WO2020045609A1

WO2020045609A1 - Resin composition, powder, adhesive and direct glazing adhesive for automobiles

Info

Publication number: WO2020045609A1
Application number: PCT/JP2019/034053
Authority: WO
Inventors: 泰史千田; 真裕加藤
Original assignee: 株式会社クラレ
Priority date: 2018-08-31
Filing date: 2019-08-30
Publication date: 2020-03-05
Also published as: TW202030261A; JPWO2020045609A1

Abstract

A resin composition which is capable of imparting functions other than adhesiveness such as high toughness, high hardness and high vibration damping properties over a wide actual working temperature range, while maintaining good adhesion to a steel sheet, and which is composed of (I) a matrix resin component that has a monomer unit containing a hetero atom, and (II) a resin component that is composed of at least one substance selected from the group consisting of a block copolymer having a polymer block (A) derived from an aromatic vinyl compound and a polymer block (B) derived from a conjugated diene compound, a styrene resin, a conjugated diene polymer and an olefin resin, with the average dispersion diameter of the resin component (II) in the resin composition being from 10 μm to 5,000 μm; a powder which uses this resin composition; an adhesive; and a direct glazing adhesive for automobiles.

Description

Resin composition, powder, adhesive, and direct glazing adhesive for automobile

The present invention relates to a resin composition, a powder, an adhesive, and a direct glazing adhesive for automobiles.

For example, in automotive applications, direct glazing (DG), in which a window glass is directly bonded to a body without a rubber gasket, because the rigidity of the vehicle body can be improved, the appearance is excellent, and the degree of freedom in design is high. Studies on adhesives for use have been advanced (for example, see Patent Document 1). Since vibrations occur in various machines such as automobiles, there is a need for a means for solving the problems caused by the vibrations. For example, in the case of the above-mentioned DG adhesive, means for reducing road noise in a wide temperature range has been required.
In recent years, there has been an increasing demand for further reducing noise in automobiles, and there has been a demand for a DG adhesive capable of further improving noise reduction while maintaining the functions of the DG adhesive such as adhesiveness. ing. In addition, by replacing existing adhesives that are used to adhere members whose vibrations are to be suppressed with adhesives with high vibration damping properties, vibration and noise can be expected to be reduced. Can also lead to an expanded use of.

On the other hand, a block copolymer having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound, particularly a hydrogenated product thereof, contains a conjugated diene A structural unit derived from a compound having a vinyl bonding unit (for example, a 1,2-bonding unit and a 3,4-bonding unit) may be used as a vibration damping material (for example, see Patent Document 2). It is generally known that a loss tangent (tan δ) measured according to JIS K72444-10 is an index of damping properties.

JP 2014-122257 A JP-A-2002-284830

By adding such a block copolymer having damping properties to the adhesive, it is conceivable to impart damping properties to the adhesive and improve noise reduction. However, since the above-mentioned block copolymer is generally low in polarity, it generally has low compatibility with an adhesive having high polarity. For this reason, the block copolymer may aggregate without being mixed with the adhesive, which may cause a decrease in mechanical strength or adhesive strength.
Therefore, it is conceivable to mix and disperse powder (fine particles) obtained by pulverizing the styrene-based elastomer into the adhesive. In this case, since the block copolymer is a particle, it is necessary to sufficiently mix with the adhesive and disperse it in the adhesive. However, it is not always the case that good characteristics can be obtained simply by sufficiently mixing. For example, if both are mixed with a strong force longer than necessary, the block copolymer becomes smaller in diameter, these are networked in the composition, or the particles are aggregated and unevenly distributed, and the adhesiveness and toughness etc. It is assumed that the performance as an adhesive is impaired. Therefore, the dispersion state of the block copolymer particles in the composition is important in order to exhibit vibration damping properties without impairing the performance of the adhesive.
However, the fact is that the dispersed state of the vibration damping material in the adhesive composition is focused on, and what kind of dispersed state should be achieved has not yet been sufficiently studied.

An object of the present invention is to provide a resin composition that can have functions other than adhesiveness, such as high toughness, high hardness, and high vibration damping properties in a wide range of actual operating temperatures, while maintaining adhesiveness to a steel sheet. , An adhesive, and a direct glazing adhesive for automobiles. Another object of the present invention is to provide a powder suitable for the resin composition, the adhesive, and the automotive direct glazing adhesive.

The present inventors disperse a resin component (II) capable of exhibiting high vibration damping property in a matrix resin component (I) having a monomer unit containing a hetero atom, and convert the resin component (II) in the resin composition. It has been found that the above problems can be solved by setting the specific average dispersion diameter, and the present invention has been completed.

The present invention relates to the following [1] to [22].
[1] A matrix resin component (I) having a monomer unit containing a hetero atom, and a block having a polymer block (A) derived from an aromatic vinyl compound and a polymer block (B) derived from a conjugated diene compound. A resin composition comprising at least one resin component (II) selected from the group consisting of a copolymer, a styrene-based resin, a conjugated diene polymer, and an olefin-based resin. A resin composition wherein the average dispersion diameter of the resin component (II) is from 10 μm to 5,000 μm.
[2] The resin composition according to [1], wherein the resin component (II) satisfies the following condition (1).
Condition (1): Coefficients A ₁ to A ₃ determined by performing fitting of the following equation [I] on a relaxation curve represented by a relaxation strength y with respect to a relaxation time x measured using a pulse NMR apparatus, and The motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ ₁ to τ ₃ of each component is 0.01 to 0.25 seconds.
y = A ₁ * exp (−0.5 * (x / τ ₁ ) ² ) + A ₂ * exp (−0.5 * (x / τ ₂ ) ² ) + A ₃ * exp (−x / τ ₃ ) [I]
M = (τ ₂ * A ₂ + τ ₃ * A ₃ ) / (A ₂ + A ₃ ) [II]
[3] The resin composition according to [1] or [2], wherein the resin component (I) is a polyurethane.
[4] The resin composition according to any one of [1] to [3], wherein the resin component (I) is a moisture-curable polyurethane.
[5] The resin composition according to any one of [1] to [4], wherein the resin component (I) is a one-pack moisture-curable polyurethane comprising a polyol compound and an isocyanate compound.
[6] The resin composition according to any one of [1] to [5], wherein the resin component (II) is a powder-like freeze-ground product.
[7] The resin composition according to [6], wherein the 50% volume average diameter of the resin component (II), which is the powder-like freeze-ground product, is 0.01 mm to 1.0 mm.
[8] The resin composition according to [2], wherein the mobility parameter M of the resin component (II) is 0.01 to 0.10 seconds.
[9] The resin composition according to any one of [1] to [8], wherein the resin component (II) satisfies the following condition (2).
Condition (2): 60 ° C. measured based on JIS K7244-10 (2005) under the conditions of a distortion amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to + 100 ° C., and a heating rate of 3 ° C./min Has a shear storage modulus G ′ of 0.10 to 0.58 MPa and a peak temperature of loss tangent tan δ of −5 to + 40 ° C.
[10] A polymer in which the resin component (II) contains a structural unit derived from an aromatic vinyl compound in an amount of more than 70 mol% and a polymer block containing a structural unit derived from a conjugated diene compound in an amount of 30 mol% or more. The resin composition according to any one of [1] to [9], which is a block copolymer having a block (B).
[11] The resin composition according to any one of [1] to [10], wherein the content of the polymer block (A) in the block copolymer is 6 to 22% by mass.
[12] The resin composition according to any one of [1] to [11], wherein the hydrogenation rate of the polymer block (B) in the block copolymer is 10 to 99 mol%.
[13] The resin composition according to any one of [1] to [12], which has a loss tangent tan δ at 20 ° C. of 0.15 or more.
[14] A polymer block (A) which satisfies the following condition (1) and is derived from an aromatic vinyl compound and a polymer block (B) which has a hydrogenation ratio of 10 to 99 mol% and is derived from a conjugated diene compound. A powder comprising at least one resin component (II) selected from the group consisting of a block copolymer having the following, a styrene resin, a conjugated diene polymer, and an olefin resin.
Condition (1): Coefficients A ₁ to A ₃ determined by performing fitting of the following equation [I] on a relaxation curve represented by a relaxation strength y with respect to a relaxation time x measured using a pulse NMR apparatus, and The motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ ₁ to τ ₃ of each component is 0.01 to 0.25 seconds.
y = A ₁ * exp (−0.5 * (x / τ ₁ ) ² ) + A ₂ * exp (−0.5 * (x / τ ₂ ) ² ) + A ₃ * exp (−x / τ ₃ ) [I]
M = (τ ₂ * A ₂ + τ ₃ * A ₃ ) / (A ₂ + A ₃ ) [II]
[15] The powder according to [14], which is a freeze-ground product of the resin component (II).
[16] The powder according to [14] or [15], wherein the 50% volume average diameter is 0.01 mm to 1.0 mm.
[17] The powder according to any one of [14] to [16], wherein the mobility parameter M of the resin component (II) is 0.01 to 0.10 seconds.
[18] The powder according to any one of [14] to [17], wherein the resin component (II) satisfies the following condition (2).
Condition (2): 60 ° C. measured under the conditions of JIS K7244-10 (2005), distortion amount 0.1%, frequency 1 Hz, measurement temperature −70 to + 100 ° C., and heating rate 3 ° C./min. Has a shear storage modulus G ′ of 0.10 to 0.58 MPa and a peak temperature of loss tangent tan δ of −5 to + 40 ° C.
[19] A polymer in which the resin component (II) contains a structural unit derived from an aromatic vinyl compound in excess of 70 mol% and a polymer containing a structural unit derived from a conjugated diene compound in an amount of 30 mol% or more. The powder according to any one of [14] to [18], which is a block copolymer having a block (B).
[20] The powder according to any one of [14] to [19], wherein the content of the polymer block (A) in the block copolymer is 6 to 22% by mass.
[21] An adhesive containing the resin composition according to any one of [1] to [13].
[22] A direct glazing adhesive for automobiles, comprising the resin composition according to any one of [1] to [13].

