the interfacial tension between the crystalline polyolefin and the styrenic thermoplastic elastomer and the uncrosslinked rubber decreases, and as a result, the particle size of the uncrosslinked rubber forming the dispersed phase becomes fine. Therefore, the characteristics of both compositions can be expressed more effectively.

As the compatibilizing agent, for example, both the above-mentioned crystalline polyolefin and styrene thermoplastic elastomer and uncrosslinked rubber (hereinafter abbreviated as “uncrosslinked rubber” in this paragraph) contained in the ethylene-propylene rubber compound. Alternatively, a polymer having one structure, a polymer having an epoxy group, a carboxy group, a carbonyl group, a halogen group, an amino group, an oxazoline group, or a hydroxy group that can react with a polyolefin, a thermoplastic resin, or an uncrosslinked rubber can be given.
Specifically, hydrogenated styrene butadiene block copolymer (SEBS) and its maleic acid modified product; ethylene propylene copolymer (EPR), ethylene propylene diene terpolymer (EPDM) and their maleic acid modified product EPDM-styrene and its maleic acid modified product; EPDM-acrylonitrile graft copolymer and its maleic acid modified product; styrene-maleic acid copolymer; reactive phenoxin and the like.
The compatibilizers can be used alone or in combination of two or more.
The compatibilizing agent can be appropriately selected according to the types of the thermoplastic resin and the uncrosslinked rubber.

  The addition amount of the compatibilizer is 0.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the crystalline polyolefin and the styrene thermoplastic elastomer and the ethylene-propylene rubber compound described above from the viewpoint of compatibility. Is preferred.

The above-described crystalline polyolefin and styrene-based thermoplastic elastomer (hereinafter referred to as “thermoplastic polymer” in this paragraph to [0086] paragraph) and ethylene-propylene rubber in the thermoplastic elastomer composition of the present invention. The content of the compound (hereinafter abbreviated as “uncrosslinked rubber compound” in the present paragraph to [0086] paragraph) will be described below.
From the viewpoint that the thermoplastic polymer and the uncrosslinked rubber compound are excellent in rubber-like elasticity, the mass ratio of the thermoplastic polymer to the uncrosslinked rubber compound (thermoplastic polymer / uncrosslinked rubber compound) is preferably 85 / It is 15-15 / 85, More preferably, it is 50 / 50-15 / 85. The criticality of this ratio depends on the relationship between the volume ratio and the viscosity ratio of the thermoplastic polymer and the uncrosslinked rubber compound.
That is, in the thermoplastic elastomer composition of the present invention, even if an uncrosslinked rubber compound and a thermoplastic polymer are simply kneaded in a molten state, the desired thermoplastic elastomer composition having a dispersed structure cannot always be obtained. In order for the thermoplastic polymer to constitute the continuous phase and the uncrosslinked rubber compound to constitute the dispersed phase, the value of α ₁ obtained by the following formula (1) may be less than 1.

α ₁ = (φ _R / φ _P ) × (η _P / η _R ) (1)

Wherein, phi _R is Not in the volume fraction of the uncrosslinked rubber compound, phi _P is the volume fraction of the thermoplastic polymer, eta _R temperatures and shear rate conditions at the time of kneading the thermoplastic polymer and an uncrosslinked rubber compound The melt viscosity of the crosslinked rubber compound, and η _P represents the melt viscosity of the thermoplastic polymer under the temperature and shear rate conditions when the thermoplastic polymer and the uncrosslinked rubber compound are kneaded.
When the value of α ₁ is 1 or more, the dispersion structure of the thermoplastic elastomer composition of the present invention is reversed, and the uncrosslinked rubber compound may become a continuous phase.

Moreover, it is preferable that 0.5 ≦ η _R / η _P ≦ 3.0. In such a range, uncrosslinked rubber can be dispersed as particles having a size of about 0.1 to several tens of μm in the thermoplastic polymer.

In this specification, the melt viscosity refers to the melt viscosity of each component at an arbitrary temperature during kneading. The melt viscosity of the polymer component varies depending on temperature, shear rate (sec ⁻¹ ) and shear stress. For this reason, in general, the polymer component in the molten state is allowed to flow in the capillary tube at an arbitrary temperature in the molten state, particularly in the temperature range during kneading, and the stress and shear rate are measured. By applying the value of the shear rate to the following formula (2), the melt viscosity η of the polymer component can be obtained.

  For the measurement of the melt viscosity, for example, a capillary rheometer capilograph 1C manufactured by Toyo Seiki Co., Ltd. can be used.

The thermoplastic elastomer composition of the present invention has a Shore A hardness of 65 or less, a compression set of 50% or less, a tensile strength of 4.5 MPa or more, and physical properties after dynamic crosslinking, which will be described later. The viscosity under the conditions of ° C and a shear rate of 100 s ^-1 is preferably 2000 Pa · s or less.

Here, the Shore A hardness is a “durometer” defined by JIS K6253-1997 using a sheet (thickness 2 mm, length 200 mm, width 25 mm) obtained by heating and pressurizing the thermoplastic elastomer composition to 180 ° C. It is a value measured by “hardness test (type A)”.
The Shore A hardness is more preferably 45 to 65, and even more preferably 45 to 55. In such a range, the thermoplastic elastomer composition is excellent in flexibility.

The compression set was measured using a cylindrical sample prepared in accordance with JIS K6262: 1997 under the conditions of 100 ° C. and 22 hours in accordance with the “compression set test” defined in JIS A5756: 1997. Value.
The compression set is more preferably 15 to 50%, and further preferably 15 to 30%. In such a range, the thermoplastic elastomer composition is not easily crushed by compression.

The tensile strength is a value measured using a similar sheet in accordance with the “tensile test” defined in JIS A5756: 1997.
The tensile strength is more preferably 4.5 to 10 MPa, and further preferably 6 to 10 MPa.