According to the present invention, a resin composition capable of having functions other than adhesiveness, such as high toughness, high hardness, and high vibration damping properties in a wide range of actual operating temperatures, while maintaining adhesiveness to a steel sheet, And a direct glazing adhesive for automobiles. Further, according to the present invention, it is possible to provide a powder suitable for the resin composition, the adhesive, and the direct glazing adhesive for automobiles.

4 is a graph showing temperature characteristics of loss tangent tan δ of the resin compositions of Examples 1 to 4 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described. It should be noted that embodiments in which the items described in this specification are arbitrarily selected or arbitrarily combined are also included in the present invention. Further, in the present specification, a rule that is preferable can be arbitrarily adopted, and a combination of preferable ones is more preferable. In this specification, the description “XX to YY” means “XX or more and YY or less”.

[Configuration of resin composition]
The resin composition according to the embodiment of the present invention includes a matrix resin component (I) having a monomer unit containing a hetero atom, and a polymer block (A) derived from an aromatic vinyl compound and a polymer resin derived from a conjugated diene compound. A resin composition comprising a block copolymer having a united block (B), a styrene resin, a conjugated diene polymer, and at least one resin component (II) selected from the group consisting of olefin resins. The resin composition has an average dispersion diameter of the resin component (II) in the resin composition of 10 μm to 5,000 μm.
First, each component constituting the resin composition will be described.

The matrix resin component (I) is a resin component serving as a dispersion substrate (dispersion medium) of the resin composition, and a resin component (II) described later is dispersed in the matrix resin component (I). The matrix resin component (I) is a resin component having a monomer unit containing a hetero atom, and may contain a curable resin component such as a prepolymer or an oligomer. The matrix resin component (I) may contain a catalyst used in the production process, a curing agent (a cross-linking agent, a polymerization initiator, a co-reactant, etc.) used as necessary.
The matrix resin component (I) is preferably a urethane resin (polyurethane), a melamine resin, a urea resin, a phenol resin, a vinyl acetate resin, an ethylene / vinyl acetate resin, an epoxy resin, a cyanoacrylate resin, an acrylic resin, a chloroprene rubber, a nitrile rubber. , Silicone rubber, and polyurethane is particularly preferable. As the polyurethane, a moisture-curable polyurethane is preferable, and a one-component moisture-curable polyurethane is more preferable. Here, the polyurethane is a polymer having a urethane bond, and the “polyurethane” in the present invention is an oligomer having a urethane bond or a prepolymer having a urethane bond (hereinafter, may be referred to as “urethane prepolymer”). , A cured product of the prepolymer, a polyurethane composition and a urethane composition.
The prepolymer having a urethane bond may be a polymer obtained by reacting a polyol and an excess of diisocyanate with respect to the polyol, and since such a prepolymer contains unreacted isocyanate groups, it reacts with, for example, moisture. Thus, a cured product can be obtained. The cured product of the prepolymer means a product obtained by reacting the prepolymer with, for example, moisture, a curing agent, and the like, and curing the prepolymer. When the matrix resin component (I) of the present invention is a polyurethane, the resin component (I) includes, in addition to the above-mentioned oligomer, prepolymer, and cured product of the prepolymer, a component for producing them. Certain polyol compounds, isocyanate compounds, catalysts, curing agents, and the like may be included, but in the present specification, a composition containing at least one of these components may be referred to as a “polyurethane composition” or a “urethane composition”. . Similarly, moisture-curable polyurethane may be referred to as "moisture-curable polyurethane composition", and one-component moisture-curable polyurethane may be referred to as "one-component moisture-curable polyurethane composition".

The polyurethane is formed using a polyol compound (U) having two or more hydroxy groups in one molecule and an isocyanate compound (V) having two or more isocyanate groups in one molecule. Is preferred.

(Polyol compound (U))
The polyol compound (U) is not particularly limited as long as it can react with the isocyanate compound (V) described below.

Examples of the polyol compound (U) include low molecular weight polyhydric alcohols, polyether polyols, polyester polyols, other polyols, and mixtures thereof.

Examples of low molecular weight polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, Glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, pentaerythritol; saccharides such as sorbitol;

The polyether polyol is obtained, for example, by adding at least one compound selected from alkylene oxide and styrene oxide to at least one compound selected from the above-mentioned low molecular weight polyhydric alcohol, aromatic diol compound, amine compound and alkanolamine compound. And a ring-opening polymerization of a cyclic ether monomer such as butylene oxide (tetramethylene oxide) and tetrahydrofuran.

Examples of the aromatic diol compound include resorcinol (m-dihydroxybenzene), xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; bisphenol A structure (4,4 ′ Diol compounds having a bisphenol skeleton such as bisphenol F structure (4,4′-dihydroxyphenylmethane), brominated bisphenol A structure, hydrogenated bisphenol A structure, bisphenol S structure and bisphenol AF structure. Can be Examples of the amine compound include ethylene diamine and hexamethylene diamine. Examples of the alkanolamine compound include ethanolamine and propanolamine. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polypropylene triol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol, polytetraethylene glycol; sorbitol-based polyols; bisphenol A (4,4′-dihydroxy Phenylpropane) and a polyether polyol obtained by adding an alkylene oxide.

Examples of the polyester polyol include a condensation-based polyester polyol, a lactone-based polyol, and a polycarbonate polyol.

The condensation-based polyester polyol is, for example, a condensation reaction of at least one compound selected from the above-mentioned low molecular weight polyhydric alcohol, the above-mentioned aromatic diol compound, the above-mentioned amine compound and the above-mentioned alkanolamine compound with a polybasic carboxylic acid. It is manufactured by.

Examples of the polybasic carboxylic acids include, for example, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, dimer acid, and pyromellitic acid And low-molecular-weight carboxylic acids, oligomeric acids, castor oil, and hydroxycarboxylic acids such as reaction products of castor oil and ethylene glycol (or propylene glycol).

The lactone-based polyol has, for example, hydroxyl groups at both ends produced by ring-opening polymerization of lactone. Examples of the lactone include ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, and the like.

アクリル Other polyols include acrylic polyols and the like.

Among these polyol compounds (U), when used as a composition containing the reaction product of the urethane composition, for example, a one-part moisture-curable polyurethane composition, the balance between the hardness and elongation at break of the obtained cured product is excellent. Polyether polyols and polypropylene glycols are preferred, and polypropylene glycols are more preferred, since a cured product having such physical properties can be obtained at low cost.

重量 The weight average molecular weight of the polyol compound (U) is preferably from 100 to 10,000, and more preferably from 100 to 8,000. When the weight average molecular weight is in this range, the physical properties (for example, hardness, breaking strength, breaking elongation) and viscosity of the prepolymer produced by the reaction with the isocyanate compound (V) described below become favorable. The weight average molecular weight of the polyol compound (U) is a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

These polyol compounds (U) may be used alone or in combination of two or more.

(Isocyanate compound (V))
The isocyanate compound (V) is not particularly limited as long as it has two or more isocyanate groups in one molecule. Examples of the isocyanate compound (V) include tolylene diisocyanate, diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, Aromatic polyisocyanates such as triphenylmethane triisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl; transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis ( Isocyanatomethyl) cyclohexane Carbodiimide-modified isocyanate compounds of these isocyanate compounds, isocyanurate-modified isocyanate compounds; alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate and the like.

中でも Among these isocyanate compounds (V), aromatic polyisocyanates are preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are more preferable, because the adhesiveness is further improved.

These isocyanate compounds (V) may be used alone or in combination of two or more.