The viscosity is a value measured using the obtained thermoplastic elastomer composition, using a capillary rheometer, at a shear rate of 100 s ⁻¹ at 180 ° C.
The viscosity under the conditions of 180 ° C. and a shear rate of 100 s ⁻¹ is preferably 3000 Pa · s or less, more preferably 500 to 2000 Pa · s, and even more preferably 500 to 1000 Pa · s. In such a range, the fluidity is excellent and the workability is excellent.

The thermoplastic elastomer composition of the present invention is obtained by dynamically crosslinking a mixture containing the above-described crystalline polyolefin, styrene thermoplastic elastomer, ethylene-propylene rubber compound, a crosslinking agent, and various additives such as a filler. Can be manufactured.
The dynamic crosslinking is described in detail below.

In the dynamic crosslinking, the above-mentioned crystalline polyolefin, styrene thermoplastic elastomer and ethylene-propylene rubber compound are supplied in advance to a kneader such as a twin-screw kneading extruder and melt kneaded (in a state where the crystalline polyolefin is melted). Kneading, the same applies hereinafter), and the ethylene-propylene rubber compound is dispersed as a dispersed phase (domain) in the crystalline polyolefin and styrene thermoplastic elastomer forming the continuous phase (matrix phase).
Here, it is mentioned as one of the preferred embodiments that a crosslinking agent is added under kneading to obtain a mixture, and at least a part of the uncrosslinked rubber of the ethylene-propylene rubber compound in the mixture is crosslinked to obtain a crosslinked rubber. .

Here, as a condition for melt kneading, the shear rate during kneading is preferably 500 to 7500 sec ⁻¹ . The total kneading time is preferably 30 seconds to 10 minutes, and the vulcanization time after addition is preferably 15 seconds to 5 minutes.

The crosslinking agent used for the dynamic crosslinking is not particularly limited because it can be appropriately determined according to the composition of the uncrosslinked rubber to be used, and examples thereof include those exemplified above.
Moreover, in the said dynamic bridge | crosslinking, the crosslinking adjuvant illustrated above can be used with a crosslinking agent as needed.

Further, in the dynamic crosslinking, various additives exemplified above can be used as necessary.
Here, the addition of various additives may be performed during the above-described kneading operation, but may be previously mixed before kneading. At this time, a crosslinking agent can also be mixed in advance in the ethylene-propylene rubber compound, and the ethylene-propylene rubber compound can be crosslinked when kneaded with the crystalline polyolefin and the styrene thermoplastic elastomer.

  The kneader used for kneading the crystalline polyolefin and the styrene thermoplastic elastomer and the ethylene-propylene rubber compound is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a twin-screw kneading extruder. . One preferred embodiment of the dynamic crosslinking is to use a twin-screw kneading extruder. Further, two or more types of kneaders can be used and kneaded sequentially.

In the present invention, the dynamic cross-linking has two screws having a screw length (La) / screw diameter (D) of 40 or more from the center position of the material input port, and each of these screws, The first kneading region has a screw length (La) / screw diameter (D) from the center position of the material inlet in a range of 5 to 15, and the screw length (Lb ) / It is preferably carried out using a twin-screw kneading extruder having at least four kneading segments having a screw diameter (D) of 1 or less.
Here, the screw length (La) is the screw length from the center position of the material input port of the twin-screw kneading extruder, that is, the total length of the screw.
On the other hand, the screw length (Lb) is the length of a part of the screw in the first kneading region, that is, the length of the kneading segment.

  By performing dynamic crosslinking using such a twin-screw kneading extruder, rubber dispersion in the resulting thermoplastic elastomer composition of the present invention is improved, and occurrence of abnormal appearance after crosslinking can be prevented. This is considered to be because dispersion at the initial stage of crosslinking can be increased and heat generation can be suppressed.

Moreover, in this invention, it is preferable that the temperature in the 1st kneading | mixing area | region of the said biaxial kneading extruder is the temperature below the melting point of the crystalline polyolefin mentioned above.
When the temperature is equal to or lower than the melting point of the crystalline polyolefin, the cooling effect at the initial dispersion can be further enhanced, and the occurrence of abnormal appearance after crosslinking of the resulting thermoplastic elastomer composition of the present invention can be further prevented. . This is considered to be because excessive vulcanization progress can be suppressed in the initial stage of crosslinking.

Furthermore, in the present invention, it is preferable that the screw of the twin-screw kneading extruder further has a second kneading region in which the screw length (Lb) / screw diameter (D) is 10 or more. .
By having the 2nd kneading | mixing area | region, the dispersion | distribution and distribution effect of an ethylene-propylene type rubber compound are heightened, the further fine dispersion is attained, and the thermoplastic elastomer composition of the outstanding external appearance can be obtained.

By dynamically crosslinking the mixture in this manner, at least a part of the ethylene-propylene rubber compound becomes a crosslinked rubber, and the crosslinked rubber is dispersed in a particulate form in the crystalline polyolefin and the styrene thermoplastic elastomer. A plastic elastomer composition is obtained.
The particle diameter of the crosslinked rubber is preferably about 0.1 to several tens of μm from the viewpoint of excellent mechanical strength.

The obtained thermoplastic elastomer composition can be extruded from a kneading extruder into strands, cooled with water or the like, then pelletized with a resin pelletizer, and then molded and processed. Examples of the molding include injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, and calendar molding.
The prepared high-temperature thermoplastic elastomer composition can be placed and filled on an adherend such as glass from an extrusion nozzle with an extruder, for example. Further, the thermoplastic elastomer composition can be coextruded with an adhesive such as a hot melt adhesive and placed on glass.

  When the thermoplastic elastomer composition of the present invention is extruded and processed, the molding temperature for molding the thermoplastic elastomer composition is preferably 130 to 230 ° C, more preferably 160 to 180 ° C. preferable. In such a range, thermal degradation can be suppressed. Moreover, it is preferable that extrusion pressure is 5-15 Mpa.