The amount of the isocyanate compound (V) to be used with respect to 100 parts by mass of the polyol compound (U) is preferably in the range of 1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and still more preferably 1 to 100 parts by mass. It is. When the isocyanate compound (V) is used in the above range, the polyol compound (U) and the isocyanate compound (V) react at an appropriate quantitative ratio, and a cured product obtained from a reaction product of the urethane composition to be produced, In addition, physical properties (eg, hardness, breaking strength, breaking elongation) of a cured product obtained from the moisture-curable polyurethane composition containing the reaction composition are improved.

(Method for producing urethane composition)
The urethane composition can be prepared by mixing the polyol compound (U) with the isocyanate compound (V) and other components (for example, a powder component and a plasticizer described later) included as necessary. The mixing apparatus is not particularly limited, and includes, for example, a roll, a kneader, a pressure kneader, a Banbury mixer, a horizontal mixer (for example, a Ledige mixer), a vertical mixer (for example, a planetary mixer, etc.), an extruder, and a universal stirring. Machine.
In preparing the resin composition, in order to disperse the resin component (II) satisfactorily in the composition without deteriorating the performance as an adhesive, as described below, the polyol compound (U) And a resin component (II), and a plasticizer and a filler used as necessary, and then adding and mixing an isocyanate compound (V), and further adding and mixing a catalyst to thereby form a urethane composition. And a resin composition is preferably prepared.

The urethane composition is suitable as a raw material for a moisture-curable polyurethane composition described later. The urethane composition used as a raw material of the moisture-curable polyurethane composition is desirably manufactured through the following mixing step and dehydration step.

(Mixing process)
First, a preliminary mixture is prepared by mixing the polyol compound (U), a resin component (II) described later, and a component (for example, a powder component) included as necessary. When the preliminary mixture contains the polyol compound (U), the resin component (II), and the powder component, it usually becomes a paste-like mixture.

混合 The mixing device for preparing the premix is not particularly limited, and a mixing device for preparing the urethane composition described above can be used.

混合 In addition, the mixing temperature, the mixing time, and the rotation speed of the stirring member in the mixing step can be appropriately set according to the type of the polyol compound (U), the resin component (II), and the components included as necessary. The mixing temperature is preferably about 20 to 110 ° C. The mixing time is preferably from 30 minutes to 4 hours, more preferably from 30 minutes to 2 hours. The rotation speed of the stirring member is preferably about 20 to 300 rpm.

(Dehydration step)
It is desirable that the preliminary mixture obtained in the mixing step be further subjected to a dehydration step. This dehydration step is a step of removing at least a part of the residual moisture in the preliminary mixture. The method for removing the residual moisture is not particularly limited. For example, dehydration is performed at a temperature of about 30 to 60 ° C. under reduced pressure (1.2 kPa or less, preferably 0.6 to 1.2 kPa) for 30 minutes or more. Method. Further, the dehydration step may also serve as the mixing step. In this case, mixing and dehydration may be performed preferably at a rotation speed of the stirring member of 20 to 300 rpm under the temperature and reduced pressure conditions in the dehydration step. As the time of the dehydration step also serving as the mixing step, a time for dehydration may be added to the above-mentioned preferable mixing time, and for example, a total of 3 to 5 hours for the mixing and dehydration time is preferable.

では In the dehydration step, the water content of the premix is preferably adjusted to 0.050% by mass or less, more preferably to 0.025% by mass or less, and further preferably to 0.015% by mass or less. The water content of the premix can be measured by the Karl Fischer method. For example, an electrolytic solution containing iodide ion, sulfur dioxide, and alcohol as main components as Karl Fischer reagents (for example, Aquamicron CXU, manufactured by API Corporation) according to coulometric titration based on JIS K0068 (2001) Can be measured using a moisture measuring device (for example, manufactured by Mitsubishi Chemical Corporation).

By mixing the polyol compound (U), the resin component (II), and the premix containing the components included as necessary with the polyisocyanate compound (V) through the above-described mixing step and dehydration step, moisture A suitable urethane composition can also be produced for the curable polyurethane composition. The mixing device for mixing the premix and the polyisocyanate compound (V) is not particularly limited, and a mixing device for producing the above-described urethane composition can be used.

The moisture-curable polyurethane composition is prepared by mixing a mixture containing a prepolymer (reaction product) by a reaction of the urethane composition (mainly, a urethane prepolymer formation reaction by a reaction between the polyol compound (U) and the isocyanate compound (V)). Then, the mixture can be prepared by mixing such a mixture with an isocyanate compound (V ′) having two or more isocyanate groups in one molecule.

The isocyanate compound (V ') contained in the moisture-curable polyurethane composition is not particularly limited as long as it is an isocyanate compound having two or more isocyanate groups in one molecule, and isocyanate compound (V') contained in the urethane composition And the like. That is, specific examples of the isocyanate compound (V ′) include polyisocyanates such as diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and norbornane diisocyanatomethyl. These are used alone. Or two or more of them may be used in combination.

Examples of the isocyanate compound (V ′) contained in the moisture-curable polyurethane composition include, in addition to the isocyanate compound (V), a reaction product of the above-mentioned polyisocyanate and triol; a biuret form of the polyisocyanate, an isocyanurate form And the like. These may be used alone or in combination of two or more. Here, the triol is not particularly limited as long as it has three hydroxy groups in one molecule. For example, 1,2,5-hexanetriol, 1,2,6-hexanetriol, Examples thereof include 2,3-propanetriol, 1,2,3-benzenetriol, 1,2,4-benzenetriol, trimethylolethane, and trimethylolpropane. As the isocyanate compound (V ′), a reaction product of hexamethylene diisocyanate and trimethylolpropane, a biuret of hexamethylene diisocyanate, and an isocyanate of hexamethylene diisocyanate are used because the adhesive effect is more excellent. It is preferably at least one member selected from the group consisting of a nullate form.

作製 When preparing a mixture containing the above-described prepolymer, it is desirable to go through the following prepolymer generation step.

(Prepolymer generation step)
In the prepolymer production step, a pre-mixture containing the polyol compound (U), the resin component (II), and the components included as necessary is preferably obtained through the above-described mixing step and dehydration step from the urethane composition; This is a step of obtaining the above prepolymer from a resin composition obtained by mixing with the polyisocyanate compound (V).

Alternatively, the prepolymer may be mixed with the polyol compound (U), the resin component (II), and a premix containing the components included as required and the polyisocyanate compound (V) simultaneously or continuously to form a prepolymer. Good. Conditions for forming the prepolymer can be appropriately set according to the types of the polyol compound (U) and the isocyanate compound (V) contained in the urethane composition. For example, during or after mixing the premix and the polyisocyanate compound (V), it is preferable that the temperature of the mixture be equal to or higher than the melting point of the isocyanate compound (V) under stirring conditions. Further, the production of the prepolymer is preferably carried out under an atmosphere of an inert gas such as nitrogen or argon or under reduced pressure.

(4) In the prepolymer production step, it is preferable to mix the isocyanate compound (V) with the premix, and then to mix a catalyst for promoting the prepolymer production reaction. The type of the catalyst is not particularly limited, but a metal catalyst, an amine catalyst and the like are preferable. These catalysts may be used in combination. Thereby, the viscosity of the produced prepolymer can be favorably maintained. For example, when the powder component is contained in the pre-mixture, it is considered that the addition of the above-mentioned catalyst does not cause a rapid reaction of forming the prepolymer, thereby maintaining a good viscosity.

有機 Examples of the metal catalyst include organometallic catalysts. Examples of the organometallic catalyst include dimethyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate (DOTL), dioctyltin dilaurate, dibutyltin diacetate, and a bismuth-based catalyst (for example, inorganic bismuth (Neostan U- 600, U-660)).

Examples of the amine catalyst include triethylenediamine, bis (dimethylaminoethyl) ether, di (N, N-dimethylaminoethyl) amine and the like.

When the above catalyst is used, the amount of the catalyst is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total of the polyol compound (U) and the polyisocyanate compound (V) contained in the urethane composition. 0.001 to 5 parts by mass.

(Moisture-curable polyurethane composition forming step)
In the step of producing the moisture-curable polyurethane composition, the mixture containing the above-described prepolymer and an isocyanate compound (V ′) having two or more isocyanate groups in one molecule are mixed, and the moisture-curable polyurethane composition, typically Specifically, it is a step of obtaining a one-pack moisture-curable polyurethane composition. The obtained moisture-curable polyurethane composition contains at least the powder, the prepolymer, and the isocyanate compound (V ′).

Here, the method of mixing the mixture containing the prepolymer and the isocyanate compound (V ′) is not particularly limited, and for example, a method of mixing with the same apparatus as the mixing apparatus used in the step of mixing the urethane composition is preferable. is there. The mixing temperature is not particularly limited, but it is preferable that the mixing be performed at a temperature equal to or higher than the melting point of the isocyanate compound (V ') added as a component of the moisture-curable polyurethane composition. The atmosphere at the time of mixing is not particularly limited, but the mixing is preferably performed under an inert gas atmosphere such as nitrogen or argon or under reduced pressure.