The molding temperature and extrusion pressure when the thermoplastic elastomer composition of the present invention is processed by coextrusion molding with a hot melt adhesive are the same as described above.
Moreover, the coextrusion molding machine which can be used is not specifically limited. For example, a conventionally well-known thing is mentioned.

  Applications of the thermoplastic elastomer composition of the present invention include, for example, glazing gaskets such as glazing channels, beads, sealing, and packing.

  Examples of adherends to which the thermoplastic elastomer composition of the present invention can be used include metals such as stainless steel and aluminum, glass, coated plates, plastics, rubbers, and ceramics.

In the case of bonding the thermoplastic elastomer composition of the present invention to glass, one preferred embodiment is to use a hot-melt adhesive.
Hot melt adhesives include base polymers such as rubber and polyolefin, and additives such as tackifiers, plasticizers, rubber compositions, waxes, inorganic fillers, anti-aging agents, other polymers, etc. The thing containing these is mentioned as a preferable aspect. The amount ratio between the base polymer and the additive is not particularly limited. For example, a conventionally well-known thing is mentioned.

Specific examples of rubber include butyl rubber, styrene butadiene copolymer (SBR), ethylene-propylene copolymer (EPR), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-butylene. Examples thereof include a block copolymer (SEBS) and a styrene-ethylene-propylene block copolymer (SEPS). Of these, butyl rubber, EPR, SIS, SEBS, and SEPS are preferable examples.
The rubbers can be used alone or in combination of two or more.

Specific examples of the polyolefin include atactic-polypropylene (APP) and poly α-olefin.
Specific examples of the tackifier include rosin resin, terpene resin, petroleum resin, coumarone indene resin, modified products thereof, hydrogenated product, and the like. When based on styrene butadiene copolymer (SBR) and / or butyl rubber, petroleum resin systems and / or terpene resin systems are preferred.

Specific examples of the plasticizer include phthalic acid esters, glycol esters, and hydrocarbon plasticizers (polybutene, polyisobutylene, ethylene-propylene oligomer).
Specific examples of the wax include paraffin wax, microcrystalline wax, low molecular weight polyethylene, low molecular weight polypropylene, and Fischer-Tropsch wax.

Specific examples of the inorganic filler include calcium carbonate, talc, white carbon, silica, and carbon black.
Specific examples of the anti-aging agent include phenol-based and amine-based agents.
In addition, for example, various antioxidants, ultraviolet absorbers, and silane coupling agents can be contained.

Conventionally, thermoplastic elastomer compositions used in glazing gaskets contain a large amount of oil and / or plasticizer as a rubber softener.
However, when a glazing gasket is produced using such a thermoplastic elastomer composition and the obtained glazing gasket is bonded to a multilayer glass with a hot melt adhesive, the oil and / or the plasticizer is thermoplastic. The present inventor has found that the elastomer composition shifts to a hot melt adhesive and reduces the adhesive strength of the hot melt adhesive.
Therefore, the present inventor uses a thermoplastic elastomer composition containing an ethylene-propylene rubber compound having a predetermined viscosity, and reduces the oil and / or plasticizer contained in the thermoplastic elastomer composition. It has been found that the oil and / or plasticizer is prevented from shifting from the thermoplastic elastomer composition to the hot melt adhesive, and is excellent in adhesiveness between the thermoplastic elastomer composition and the hot melt adhesive.

In addition, the present inventor has found that the fluidity of the thermoplastic elastomer composition decreases when the amount of oil and / or plasticizer in the thermoplastic elastomer composition is simply reduced.
Therefore, the present inventor has a thermoplastic elastomer composition that is excellent in fluidity and can suppress the transition to a hot melt adhesive by including an ethylene-propylene rubber compound having a Mooney viscosity of 35 or less at 100 ° C. They found out that things could be obtained.

Next, the laminated body of this invention is demonstrated below.
The laminate of the present invention has a hot-melt adhesive between the thermoplastic elastomer composition of the present invention and glass.

The glass used in the laminate of the present invention is not particularly limited, and conventionally known ones can be used.
Moreover, the hot melt adhesive used for the laminate of the present invention is not particularly limited, and those exemplified above can be used. Of these, butyl, EPR, SEBS, and SBR are preferred examples.

Specifically, as a method for producing the laminate of the present invention, for example, a hot melt adhesive applied on glass and a molded body made of the thermoplastic elastomer composition of the present invention are bonded to each other to form a laminate. And a method of producing a laminate by co-extrusion of a hot melt adhesive and the thermoplastic elastomer composition of the present invention on glass.
Here, the thermoplastic elastomer composition of the present invention can be formed into a molded body by, for example, injection molding, extrusion molding, compression molding, vacuum molding, calendar molding, or the like.
The conditions for extrusion molding of the thermoplastic elastomer composition of the present invention are the same as described above.
The conditions for coextrusion molding of the thermoplastic elastomer composition of the present invention with a hot melt adhesive are the same as described above.

  The usage-amount of the thermoplastic elastomer composition in the case of manufacture of the laminated body of this invention is not specifically limited, For example, it can select suitably according to a use. Specifically, for example, when the thermoplastic elastomer composition is used as a glazing gasket, the amount of the thermoplastic elastomer composition used is 200 per glazing gasket per meter from the viewpoint of increasing the adhesion between the glass and the sash. It is preferably ˜600 g, more preferably 350 to 450 g.

  Since the thermoplastic elastomer composition of the present invention used for the laminate of the present invention has thixotropy, when the thermoplastic elastomer composition is extrusion-molded or co-extruded on glass, it should be applied with a thickness on the glass. Can do. The thickness of the thermoplastic elastomer composition applied on the glass is preferably 0.5 to 10 mm from the viewpoint of cooling and solidification.

  It is preferable that the usage-amount of a hot-melt-type adhesive agent is 5-20g per 1 meter of glazing gasket from a water-tight viewpoint.