Further, the moisture-curable polyurethane composition contains a curing catalyst to induce moisture-curing of the obtained moisture-curable polyurethane composition (typically, a one-component moisture-curable polyurethane composition). Is preferred. Thereby, the adhesiveness of the obtained moisture-curable polyurethane composition is more excellent.

硬化 The curing catalyst is not particularly limited as long as it induces moisture curing, and a conventionally known curing catalyst can be used. As the curing catalyst, for example, the organometallic catalyst exemplified as the catalyst that can be used in the above-mentioned prepolymer production step can be mentioned.

When the above curing catalyst is used, the compounding amount thereof is determined by mixing the polyol compound (U) contained in the urethane composition with the isocyanate compound (V) and the isocyanate compound (V ′) newly added to the moisture-curable polyurethane composition. 0.001 to 10 parts by mass, preferably 0.001 to 5 parts by mass, based on 100 parts by mass in total.

<Resin component (II)>
The resin component (II) includes a block copolymer (IIa) having a polymer block (A) derived from an aromatic vinyl compound and a polymer block (B) derived from a conjugated diene compound, and an olefin resin (IIb). ), Styrene resin (IIc), and conjugated diene polymer (IId).

(Block copolymer (IIa))
The block copolymer (IIa) that can be used as the resin component (II) includes a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound. (B), and preferably a hydrogenated product of the block copolymer. In the present specification, a hydrogenated product of a block copolymer may also be referred to as a hydrogenated block copolymer.
Preferably, a block having a polymer block (A) containing more than 70 mol% of a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing 30 mol% or more of a structural unit derived from a conjugated diene compound. It is a copolymer.

The content of the polymer block (A) in the block copolymer (IIa) (when there are a plurality of polymer blocks (A), the total content thereof) is preferably 3% by mass or more, and more preferably 6% by mass or more. It is more preferably at least 10% by mass. Further, it is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 35% by mass or less, even more preferably 22% by mass or less, particularly preferably 18% by mass or less, and most preferably 16% by mass or less. For example, the content is preferably 3 to 80% by mass, more preferably 6 to 22% by mass, and still more preferably 10 to 16% by mass. By setting the content of the polymer block (A) to 3% by mass or more, mechanical properties are improved, and by setting the content to 80% by mass or less, moldability is improved.
The content of the polymer block (A) in the block copolymer is a value determined by ¹ H-NMR measurement, and more specifically, a value measured according to the method described in Examples.

(Polymer block (A))
The polymer block (A) contains, for example, more than 70 mol% of a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as “aromatic vinyl compound unit”), and is preferably used from the viewpoint of mechanical properties. Is 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more, and may be substantially 100 mol%.

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p -Methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl- 2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-di Lorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro -P-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β- Chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene , M-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethyl Styrene, a styrene derivative substituted with a silyl group, indene, vinyl naphthalene, and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of the balance between the production cost and the physical properties.

However, as long as the objects and effects of the present invention are not hindered, the polymer block (A) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter referred to as “another unsaturated monomer”). May be abbreviated as "unit") at a ratio of less than 30 mol%. Examples of the other unsaturated monomers include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinyl carbazole, β And at least one selected from the group consisting of -pinene, 8,9-p-menthen, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran and the like. When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited, and may be random or tapered.
The content of the structural unit derived from the other unsaturated monomer in the polymer block (A) is preferably 10 mol% or less, more preferably 5 mol% or less, and further preferably 0 mol%.

The block copolymer (IIa) may have at least one of the polymer blocks (A). When the block copolymer has two or more polymer blocks (A), the polymer blocks (A) may be the same or different. In the present specification, “different polymer blocks” refers to the monomer units constituting the polymer block, the weight average molecular weight, the stereoregularity, and when there are a plurality of monomer units, the ratio of each monomer unit and the It means that at least one of the forms of polymerization (random, gradient, block) is different.
In the present embodiment, the block copolymer (IIa) preferably has two polymer blocks (A).

The weight average molecular weight (Mw) of the polymer block (A) included in the block copolymer (IIa) is not particularly limited, but at least one of the polymer blocks (A) included in the block copolymer. The weight average molecular weight of the polymer block (A) is preferably from 3,000 to 60,000, more preferably from 4,000 to 50,000. When the block copolymer has at least one polymer block (A) having a weight average molecular weight within the above range, the mechanical strength is further improved and the film formability is excellent.

All the “weight average molecular weights” described in the present specification and the claims are weight average molecular weights in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement. The method described can be followed. The weight average molecular weight of each polymer block (A) of the block copolymer can be determined by measuring a sampled liquid every time polymerization of each polymer block is completed in the production process. For example, in the case of a triblock copolymer having an A1-BA2 structure, the weight average molecular weights of the first polymer block A1 and the polymer block B are determined by the above method, and the weight average molecular weight of the block copolymer is By subtracting them, the weight average molecular weight of the second polymer block A2 can be determined. As another method, in the case of a triblock copolymer having an A1-BA2 structure, the total weight average molecular weight of the polymer block (A) is determined by dividing the weight average molecular weight of the block copolymer by ¹ H- It is calculated from the total content of the polymer block (A) confirmed by NMR measurement, the weight average molecular weight of the first deactivated polymer block A1 is calculated by GPC measurement, and the second weight is calculated by subtracting this. The weight average molecular weight of the united block A2 can also be determined.

(Polymer block (B))
The polymer block (B) is a polymer block containing, for example, 30 mol% or more, preferably 50 mol% or more, more preferably 65 mol% or more, and still more preferably 80 mol% or more, of a structural unit derived from a conjugated diene compound. All of the polymer blocks (B) may be structural units derived from a conjugated diene compound. That is, the structural unit derived from the conjugated diene compound contained in the polymer block (B) can be set to 100 mol%.
The conjugated diene compound preferably contains isoprene, more preferably contains 20% by mass or more, more preferably contains 40% by mass or more, and further more preferably contains 70% by mass or more. Or 90% by mass or more.

The polymer block (B) may contain 30 mol% or more of a structural unit derived from isoprene alone, or may contain 30 mol% or more of a structural unit derived from two or more conjugated diene compounds.
Examples of the conjugated diene compound include butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and myrcene, in addition to isoprene. As the conjugated diene compound, isoprene, a mixture of isoprene and butadiene is preferable, and isoprene is more preferable.
When the conjugated diene compound is a mixture of butadiene and isoprene, their mixing ratio [isoprene / butadiene] (mass ratio) is not particularly limited, but is preferably 5/95 to 95/5, more preferably 10/90. ９０90/10, more preferably 40/60 to 70/30, particularly preferably 45/55 to 65/35. When the mixing ratio [isoprene / butadiene] is represented by a molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, particularly preferably Preferably it is 45/55 to 55/45.

When the conjugated diene compound is a mixture of butadiene and isoprene, the ratio of the area of the peak having a chemical shift value of 24 to 25 ppm to the area of the peak having a chemical shift value of 5 to 50 ppm measured by ¹³ C-NMR. However, from the viewpoint of vibration damping properties, it is preferably 4% or less, more preferably 2% or less, further preferably 1% or less, and most preferably 0.5% or less. ^The peak having a chemical shift value of 5 to 50 ppm, as measured by ¹³ C-NMR, corresponds to all structural units in the polymer block (B), and the peak having a chemical shift value of 24 to 25 ppm is a structural unit derived from isoprene. Corresponds to a site continuous by 1,4-bonds.

In other words, the polymer block (B) preferably contains 30 mol% or more of a structural unit derived from isoprene (hereinafter, may be abbreviated as “isoprene unit”), and the polymer block (B) is preferably a mixture of isoprene and butadiene. It is also preferable to contain 30 mol% or more of a structural unit derived from it (hereinafter, may be abbreviated as "mixture unit of isoprene and butadiene").
When the polymer block (B) has two or more types of structural units, the bonding forms thereof are random, tapered, completely alternating, partially block-shaped, block, or a combination of two or more types thereof. Can consist of

(Vinyl bond amount of polymer block (B))
When the structural unit constituting the polymer block (B) is any one of an isoprene unit, a mixture unit of isoprene and butadiene, the bonding form of each of isoprene and butadiene is 1,2-bond in the case of butadiene, In the case of isoprene, 1,4-bond can be 1,2-bond, 3,4-bond, or 1,4-bond.
In the block copolymer (IIa), the total content of the 3,4-linkage units and 1,2-linkage units (that is, the amount of vinyl linkages) in the polymer block (B) is preferably at least 50 mol%, It is more preferably at least 60 mol%, further preferably at least 65 mol%, still more preferably at least 70 mol%. Although not particularly limited, the upper limit of the vinyl bond amount in the polymer block (B) may be 90 mol%, 88 mol%, or 85 mol%. Is also good. Here, the vinyl bond amount is a value calculated by ¹ H-NMR measurement according to the method described in Examples.
Increasing the vinyl bond amount of the polymer block (B) tends to increase compatibility with the matrix resin component (I), which is advantageous for dispersing the resin component (II) in the resin composition. .