The measurement of the adhesive strength of the laminate of the present invention will be described below.
One glass having a length of 200 mm, a width of 25 mm, and a thickness of 3 mm is prepared as an adherend. Also,
The thermoplastic elastomer composition of the present invention is heated and pressurized to 200 to 230 ° C. using a hot press to obtain a sheet-like sample having a length of 200 mm, a width of 25 mm, and a thickness of 2 mm.
An SBR type hot melt adhesive is applied to glass in an amount of 0.05 to 0.1 g / cm ² , and the hot melt adhesive and the obtained sheet-like sample are adhered to form a laminate.
Next, the obtained laminate was placed in an environment of 23 ° C. and 50% RH for 1 week to obtain a sample for evaluating adhesive strength. Using a tensile tester as a measuring instrument, a 90 ° peel test was performed on the adhesive strength evaluation sample under the condition of a gripper moving speed of 50 mm / min, and the adhesive strength was measured.

  The adhesive strength of the laminate of the present invention measured by the above test is preferably 1 N / mm or more. In such a range, it can be said that the adhesive strength with the hot melt adhesive is excellent. Moreover, it is preferable that the adhesive strength of the laminated body of this invention is 1-5 N / mm, and it is more preferable that it is 2.5-5 N / mm.

  Examples of the use of the laminate of the present invention include multilayer glass, automotive glass, and architectural glass.

Next, the glazing gasket of the present invention will be described below.
The glazing gasket of the present invention is obtained from the thermoplastic elastomer composition of the present invention.

  The manufacturing method of the glazing gasket of the present invention is not particularly limited. For example, (1) a method of previously forming a glazing gasket by extrusion molding, (2) a cavity in a mold in which glass (for example, multi-layer glass) is arranged A method in which glass and glazing gasket are integrally formed by a so-called encap method in which a resin is injected into a space. (3) A molding die and a multilayer glass are relatively placed on the outer peripheral surface of the glass plate of the multilayer glass. And the thermoplastic elastomer composition is extruded from a molding die and solidified to produce a multilayer glass and a glazing gasket.

  Examples of the extrusion molding machine that can extrude the thermoplastic elastomer composition from the molding die by relatively moving the molding die and the multilayer glass include those conventionally known. Moreover, when extruding the glazing gasket of this invention on glass, the thermoplastic elastomer composition and hot-melt-type adhesive to be used can be coextruded using a coextrusion molding machine. Such a coextrusion molding machine is not particularly limited, and examples thereof include conventionally known ones.

  Among these, from the viewpoint of production efficiency, the extruder (3) and the co-extrusion machine are preferable.

  The amount of the thermoplastic elastomer composition used in the production of the glazing gasket of the present invention is not particularly limited. The amount of the thermoplastic elastomer composition used is preferably 200 to 600 g, more preferably 350 to 450 g, per 1 m of the outer circumference of the multilayer glass from the viewpoint of increasing the adhesion between the glass and the sash.

  Since the thermoplastic elastomer composition of the present invention used in the production of the glazing gasket of the present invention has thixotropy, when the thermoplastic elastomer composition is extruded or coextruded on glass, it is formed on the glass. Can be constructed with thickness. The thickness of the thermoplastic elastomer composition applied on the glass is preferably 0.5 to 10 mm from the viewpoint of cooling and solidification.

The mechanical properties of the glazing gasket of the present invention are as follows: Shore A hardness is 65 or less, compression set (100 ° C. × 22 hours) is 50% or less, tensile strength is 4.5 MPa or more, and 180 ° C. The preferred embodiment is that the viscosity under the condition of a shear rate of 100 s ⁻¹ is 3000 Pa · s or less.
Each mechanical property is the same as described above.

  The shape of the glazing gasket of the present invention is not particularly limited. When the glazing gasket of the present invention is for a multilayer glass, for example, a substantially U-shape, U-shape, L-shape, and a shape that is symmetrically divided on the surfaces of the two outermost glasses of the multilayer glass. .

The glazing gasket of the present invention can be bonded to glass with a hot-melt adhesive. The hot-melt adhesive that can be used is the same as described above.
The hot melt adhesive can be pre-applied to the glass and / or the glazing gasket of the present invention before bonding the glazing gasket of the present invention.

When the glazing gasket of the present invention is adhered to glass with a hot melt adhesive, the adhesive strength between the glazing gasket and the hot melt adhesive is preferably 1 N / mm or more. In such a range, it can be said that the adhesive strength with the hot melt adhesive is excellent. Moreover, it is preferable that the adhesive strength of the laminated body of this invention is 1-5 N / mm, and it is more preferable that it is 2.5-5 N / mm.
The method for measuring the adhesive strength is the same as described above.

  The glazing gasket of the present invention can be used for glass, for example. It is mentioned as one of the preferable aspects that it is for multilayer glass.

Next, the multilayer glass with a glazing gasket of the present invention will be described.
The double-glazed glass with a glazing gasket of the present invention has a hot-melt adhesive between the double-glazed glass and the glazing gasket of the present invention.

  The multilayer glass used in the production of the multilayer glass with a glazing gasket of the present invention is not particularly limited. For example, two glass plates are opposed to each other through a spacer, the glass plate and the spacer are brought into close contact with a sealant such as butyl, and the internal air layer and the outside air are blocked, and then the opposed glass What is manufactured with the method of sealing the space | gap comprised by the inner surface of a board | plate and the spacer outer periphery with the normal temperature curable sealing material like a polysulfide type | system | group or a silicone type is mentioned.

  The glazing gasket used in the production of the multilayer glass with the glazing gasket of the present invention is not particularly limited as long as it is the glazing gasket of the present invention.

  The hot melt adhesive used in the production of the multi-layer glass with a glazing gasket of the present invention is not particularly limited. The hot melt adhesive is the same as described above.

The multilayer glass with a glazing gasket of the present invention is not particularly limited for its production. For example, (1) a method in which a hot-melt adhesive is applied to a glazing gasket and / or multilayer glass previously formed by extrusion molding, and these are bonded together, and (2) a hot-melt adhesive is applied. The multi-layer glass and the glazing gasket are integrally formed by a so-called encap method in which the multi-layer glass is disposed in the cavity space in the mold and the thermoplastic elastomer composition of the present invention is injected into the peripheral edge of the multi-layer glass. Method, (3) on the outer peripheral edge of the glass plate of the double-glazed glass, relatively moving the forming die and the double-glazed glass, extruding the thermoplastic elastomer composition of the present invention from the forming die, solidifying, Examples thereof include a method of integrating the double-glazed glass and the glazing gasket of the present invention.
In addition, when the thermoplastic elastomer composition of the present invention is extruded on glass, the thermoplastic elastomer composition and the hot melt adhesive can be coextruded.
Among these, from the viewpoint of production efficiency, the extruder (3) and the co-extrusion machine are preferable.
Thus, the multilayer glass with a glazing gasket of the present invention can be obtained by bonding the multilayer glass and the glazing gasket of the present invention with a hot-melt adhesive.

  The amount of the thermoplastic elastomer composition used in the production of the multi-layer glass with a glazing gasket of the present invention is not particularly limited. The amount of the thermoplastic elastomer composition used is preferably 200 to 600 g, more preferably 350 to 450 g, per 1 m of the outer circumference of the multilayer glass from the viewpoint of increasing the adhesion between the glass and the sash.

  When the thermoplastic elastomer composition of the present invention used in the production of the double-glazed glass with a glazing gasket of the present invention has thixotropy, the thermoplastic elastomer composition is extruded or coextruded on the glass. It can be applied to glass with a thickness. The thickness of the thermoplastic elastomer composition applied on the glass is preferably 0.5 to 10 mm from the viewpoint of cooling and solidification.

  It is preferable that the usage-amount of a hot-melt-type adhesive agent is 5-20g per 1 meter of glazing gasket from a water-tight viewpoint.

In the multilayer glass with a glazing gasket of the present invention, the adhesive strength between the glazing gasket and the hot-melt adhesive is preferably 1 N / mm or more. In such a range, it can be said that the adhesive strength with the hot melt adhesive is excellent. Moreover, it is preferable that the adhesive strength of the laminated body of this invention is 1-5 N / mm, and it is more preferable that it is 2.5-5 N / mm.
The method for measuring the adhesive strength is the same as described above.

  The double-glazed glass with a glazing gasket of the present invention is used as an architectural window glass or door by further attaching, for example, an aluminum or stainless steel glazing material to the peripheral edge of the double-glazed glass with the glazing gasket of the present invention. Can do.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Preparation of EPDM rubber compound (1) EPDM rubber compound 1 (uncrosslinked rubber)
In the components and quantity ratios shown in Reference Examples 1 and 4 and Comparative Examples 1 to 4 in Table 1, oil-extended EPDM (trade name: JSR EP501EF, manufactured by JSR, 40 parts by mass of paraffinic oil with respect to 100 parts by mass of EPDM) Partly contained. The same shall apply hereinafter) and a liquid ethylene α-olefin copolymer (trade name: Lucant HC-2000, η40: 37500 mm ² / s, η40 / η100: 19, manufactured by Mitsui Chemicals, the same shall apply hereinafter). And calcium carbonate (Super S, manufactured by Maruo Calcium Co., Ltd., the same shall apply hereinafter), carbon black (Seest V, manufactured by Tokai Carbon Co., Ltd., and so forth), and stearic acid (Beadstearic acid NY, manufactured by Nippon Oil & Fats Co., Ltd. The same) and zinc oxide (Zinc Hana No. 3, Shodo Chemical Industry Co., Ltd., the same shall apply hereinafter) at 100 ° C. using a Banbury mixer, and rubber By pelleting at at about 100 ° C. pelletizer to obtain EPDM rubber compound 1.

(2) EPDM rubber compound 2 (uncrosslinked rubber)
Oil-extended EPDM and liquid polybutene (trade names: Nisseki Polybutene HV-300, η40: 26000 mm ² / s, η40 / η100: 44, new in the components and amount ratios shown in Examples 2 and 3 in Table 1. Nippon Oil Co., Ltd., the same shall apply hereinafter), calcium carbonate, carbon black, stearic acid, and zinc oxide are kneaded at 100 ° C. using a Banbury mixer and pelletized at about 100 ° C. with a rubber pelletizer. As a result, EPDM rubber compound 2 was obtained.

(3) EPDM rubber compound 3 (uncrosslinked rubber)
In the components and quantity ratios shown in Comparative Example 5 in Table 1, oil-extended EPDM, calcium carbonate, carbon black, stearic acid, and zinc oxide were kneaded at 100 ° C. using a Banbury mixer, and rubber EPDM rubber compound 3 was obtained by pelletizing at about 100 ° C. with a pelletizer.

(4) EPDM rubber compound 4 (uncrosslinked rubber)
A Banbury mixer containing oil-extended EPDM, liquid ethylene α-olefin copolymer, calcium carbonate, carbon black, stearic acid, and zinc oxide in the components and quantitative ratios shown in Comparative Example 6 of Table 1. EPDM rubber compound 4 was obtained by kneading at 100.degree. C. and pelletizing at about 100.degree. C. with a rubber pelletizer.

  For the prepared EPDM rubber compounds 1 to 4, the Mooney viscosity at 100 ° C. was measured according to JIS K6300-1: 2001 using a Mooney viscometer (L-shaped rotor) with a preheating time of 1 minute and a test temperature of 100 ° C. It was measured by the described “Mooney viscosity test”. The results are shown in Table 1 below.