Further, the total weight average molecular weight of the polymer block (B) of the block copolymer is preferably 15,000 to 800,000 before hydrogenation, from the viewpoint of vibration damping properties and the like, It is more preferably from 20,000 to 400,000, further preferably from 20,000 to 300,000, particularly preferably from 30,000 to 300,000, and most preferably from 40,000 to 300,000.

The polymer block (B) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound, as long as the object and effects of the present invention are not hindered. In this case, in the polymer block (B), the content of the structural unit derived from a polymerizable monomer other than the conjugated diene compound is preferably 70 mol% or less, more preferably 50 mol% or less, and still more preferably. Is at most 35 mol%, particularly preferably at most 20 mol%. The lower limit of the content of the structural unit derived from another polymerizable monomer other than the conjugated diene compound is not particularly limited, but may be 0 mol%, 5 mol%, or 10 mol%. %.
Examples of the other polymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinyl Aromatic vinyl compounds such as naphthalene and vinylanthracene, and methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3- Preferable examples include at least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and the like. Among them, styrene, α-methylstyrene and p-methylstyrene are preferred, and styrene is more preferred.
When the polymer block (B) contains a structural unit derived from a polymerizable monomer other than the conjugated diene compound, a specific combination thereof is preferably isoprene and styrene.
When the polymer block (B) contains a structural unit derived from a polymerizable monomer other than the conjugated diene compound, the bonding form is not particularly limited and may be random or tapered. Random is preferred.

The block copolymer only needs to have at least one polymer block (B). When the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.
In the present invention, the block copolymer preferably has only one polymer block (B).

The content of the polymer block (B) in the block copolymer (IIa) (the total content thereof when having a plurality of polymer blocks (B)) is not particularly limited, but is preferably 20 to 97% by mass. , More preferably 78 to 94% by mass, and even more preferably 84 to 90% by mass. By setting the content of the polymer block (B) to 20% by mass or more, the moldability is increased, and by setting the content to 97% by mass or less, the mechanical strength is increased.

(Binding mode of polymer block (A) and polymer block (B))
The type of the block copolymer is not limited as long as the polymer block (A) and the polymer block (B) are bonded, and may be linear, branched, radial, or a combination of these two types. Any combination of the above combinations may be used. Among them, the bonding form of the polymer block (A) and the polymer block (B) is preferably linear, and as an example, the polymer block (A) is A and the polymer block (B) is When represented by B, a diblock copolymer represented by AB, a triblock copolymer represented by ABA or BAB, and a tetrablock copolymer represented by ABAB A block copolymer, a pentablock copolymer represented by ABABA or BABAB, an (AB) nX-type copolymer (X is a residue of the coupling agent) Represents a group, and n represents an integer of 3 or more). Among them, a linear triblock copolymer or a diblock copolymer is preferable, and an ABA triblock copolymer is preferably used from the viewpoint of flexibility, ease of production, and the like.
Here, in the present specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent or the like, the entirety of the bonded polymer blocks is treated as one polymer block. It is. Accordingly, the polymer block which should be strictly described as YXY (X represents a coupling residue), including the above examples, needs to be particularly distinguished from the single polymer block Y. Except for a certain case, Y is displayed as a whole. In the present specification, such a polymer block containing a coupling agent residue is handled as described above, and therefore, for example, it contains a coupling agent residue, and strictly speaking, ABXBA ( X represents a residue of a coupling agent), and the block copolymer is described as ABA, and is treated as an example of a triblock copolymer.

The block copolymer (IIa) may not be hydrogenated, but is preferably a hydrogenated product. The polymer block (B) in the block copolymer (IIa) is preferably based on the total number of moles of the carbon-carbon double bonds of the polymer block (B) in the block copolymer (IIa). The hydrogenation is 10 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, and still more preferably 85 mol% or more.
When the polymer block (B) is hydrogenated by at least 10 mol%, heat resistance and weather resistance are easily improved. The value may be referred to as a hydrogenation rate (hydrogenation rate). The upper limit of the hydrogenation rate is not particularly limited, but the upper limit may be 99 mol%, may be 97 mol%, may be 95 mol%, may be 93 mol%.
The above hydrogenation rate is a value obtained by measuring the content of carbon-carbon double bonds in the structural unit derived from the conjugated diene compound in the polymer block (B) by ¹ H-NMR measurement after hydrogenation. More specifically, it is a value measured according to the method described in Examples.
The hydrogenation rate of the polymer block (B) can be adjusted by, for example, changing the amount of a catalyst used for hydrogenation. Therefore, the hydrogenation rate can be adjusted to the above range by adjusting the amount of the catalyst used during hydrogenation.

(Weight average molecular weight (Mw) of hydrogenated block copolymer)
The weight average molecular weight (Mw) of the hydrogenated block copolymer determined by gel permeation chromatography in terms of standard polystyrene is preferably from 20,000 to 800,000, more preferably from 30,000 to 500,000, and still more preferably. Is from 30,000 to 400,000, particularly preferably from 40,000 to 350,000, most preferably from 50,000 to 300,000. When the weight average molecular weight of the block copolymer is 20,000 or more, heat resistance increases, and when it is 800,000 or less, moldability becomes good.

The block copolymer (IIa) may have a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group in the molecular chain and / or at the molecular terminal, as long as the objects and effects of the present invention are not impaired. It may have one kind or two or more kinds, and may have no functional group.

(Method for producing block copolymer (IIa))
The block copolymer (IIa) can be produced by, for example, a solution polymerization method, an emulsion polymerization method, or a solid phase polymerization method. Among them, a solution polymerization method is preferable, and for example, known methods such as an ionic polymerization method such as anionic polymerization and cationic polymerization, and a radical polymerization method can be applied. Among them, the anionic polymerization method is preferable. In the anionic polymerization method, in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base, an aromatic vinyl compound and at least one selected from the group consisting of a conjugated diene compound and isobutylene are sequentially added, A block copolymer is obtained, and a coupling agent is added and reacted as needed. Furthermore, a hydrogenated block copolymer can be obtained by hydrogenating the block copolymer.

Examples of the organolithium compound that can be used as a polymerization initiator for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and the like. Examples of the dilithium compound that can be used as the polymerization initiator include naphthalenedilithium, dilithiohexylbenzene, and the like.
Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate.
The amounts of these polymerization initiators and coupling agents used are appropriately determined according to the desired weight average molecular weight of the target block copolymer. Usually, an initiator such as an alkyl lithium compound or a dilithium compound is used in a ratio of 0.01 to 0.2 parts by mass per 100 parts by mass of the total of monomers such as an aromatic vinyl compound and a conjugated diene compound used for polymerization. When a coupling agent is used, it is preferably used in a proportion of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the monomers.

The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. Examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. And the like. Further, the polymerization reaction is carried out at a temperature of usually 0 to 100 ° C., preferably 10 to 70 ° C., for 0.5 to 50 hours, preferably 1 to 30 hours.

Also, by adding a Lewis base as a cocatalyst (vinylating agent) during the polymerization, the content (vinyl bond amount) of 3,4-bond and 1,2-bond of the polymer block (B) is increased. However, in the present embodiment, it is preferable to use 2,2-di (2-tetrahydrofuryl) propane [DTHFP] as the Lewis base. By using the DTHFP, it is possible to increase both the vinyl bond amount and the hydrogenation rate under mild conditions while containing isoprene as a conjugated diene compound, and to obtain a block copolymer having excellent mechanical properties. It becomes easier to obtain additives.

Conventionally, in order to increase the amount of vinyl bonds in the hydrogenated product of the block copolymer, a Lewis base is usually used as a vinylating agent. As the Lewis base, ethers such as tetrahydrofuran (THF) and amines such as N, N, N ', N'-tetramethylethylenediamine (TMEDA) have been used (paragraph [0028] of Patent Document 2). reference).
Incidentally, a hydrogenated product of a block copolymer having a polymer block (A) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing a structural unit derived from a conjugated diene compound For example, when the polymer block (B) is composed of only butadiene, it is relatively easy to achieve both a high vinyl bond amount and a high hydrogenation rate even by a conventional method because of its low steric barrier.
However, from the viewpoint of enhancing the vibration damping properties under the actually used temperature conditions, it is effective that the polymer block (B) contains isoprene. However, when isoprene is contained, the polymer block (B) has a high steric barrier. Therefore, it was difficult to increase both the vinyl bond amount and the hydrogenation rate.
Further, for example, as in Production Example 7 of WO 2015/156334, an example in which both the amount of vinyl bonds and the hydrogenation rate are high is also found, but in this document, TMEDA is used as a vinylating agent. Since TMEDA deactivates the hydrogenation catalyst, it is necessary to use a large amount of the hydrogenation catalyst. In this case, although the cause is not clear, even if the vinyl bond amount and the hydrogenation rate are numerically high, the hydrogenation catalyst is actually used. It has been difficult to enhance the vibration damping properties under the temperature conditions required.
Further, when a large amount of the hydrogenation catalyst is used as described above, nucleus hydrogenation in which the benzene ring of the polymer block (A) is hydrogenated occurs, and mechanical properties required as a vibration damping material cannot be obtained. It turned out that the problem arises.
The present inventors have found that by using DTHFP as a vinylating agent, even a block copolymer containing isoprene can achieve both a high vinyl bond amount and a hydrogenation rate under mild conditions without using a large amount of a hydrogenating agent. I found what I could do. By balancing high vinyl bond content and hydrogenation rate under mild conditions, it is possible to obtain a block copolymer with a high hydrogenation rate and high vibration damping properties under the temperature conditions actually used. .

Other Lewis bases may be used together with the DTHFP as long as the effects of the present invention are not impaired. Other Lewis bases include, for example, ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine; N, N, N ', N'-tetramethylenediamine; Examples include amines such as methylmorpholine.
The amount of DTHFP to be added is determined by how much the amount of vinyl bond of the isoprene unit and / or butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of the Lewis base to be added is usually 0.1 to 1 per gram atom of lithium contained in the alkyllithium compound or the dilithium compound used as the polymerization initiator, from the viewpoint of satisfying the preferable condition of the vinyl bond amount. It is preferably used in the range of 2,000 mol, preferably 0.3 to 100 mol, most preferably 0.5 to 10 mol.

After the polymerization is carried out by the above-described method, an active hydrogen compound such as alcohols, carboxylic acids, and water is added to stop the polymerization reaction. Thereafter, a hydrogenated copolymer (hydrogenation reaction) is performed in an inert organic solvent in the presence of a hydrogenation catalyst, whereby a hydrogenated copolymer can be obtained. In the hydrogenation reaction, the hydrogen pressure is 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, and the reaction temperature is 20 to 250 ° C., preferably 50 to 180 ° C., and more preferably 70 to 180 ° C. The reaction can be carried out at a temperature of up to 180 ° C and a reaction time of usually 0.1 to 100 hours, preferably 1 to 50 hours.
Examples of the hydrogenation catalyst include Raney nickel; a transition metal compound, an alkylaluminum compound, and an alkyllithium compound, from the viewpoint of performing the hydrogenation reaction of the polymer block (B) while suppressing the nuclear hydrogenation of the aromatic vinyl compound. Ziegler catalysts; metallocene catalysts; and the like. From the same viewpoint as above, among them, Ziegler catalysts are preferred, Ziegler catalysts composed of a combination of a transition metal compound and an alkylaluminum compound are more preferred, and Ziegler catalysts composed of a combination of a nickel compound and an alkylaluminum compound (Al / Ni-based Ziegler catalyst) is more preferred.

The hydrogenated block copolymer obtained in this manner is coagulated by pouring the polymerization reaction solution into methanol or the like, and then heating or drying under reduced pressure, or pouring the polymerization reaction solution together with steam into hot water to form a solvent. Can be obtained by subjecting to so-called steam stripping to remove by azeotropic distillation, followed by heating or drying under reduced pressure.

The hydrogenated block copolymer thus obtained is not particularly limited, but the used Lewis base tends to remain in the polymer. That is, the hydrogenated block copolymer may contain 2,2-di (2-tetrahydrofuryl) propane [DTHFP] in some cases, and usually has a tendency to contain DTHFP in an amount of 5 ppm by mass or more. , DTHFP may be contained in an amount of 10 ppm by mass or more. The upper limit of the content of DTHFP may be 2,000 mass ppm, may be 1,000 mass ppm, may be 500 mass ppm, may be 250 mass ppm, and may be 50 mass ppm. It may be ppm by mass or 30 ppm by mass.
On the other hand, according to the above production method, the hydrogenated block copolymer is a Lewis base (vinylating agent) other than DTHFP, specifically, dimethyl ether, diethyl ether, tetrahydrofuran (THF), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Triethylamine, N, N, N ', N'-tetramethylenediamine (TMEDA) and N-methylmorpholine are not contained, or their contents tend to be 1 ppm or less.
The content of the Lewis base in the hydrogenated block copolymer is not particularly limited, but can be determined by gas chromatography.

(Olefin-based resin (IIb))
Examples of the olefin resin (IIb) that can be used as the resin component (II) include a polyolefin resin obtained by polymerizing an olefin, and an olefin polymer.
Examples of the olefin constituting the polyolefin resin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like. The olefin constituting the polyolefin-based resin may be used alone or in combination of two or more. In particular, examples of the polypropylene resin which is one of the polyolefin resins include homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, and propylene-ethylene-butene random copolymer. Copolymer, propylene-pentene random copolymer, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, propylene-ethylene-hexene random copolymer, and the like. Can be Further, these polypropylene resins may be added to unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc .; unsaturated dicarboxylic acids such as maleic acid, citraconic acid and itaconic acid; those unsaturated monocarboxylic acids or unsaturated dicarboxylic acids. Modified polypropylene resins obtained by graft copolymerizing a modifier such as an acid ester, amide or imide; an unsaturated dicarboxylic anhydride such as maleic anhydride, citraconic anhydride, and itaconic anhydride can also be used.

The olefin polymer is at least one olefin polymer selected from the group consisting of ethylene-propylene-diene copolymer (EPDM) rubber, ethylene-vinyl acetate copolymer (EVA) and polyethylene resin. is there.
Dienes usable as raw materials for the ethylene-propylene-diene copolymer rubber include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1,6-heptadiene. Chain non-conjugated dienes such as, 7-methyl-1,6-octadiene; cyclohexadiene, dichloropentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 Cyclic non-conjugated dienes such as isopropylidene-2-norbornene and 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5 -Norbornene, 2-propenyl-2,2-norbornadiene, 1 3,7-octatriene, 1,4,9- decatriene like triene such as.

(Styrene resin (IIc))
Examples of the styrene resin (IIc) that can be used as the resin component (II) include poly-α-methylstyrene, α-methylstyrene / styrene copolymer, styrene monomer copolymer, styrene monomer / aromatic monomer copolymer. Coalescence and the like.

(Conjugated diene polymer (IId))
As the conjugated diene polymer (IId) that can be used as the resin component (II), a homopolymer or copolymer of a conjugated diene monomer, or a conjugated diene monomer and another monomer other than an aromatic vinyl compound may be used. And a copolymer with a monomer. Examples of the other monomer include a monomer copolymerizable with the conjugated diene monomer.
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples thereof include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. One of these monomers may be used alone, or two or more thereof may be used in combination. Of these, 1,3-butadiene and isoprene are preferred, and isoprene is more preferred.
The monomer copolymerizable with the conjugated diene monomer is not particularly limited, but includes, for example, a chain olefin monomer such as ethylene, propylene and 1-butene; and a cyclic olefin monomer such as cyclopentene and 2-norbornene. Non-conjugated diene monomers such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene; methyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as ethyl acrylate; (meth) acrylonitrile, (meth) acrylamide and the like. One of these monomers may be used alone, or two or more thereof may be used in combination.
Examples of the conjugated diene polymer include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR), and ethylene-propylene-diene-based polymer. Copolymer rubber, butadiene-isoprene copolymer rubber (BIR) and the like can be mentioned. Among them, polyisoprene rubber and polybutadiene rubber are preferred, and polyisoprene rubber is more preferred.

(Physical properties of resin component (II))
The resin component (II) contained in the resin composition of the present invention preferably satisfies the following condition (1). When the resin component (II) contains at least one of the block copolymer (IIa) and the olefin-based resin (IIb), it is more preferable that the condition (1) is satisfied.
Condition (1): Coefficients A ₁ to A ₃ determined by performing fitting of the following equation [I] on a relaxation curve represented by relaxation strength y with respect to relaxation time x, measured using a pulse NMR apparatus, and The value of the motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ ₁ to τ ₃ of each component is 0.01 to 0.25 seconds.
y = A ₁ * exp (−0.5 * (x / τ ₁ ) ² ) + A ₂ * exp (−0.5 * (x / τ ₂ ) ² ) + A ₃ * exp (−x / τ ₃ ) [I]
M = (τ ₂ * A ₂ + τ ₃ * A ₃ ) / (A ₂ + A ₃ ) [II]
The above-mentioned relaxation curve is obtained by overlapping a relaxation curve derived from a total of three components, one component having relatively low mobility and two components having relatively high mobility. The fitting and the motility of each component can be obtained by fitting by the least square method.
The first term of the formula [I] is derived from the relaxation of the component having a relatively low mobility, and the second and third terms are derived from the relaxation of the component having a relatively high mobility. A ₁ corresponds to the ratio of the component having relatively low mobility, and A ₂ and A ₃ correspond to the ratio of the component having relatively high mobility.