2. Preparation of thermoplastic elastomer composition (Examples 2 and 3, Reference Examples 1 and 4, and Comparative Examples 1 to 6)
Table 1 shows the EPDM rubber compound and the cross-linking agent prepared by dry blending the crystalline polyolefin shown in Table 1 and the styrene-based thermoplastic elastomer at the quantitative ratio shown in Table 1 and the component ratio shown in Table 1. The mixture was put into a twin-screw kneading extruder at a quantitative ratio, melt kneaded, and then dynamically crosslinked to prepare a thermoplastic elastomer composition. The biaxial kneading extruder at this time set the temperature in the 1st kneading area | region mentioned later to 120 degreeC, set the temperature after that to the temperature of 200 degreeC, and set the shear rate to 1000 s- ¹ .
In Comparative Example 6, since the Mooney viscosity at 100 ° C. of EPDM rubber compound 4 exceeded 35, the EPDM rubber compound became a continuous layer, and the mixture became powdery, so that a thermoplastic elastomer composition could be prepared. There wasn't.

Here, the twin-screw kneading extruder has two screws having a screw length (La) / screw diameter (D) of 49 from the center position of the material input port, and each of these screws is used as a material input port. The first kneading region has a screw length (La) / screw diameter (D) from the center position of 8 to 14, and in this first kneading region, the screw length (Lb) / screw diameter (D ) Was used having 6 kneading segments with 1.
Further, the screw of this twin-screw kneading extruder had a second kneading region in a range where screw length (Lb) / screw diameter (D) was 15.
Furthermore, the temperature in the first kneading region of this twin-screw kneading extruder was set to a temperature not higher than the melting point of the crystalline polyolefin.

Details of the components shown in Table 1 are as follows.
PP1: Crystalline polypropylene (Sun Allomer PMA 20V, MFR: 45, Viscosity at a shear rate of 100 s ⁻¹ at 180 ° C .: 330 Pa · s, manufactured by Sun Allomer)
PP2: Crystalline polypropylene (Sun Allomer PM731M, MFR: 9.5, viscosity at 180 ° C. and shear rate of 100 s ⁻¹ : 650 Pa · s, manufactured by Sun Allomer)
H-SBR1: hydrogenated styrene butadiene random copolymer (DYNARON 1321P, MFR: 10, viscosity at 180 ° C. and shear rate of 100 s ⁻¹ : 1600 Pa · s, Shore A hardness: 41, manufactured by JSR)
H-SBR2: hydrogenated styrene butadiene random copolymer (DYNARON 1320P, MFR: 3.5, viscosity at shear rate of 100 s- ¹ at 180 ° C .: 2300 Pa · s, Shore A hardness: 41, manufactured by JSR)
SEBS: hydrogenated styrene butadiene block copolymer (Tuftec H1052, MFR: 13, viscosity at a shear rate of 100 s ⁻¹ at 180 ° C .: 1300 Pa · s, Shore A hardness: 57, manufactured by Asahi Kasei Corporation)

・ Oil-extended EPDM: 100 parts by weight of EPDM containing 40 parts by weight of paraffinic oil (JSR EP501EF, manufactured by JSR)
・ Calcium carbonate: Super S, manufactured by Maruo Calcium Co., Ltd. ・ Carbon black: Seast V, manufactured by Tokai Carbon Co., Ltd. ・ Stearic acid: Beads stearic acid NY, manufactured by Nippon Oil & Fats Co., Ltd. Liquid polybutene: Liquid polybutene (trade name: Nisseki Polybutene HV-300, η40: 26000 mm ² / s, η40 / η100: 44, manufactured by Nippon Oil Corporation)
Liquid ethylene α-olefin copolymer (trade name: Lucant HC-2000, η40: 37500 mm ² / s, η40 / η100: 19, manufactured by Mitsui Chemicals)

  ・ Crosslinking agent: brominated phenol, tackolol 250-I, manufactured by Taoka Chemical Co., Ltd.

3. Evaluation of thermoplastic elastomer composition Physical properties of thermoplastic elastomer composition (Shore A hardness, compression set, tensile strength and viscosity), adhesiveness of thermoplastic elastomer composition, water tightness between glazing gasket and sash, The long-term durability of the multilayer glass and the applicability of the thermoplastic elastomer composition were evaluated as follows. The results are shown in Table 2.
In Comparative Example 6, since the Mooney viscosity at 100 ° C. of EPDM rubber compound 4 exceeds 35 and the viscosity of the crystalline polyolefin and the styrene-based thermoplastic elastomer used in combination is low, the preparation of the thermoplastic elastomer composition I could not.

3-1. Physical Properties of Thermoplastic Elastomer Composition (1) Preparation of Sample for Evaluation The obtained thermoplastic elastomer composition is heated and pressurized to 180 ° C. using a hot press to form a sheet having a length of 200 mm, a width of 200 mm, and a thickness of 2 mm. A sample was used.
(2) Shore A hardness Using the obtained sheet-like sample, it was measured by a “durometer hardness test (type A)” defined in JIS K6253-1997.

(3) Compression set Using a cylindrical sample prepared according to JIS K6262: 1997, measurement was performed at 100 ° C. for 22 hours in accordance with a “compression set test” defined in JIS A5756: 1997.
(4) Tensile strength The obtained sheet-like sample was measured according to the “tensile test” defined in JIS A5756: 1997.
(5) Viscosity Using the obtained thermoplastic elastomer composition, the viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. was measured using a capillary rheometer.
As a result, if the viscosity is 2000 Pa · s or less, it can be evaluated that the fluidity is excellent.

3-2. Adhesiveness of thermoplastic elastomer composition One glass having a length of 200 mm, a width of 25 mm, and a thickness of 5 mm was prepared. A hot melt adhesive (Hamatite M-1500, manufactured by Yokohama Rubber Co., Ltd., the same applies hereinafter) was applied to one side of this glass in an amount of 0.1 g / cm ² , and a sheet-like sample (vertical length) was obtained thereon. 200 mm, width 25 mm, thickness 2 mm) was further laminated. After the lamination, the glass was placed in an environment of a temperature of 23 ° C. and a humidity of 50% RH for one week to obtain a laminate of glass and a thermoplastic elastomer composition.