Taking the case where the resin component (II) is a block copolymer as an example, the motility parameter M is the relaxation derived from the polymer block (B) when the behavior of the block copolymer is measured by pulsed NMR. And is an index mainly representing the motility derived from the conjugated diene. When a pulse of a predetermined frequency is applied to the block copolymer using pulse NMR, the relaxation originating from the polymer block (A), which is a component having a relatively low mobility, occurs immediately after the start of the relaxation. Relaxation due to the polymer block (B), which is a component having high motility, appears. By utilizing this phenomenon, it is possible to measure the physical properties of the polymer block (B), and to evaluate the relaxation behavior derived from the polymer block (B) by obtaining the motility parameter M by the above procedure. Can be.
The condition (1) also applies when the resin component (II) is an olefin-based resin (IIb). In this case, the mobility parameter indicates the mobility derived from the amorphous component of the olefin resin.

When the motility parameter M takes an appropriate value, vibration is effectively reduced in a temperature range in which the motility parameter is actually used, and the damping property can be improved. In addition, since the glass transition temperature Tg of the resin component (II) can be relatively increased by setting the mobility parameter M to an appropriate value, powdering by freeze-pulverization described below can be easily performed. Furthermore, as a result of increasing the glass transition temperature Tg, when dispersed in a resin composition, high strength can be imparted to the resin composition, and toughness can be increased while maintaining adhesive strength.
The motility parameter M is more preferably 0.01 to 0.10 seconds, further preferably 0.02 to 0.08 seconds, and still more preferably 0.02 to 0.06 seconds.

One method for satisfying the condition (1) is to use isoprene as a monomer for constituting a structural unit derived from a conjugated diene compound when the resin component (II) contains a block copolymer. Can be. When the resin component (II) contains an olefin-based resin, for example, 4-methyl-1-pentene can be used as a monomer.

Incidentally, fitting the resin component (II) is, in the case is intended to include styrene-based resin (IIc), the conjugated diene polymer (IId) is, by the formula [I], the _{A 1} 0 and the following formula [I '] Can be performed, and in this case, it is preferable to satisfy the following condition (1 ′).
Condition (1 ′): Coefficients A ₂ and A ₂ determined by performing fitting of the following equation [I ′] on a relaxation curve represented by a relaxation intensity y with respect to a relaxation time x measured using a pulse NMR apparatus. The value of the motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ ₂ and τ ₃ of ₃ and each component is 0.01 to 0.25 seconds.
y = A ₂ * exp (−0.5 * (x / τ ₂ ) ² ) + A ₃ * exp (−x / τ ₃ ) [I ′]
M = (τ ₂ * A ₂ + τ ₃ * A ₃ ) / (A ₂ + A ₃ ) [II]
The mobility of the resin components (IIc) and (IId) can be obtained by fitting the above relaxation curve by the least squares method using the formula [I ′].

(Condition (2))
The resin component (II) preferably satisfies the following condition (2).
Condition (2): 60 ° C. measured based on JIS K7244-10 (2005) under the conditions of a distortion amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to + 100 ° C., and a heating rate of 3 ° C./min. Has a shear storage modulus G ′ of 0.10 to 0.58 MPa and a peak temperature of loss tangent tan δ of −5 to + 40 ° C.
A test piece for measuring tan δ was pressed at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes using a press molding apparatus “NF-50T” (manufactured by Shinto Metal Industry Co., Ltd.) to produce a sheet having a thickness of 1.0 mm. The sheet was cut into a disk shape having a diameter of 8 mm to obtain a test piece.
Although there is no particular limitation on the tan δ measuring device, the test can be carried out by using a rotary rheometer “ARES G2” (manufactured by TA Instruments) or the like and sandwiching the test piece between flat plates having a diameter of 8 mm. .
By satisfying the condition (2), the temperature range in which the resin composition has appropriate hardness and high vibration damping properties can easily cover the temperature range in which the resin composition is actually used.
As a method for satisfying the condition (2), for example, a method of increasing the vinyl bond amount of the polymer block (B) can be used.

The temperature at the peak position of tan δ is more preferably −5 to + 35 ° C., further preferably 0 to + 35 ° C., still more preferably +5 to + 35 ° C., particularly preferably +5 to + 33 ° C., and most preferably +10 to + 33 ° C. It is.
The shear storage modulus G ′ at 60 ° C. is more preferably 0.1 to 1.8 MPa, still more preferably 0.2 to 1.0 MPa, and particularly preferably 0.3 to 0.55 MPa.
The temperature at the tan δ peak position of the resin component (II) can be set in the above range by increasing the vinyl bond amount of the polymer block (B) of the block copolymer. Further, in order to set the shear storage modulus G ′ of the resin component (II) at 60 ° C. within the above range, a method of adjusting the content of the polymer block (A) of the block copolymer or the polymer block (B) )), A method of increasing the vinyl bond amount can be adopted.

The resin component (II) preferably has a glass transition temperature Tg of 0 ° C. or higher, or is a crystalline resin. By satisfying any one of these conditions, freezing and pulverization can be easily performed, and the resin component (II) can be easily adjusted to a desired particle size.

(Whole resin component (II))
The resin component (II) is preferably a crumb, pellet, micropellet, or powder solid before being added to the resin composition. More preferably, it is a pulverized product in the form of micropellets or powder. Particularly preferred is a powder-like frozen and pulverized product.
The 50% volume average diameter of the powdery resin component (II) before addition to the resin composition is preferably 0.01 to 1.0 mm, more preferably 0.03 to 0.5 mm, and Preferably it is 0.05 to 0.3 mm. When the 50% volume average diameter of the powdery resin component (II) is 0.01 mm or more, powder production becomes easy, and when it is 0.5 mm or less, the mechanical strength of the resin composition increases.
The 50% volume average diameter of the powdery resin component (II) can be measured by wet laser diffraction using a sample in which powder is dispersed in water using a Mastersizer 3000 manufactured by Malvern.
The 50% volume average diameter of the powdery resin component (II) can be set in the above range by adjusting the pulverizing conditions (processing time, processing speed, etc.), selecting the mesh size of the sieve, and the like.
When the resin component (II) is in the form of crumbs, pellets, or micropellets, the diameter is preferably 0.1 to 5 mm, more preferably 0.3 to 2 mm, and still more preferably 0.5 to 2 mm. From 1 mm.

<Other ingredients>
(Powder component)
The urethane composition used as the matrix resin component (I) may include a powder component containing a filler. The powder component is not particularly limited as long as it is a component containing a filler, and may contain only the filler. In addition to the filler, for example, an antioxidant, an antioxidant, and a pigment (Dye), thixotropic agent, ultraviolet absorber, flame retardant, surfactant (including leveling agent), dispersant, dehydrating agent, adhesion imparting agent, various additives such as antistatic agent, etc. There may be.

Examples of the filler include organic or inorganic fillers of various shapes. As the filler, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, heavy calcium carbonate, sedimentation Calcium carbonate (light calcium carbonate), colloidal calcium carbonate, magnesium carbonate, zinc carbonate; limestone clay, kaolin clay, calcined clay; carbon black; these fatty acid-treated products, resin acid-treated products, urethane compound-treated products, fatty acid esters Treated products; and the like.
Among these fillers, carbon black and heavy calcium carbonate are preferable because the viscosity and thixotropy of the urethane composition are easily adjusted.
When carbon black is included as a filler in the urethane composition, a cured urethane product having excellent physical properties (eg, hardness, elongation, etc.) can be obtained. When heavy calcium carbonate is included as a filler in the urethane composition, a urethane composition having excellent deep curability can be obtained. Further, the use of pellet carbon black as a filler is preferable in that not only workability is improved, but also when dehydration is further promoted when mixed with the polyol compound (U).

Examples of the antioxidants include hindered phenolic antioxidants.

Examples of the antioxidant include butylhydroxytoluene and butylhydroxyanisole.

Examples of the above pigments include inorganic pigments such as titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and carbon black; azo pigments, phthalocyanine pigments, and quinacridone pigments , Quinacridonequinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments And organic pigments such as isoindoline pigments.

Examples of the thixotropic agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.) and Dispalon (manufactured by Kusumoto Kasei Co., Ltd.).

Examples of the adhesion-imparting agent include terpene resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin and the like.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether and the like.

Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

において In the urethane composition, the content of the powder component relative to 100 parts by mass of the polyol compound (U) is preferably 300 parts by mass or less, preferably 0 to 250 parts by mass, and more preferably 0 to 210 parts by mass. When the content of the powder component is within the above range, the viscosity of the urethane composition becomes appropriate, and the workability is improved.