Next, using the obtained laminate, a 90 ° peel test of the laminate was performed under the conditions of 23 ° C. and 50% RH, using a tensile tester as a measuring instrument, with a gripping tool moving speed of 50 mm / min. The adhesive strength was measured.
Here, the case where the adhesive strength was 1 N / mm or more was evaluated as “◯” as having excellent adhesiveness.
Further, the hot melt adhesive of the specimen after the 90-degree peeling test was subjected to GPC measurement of a substance near the interface, and the presence or absence of a molecular weight peak derived from the oil component contained in the thermoplastic elastomer composition was confirmed.

3-3. Double-glazed glass with glazing gasket and production thereof, double-glazed glass with sash and production thereof First, double-glazed glass with glazing gasket and production thereof will be described with reference to the accompanying drawings.
FIG. 1 is a schematic view schematically showing a part of a cross section of one embodiment of a multilayer glass with a glazing gasket of the present invention.
In FIG. 1, reference numeral 1 denotes a multilayer glass with a glazing gasket. The multilayer glass 1 with a glazing gasket has a multilayer glass unit 13, a glazing gasket 5, and a hot-melt adhesive 7. The hot-melt adhesive 7 bonds the glass 3 of the multilayer glass unit 13 and the glazing gasket 5.
The multilayer glass unit 13 includes two glasses 3 (vertical 950 mm, horizontal 950 mm), a spacer 9, a primary sealing material 10, and a secondary sealing material 11. The two glasses 3 are opposed to each other with a spacer 9 and a primary sealing material 10 interposed therebetween, and the secondary sealing material 11 is arranged in an open space formed by the inside of the two glasses 3 and the spacer 9. Thus, the internal space 15 formed by the inside of the two glass plates 3 and the spacer 9 is sealed. The thickness of the multilayer glass unit 13 is 18 mm.
The multi-layer glass 1 with a glazing gasket is formed on the end of the glass 3 on both sides of such a multi-layer glass unit 13 with an automatic application device (not shown) and a thermoplastic elastomer composition and a hot-melt adhesive 7. Are coextruded.
An automatic coating apparatus is not specifically limited, A conventionally well-known thing can be used. The automatic coating apparatus used in the examples of the present invention includes an I-shaped molding die, a shot pump for a thermoplastic elastomer composition, and a shot pump for a hot melt adhesive (not shown). Each shot pump has a pressure gauge for measuring the internal pressure (not shown).
The thermoplastic elastomer composition coextruded to the ends of the glass 3 on both sides by an automatic coating apparatus becomes the I-shaped glazing gasket 5 having a width of 15 mm.
The hot melt adhesive 7 is applied with a thickness of 0.2 mm.
The thermoplastic elastomer composition and the hot melt adhesive are applied to the ends of the glass 3 on both sides with the same width of 15 mm.

  The multilayer glass 1 with a glazing gasket thus obtained was fitted into an aluminum sash (not shown) to obtain a sashed multilayer glass (not shown).

3-4. Watertightness between the glazed gasket-attached double-glazed glass and the sash. The sash-coated double-glazed glass obtained as described above is fixed vertically, and the sash and glazing gasket are connected at points other than the contacts and drainage holes are sealed. Then, water is allowed to flow at 5 liters / minute for 10 minutes from the top of the sashed double-glazed glass to both sides of the sashed double-glazed glass including the glazing gasket construction part, and whether or not water enters the sash is evaluated. did.
Here, the case where water did not enter was evaluated as “◯” as being excellent in water tightness, and the case where water was less than 10 ml was evaluated as “△” as being slightly inferior in water tightness.

3-5. Long-term durability of double-glazed glass with glazing gasket A double-glazed glass unit with sash was fixed vertically, and a one-year outdoor exposure test was conducted to evaluate the long-term durability of double-glazed glass with glazing gasket.
Although there was no deterioration in the performance of the double-glazed glass (for example, dew condensation in the glass or rattling with the sash), an abnormality in the appearance of the glazing gasket (for example, peeling, slippage, gap) was observed. “△” was evaluated as inferior, and those having neither appearance abnormality nor deterioration in performance of the double-glazed glass were evaluated as “◯” as having excellent long-term durability.

3-6. Applicability of Thermoplastic Elastomer Composition When producing a multilayer glass with a glazing gasket, the applicability of the thermoplastic elastomer composition to the multilayer glass was evaluated.
When the thermoplastic elastomer composition is discharged at a discharge rate of 10 kg / h from the automatic coating and molding machine used in the above-mentioned examples, the pressure of the shot pump for the thermoplastic elastomer composition is less than 20 MPa. “◯” was evaluated as being excellent, and “X” was evaluated as being inferior in applicability when the pressure was 20 MPa or more.

As is apparent from Table 2, the thermoplastic elastomer compositions prepared in Comparative Examples 1 to 3 were a crystalline polyolefin having a viscosity of more than 500 Pa · s at a shear rate of 100 s ⁻¹ at 180 ° C. and 180 ° C. It was found that the viscosity was high and the applicability was inferior because either or any one of styrene-based thermoplastic elastomers having a viscosity at a shear rate of 100 s ^-1 exceeding 2000 Pa · s was used.
Moreover, since the thermoplastic elastomer composition prepared in Comparative Example 4 uses a styrenic thermoplastic elastomer having a Shore A hardness of more than 50, it was found that the hardness was high, and the watertightness and long-term durability were poor. .
Furthermore, since the Mooney viscosity of the EPDM rubber compound 3 at 100 ° C. of the thermoplastic elastomer composition prepared in Comparative Example 5 exceeded 35, it was found that the viscosity was high and the coating property was poor.
Further, as described above, in Comparative Example 6, the Mooney viscosity of the EPDM rubber compound 4 at 100 ° C. exceeds 35, and the viscosity of the crystalline polyolefin and the styrene thermoplastic elastomer used together is low. It became powdery and the thermoplastic elastomer composition could not be prepared.

In contrast, the thermoplastic elastomer compositions prepared in Examples 2 and 3 and Reference Examples 1 and 4 are all excellent in fluidity, mechanical properties (Shore A hardness, compression set and tensile strength) and coating. It turns out that it is excellent in property. In particular, the thermoplastic elastomer compositions prepared in Examples 2 and 3 and Reference Example 1 have better mechanical properties because the total content of the EPDM rubber compound and the crosslinking agent exceeds 75% by mass. I understand. Further, in the thermoplastic elastomer compositions prepared in Examples 2 and 3, the liquid polymer contained in the EPDM rubber compound has a kinematic viscosity at 40 ° C. of 5000 to 350,000 mm ² / s, and the kinematic viscosity at 40 ° C. and 100 ° C. Since the ratio to the kinematic viscosity (η40 / η100) is 30 or more, it can be seen that the fluidity is very excellent.
In addition, the laminates obtained from the thermoplastic elastomer compositions of Examples 2 and 3 and Reference Examples 1 and 4 are excellent in adhesiveness with a hot melt adhesive.
The double-glazed glass with a glazing gasket obtained from the thermoplastic elastomer compositions of Examples 2 and 3 and Reference Examples 1 and 4 is excellent in watertightness between the glazing gasket and the sash and excellent in long-term durability.

In addition, for the hot melt adhesive of the test body after the 90-degree peeling test of the laminate, GPC measurement of a substance in the vicinity of the interface is performed to confirm the presence or absence of a molecular weight peak derived from the oil component contained in the thermoplastic elastomer composition. did.
As a result, in Examples 2 and 3, Reference Examples 1 and 4, and Comparative Examples 1 to 5, no molecular weight peak derived from the oil component was detected.

FIG. 1 is a schematic view schematically showing a part of a cross section of one embodiment of a multilayer glass with a glazing gasket of the present invention.

Explanation of symbols

1: Multi-layer glass with glazing gasket 3: Glass 5: Glazing gasket 7: Hot-melt adhesive 9: Spacer 10: Primary seal material 11: Secondary seal material 13: Multi-layer glass unit 15: Internal space

Claims (14)

A crystalline polyolefin having a viscosity of 500 Pa · s or less at a shear rate of 100 s ⁻¹ at 180 ° C .;
A styrenic thermoplastic elastomer having a viscosity at a shear rate of 100 s ⁻¹ at 180 ° C. of 2000 Pa · s or less and a Shore A hardness of 50 or less;
An ethylene-propylene rubber compound having a Mooney viscosity of 35 or less at 100 ° C;
The mixture containing the crosslinking agent, resulting et is by dynamic crosslinking,
A thermoplastic elastomer composition in which the ethylene-propylene rubber compound contains 25% by mass or more of a liquid polymer having a kinematic viscosity at 40 ° C. of 5000 to 350,000 mm ² / s .   The thermoplastic elastomer composition according to claim 1, wherein a total content of the ethylene-propylene rubber compound and the crosslinking agent in the mixture is 75% by mass or more.   The crystalline polyolefin is polyethylene, polypropylene, ethylene propylene copolymer, ethylene α-olefin copolymer, propylene α-olefin copolymer, ethylene propylene α-olefin copolymer, ethylene butene copolymer, propylene butene copolymer. The thermoplastic elastomer composition according to claim 1 or 2, which is at least one selected from the group consisting of a polymer and an ethylene propylene butene copolymer.   The styrene thermoplastic elastomer is at least one selected from the group consisting of a hydrogenated styrene butadiene random copolymer, a hydrogenated styrene butadiene block copolymer, and a hydrogenated styrene isoprene block copolymer. The thermoplastic elastomer composition according to any one of the above. The liquid polymer is selected from the group consisting of liquid polybutene, liquid polyisobutene, liquid polyisoprene, liquid polybutadiene, liquid poly α-olefin, liquid ethylene α-olefin copolymer, liquid ethylene propylene copolymer, and liquid ethylene butylene copolymer. The thermoplastic elastomer composition according to any one of claims 1 to 4, which is at least one selected. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the liquid polymer has a ratio of kinematic viscosity at 40 ° C to kinematic viscosity at 100 ° C (η40 / η100) of 30 or more. The thermoplastic elastomer composition according to any one of claims 1 to 6 , comprising 15% by mass or less of oil and / or plasticizer. By dynamically crosslinking the mixture, at least a part of the ethylene-propylene rubber compound becomes a crosslinked rubber, and the ethylene-propylene rubber compound is dispersed in the crystalline polyolefin and the styrene thermoplastic elastomer in the form of particles. The thermoplastic elastomer composition according to any one of claims 1 to 7 . The Shore A hardness is 65 or less, the compression set is 50% or less, the tensile strength is 4.5 MPa or more, and the viscosity under the conditions of 180 ° C. and a shear rate of 100 s ⁻¹ is 2000 Pa · s or less. Item 9. The thermoplastic elastomer composition according to any one of Items 1 to 8 . The dynamic crosslinking is performed using a twin-screw kneading extruder,
The biaxial kneading extruder has two screws having a screw length (La) / screw diameter (D) of 40 or more from the center position of the material charging port,
The screw has a first kneading region in a range where the screw length (La) / screw diameter (D) from the center position of the material charging port is 5 to 15,
In the first kneading region, at least four kneading segments having a screw length (Lb) / screw diameter (D) of 1 or less,
The thermoplastic elastomer composition according to any one of claims 1 to 9 , wherein the temperature in the first kneading region is a temperature not higher than the melting point of the crystalline polyolefin. The thermoplastic elastomer composition according to claim 10 , wherein the screw of the twin-screw kneading extruder further has a second kneading region in a range where screw length (Lb) / screw diameter (D) is 10 or more. Between the thermoplastic elastomer composition and the glass according to any one of claims 1 to 11 laminate having a hot-melt adhesive. A glazing gasket obtained from the thermoplastic elastomer composition according to any one of claims 1 to 11 . A multilayer glass with a glazing gasket having a hot-melt adhesive between the multilayer glass and the glazing gasket according to claim 13 .

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