(Plasticizer)
The resin composition may contain a plasticizer. Examples of the plasticizer include diisononyl adipate; diisononyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; Propylene glycol polyester, butylene glycol adipate polyester, and the like.

の Among these plasticizers, diisononyl adipate and diisononyl phthalate are preferred because they are excellent in compatibility and advantageous in cost.

These plasticizers may be used alone or in combination of two or more.

可塑 The content of the plasticizer based on 100 parts by mass of the total of the polyol compound (U) and the isocyanate compound (V) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass.

(Curing agent)
In order to cure the matrix resin component (I), the resin composition may contain a crosslinking agent, a photo or thermal polymerization initiator, a co-reactant, and the like as a curing agent.

[Physical properties of resin composition, etc.]
(Average dispersion diameter of resin component (II))
The average dispersion diameter of the resin component (II) in the resin composition is from 10 to 5,000 μm. The average dispersion diameter of the resin component (II) is preferably from 20 to 3,000 μm, more preferably from 30 to 1,000 μm, further preferably from 40 to 500 μm, and particularly preferably from 50 to 300 μm. If the average dispersion diameter is less than 10 μm, the productivity of the resin composition may decrease, and if it exceeds 5,000 μm, the mechanical properties of the resin composition may decrease.
When the average dispersion diameter of the resin component (II) in the resin composition is in the above range, the aggregation of the resin component (II) is suppressed without lowering the adhesiveness and strength of the adhesive, and as a result, It is presumed that the resin composition can exhibit high toughness while maintaining the tensile strength and the adhesiveness to the steel sheet, and can be provided with a function other than the adhesiveness, such as high vibration damping property in a wide practical use temperature range. You.
Further, since the resin component (II) may be pulverized to such an extent as to have an average dispersion diameter in this range, the labor required for pulverization is less likely to occur, and problems such as deactivation of the material can be avoided and cost increase can be prevented. it can.

The resin composition in which the resin component (II) is dispersed can be obtained, for example, by dispersing a powder of the resin component (II) described later in the resin composition.
In the present specification, the average dispersion diameter of the resin component (II) is determined by immersing the resin composition in a solvent in which the resin component (II) is dissolved and in which the resin component (I) is not dissolved, and then observing the surface state with a microscope. It was measured by doing

(Intensity of tan δ at 20 ° C.)
The strength of the loss tangent tan δ at 20 ° C. of the resin composition is preferably at least 0.15, more preferably at least 0.23, even more preferably at least 0.30, and preferably at least 0.30. 50 or less. When tan δ is 0.15 or more, when used as an adhesive for DG, the sound insulation of glass is improved.
In order to set the strength of the loss tangent tan δ at 20 ° C. within the above range, the resin component (II) satisfying the above condition (1) may be used.

The content of the resin component (II) with respect to the total amount of the resin composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, further preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass. It is. When the content of the resin component (II) is 50% by mass or less, it is easy to maintain the viscosity of the resin composition satisfactorily, and when the content of the resin component (II) is 5% by mass or more, the resin composition This can prevent the effect of improving the vibration damping property from being reduced.

The content of the resin component (I) relative to the total amount of the resin composition is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, further preferably 20 to 60% by mass, and particularly preferably 25 to 50% by mass. It is. When the content of the resin component (I) is 80% by mass or less, the workability is improved without the viscosity being too low, and when the content of the resin component (I) is 10% by mass or more, the viscosity becomes high. Workability is improved.

The total content of the matrix resin component (I) and the resin component (II) is preferably 100% by mass based on the total amount of the resin composition. Components other than the above-mentioned components may be included.

[powder]
The powder according to the present embodiment is a resin component that is at least one selected from the above-described block copolymer (IIa), olefin-based resin (IIb), styrene-based resin (IIc), and conjugated diene polymer (IId). A powder composed of (II), wherein the resin component (II) satisfies the above-mentioned condition (1), and further, a polymer block (IIa) of a block copolymer (IIa) capable of constituting the resin component (II) The hydrogenation ratio of B) is from 10 to 99 mol% based on the total number of moles of carbon-carbon double bonds in the polymer block (B) in the block copolymer (IIa).

Here, the block copolymer (IIa) has the same material and physical properties as described above, except that the hydrogenation ratio of the polymer block (B) is specified. The olefin resin (IIb), the styrene resin (IIc), and the conjugated diene polymer (IId) are the same as those described for the component (II) constituting the resin composition.
In the resin component (II) constituting the powder, a polymer block (A) containing more than 70 mol% of a structural unit derived from an aromatic vinyl compound and a polymer block containing 30 mol% or more of a structural unit derived from a conjugated diene compound. The fact that a block copolymer having a united block (B) is preferable is also the same as described for the resin component (II).
Further, the preferable range of the content of the polymer block (A) in the block copolymer is 6 to 22% by mass in the same manner as described for the resin component (II).

The powder is dispersed in the resin composition to improve the vibration damping properties of the resin composition, and the hydrogenation rate of the polymer block (B) is 10 mol% or more, so that the powder is added to the resin composition. When added, the powder can be improved in heat resistance and weatherability.

The powder is preferably a pulverized product of the resin component (II), particularly preferably a freeze-pulverized product.

Preferred physical properties of the resin component (II) constituting the powder (shear storage modulus G ′ at 60 ° C. is in the range of 0.10 to 0.58 MPa, tan δ peak temperature is in the temperature range of −5 to + 40 ° C.) Are the same as those described above for the resin component (II).
The 50% volume average diameter of the powder is preferably 0.01 mm to 1.0 mm, as described for the resin component (II).

方法 The method for producing the powder is not particularly limited, and a known method can be employed. Considering that the resin component (II) is a material having elasticity, the resin component (II) is frozen by a liquefied inert gas (such as nitrogen gas), then pulverized, and sieved to obtain a desired material. It is preferable to obtain a powder having a particle size range.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
Hereinafter, a method for producing the resin component (I) and the resin component (II) used in each example will be described.

(Production Examples 1 to 3) Production of Block Copolymers TPE-1 to 3 as Resin Component (II) Block copolymers TPE-1 to 3 were produced by the following procedure.
50.0 kg of cyclohexane (solvent) dried with Molecular Sieves A4 and 0.087 kg of a 10.5 mass% sec-butyllithium cyclohexane solution as an anionic polymerization initiator were placed in a pressure-resistant container dried with nitrogen and dried. -Substantially added amount of butyl lithium: 9.1 g).
After the temperature inside the pressure vessel was raised to 50 ° C., 1.0 kg of styrene (1) was added and polymerization was carried out for 30 minutes. Then, the temperature was lowered to 40 ° C. and 2,2-di (2-tetrahydrofuryl) propane [DTHFP] After adding 0.032 kg, 14.64 kg of isoprene was added over 5 hours, and the mixture was polymerized for 1 hour. Thereafter, the temperature was raised to 50 ° C., 1.0 kg of styrene (2) was added, polymerization was performed for 30 minutes, methanol was added to stop the reaction, and a reaction solution containing a triblock copolymer of polystyrene-polyisoprene-polystyrene. I got
After the temperature of the reaction solution was raised to 50 ° C., the hydrogen pressure was increased to 1 MPa, and then a Ziegler-based catalyst (hydrogenation catalyst) formed from nickel octylate and trimethylaluminum was added under a hydrogen atmosphere. The reaction was continued until the absorption of hydrogen ceased. After allowing the reaction mixture to cool and release pressure, the Ziegler catalyst was removed by washing with water, and the mixture was dried under vacuum to obtain a hydrogenated product of the polystyrene-polyisoprene-polystyrene triblock copolymer of Production Example 1 ( TPE-1) was obtained.
In Production Examples 2 and 3, the raw materials and the amounts used were changed to those shown in Table 1, and hydrogenated block copolymers (hydrogenated products of triblock copolymers of polystyrene-polyisoprene-polystyrene) were used. TPE-2 and 3 were obtained. Specifically, the amount of styrene added was 1.5 kg in both the first and second stages, and the amount of the cyclohexane solution of sec-butyllithium having a concentration of 10.5 mass%, which was an anionic polymerization initiator, was 0.166 kg. The hydrogenated block copolymer TPE-1 was replaced with 13.6 kg of isoprene instead of 14.64 kg of isoprene, the diene polymerization temperature was 50 ° C., and no Lewis base was used as the conjugated diene. Similarly, TPE-2 was produced. The addition amount of styrene was 1.7 kg in both the first and second stages, the amount of 10.5 mass% sec-butyllithium cyclohexane solution used as an anionic polymerization initiator was 0.101 kg, and The above water was used, except that 13.3 kg of isoprene was used instead of 14.64 kg of isoprene as the diene, and 0.065 kg of N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was used as the Lewis base. TPE-3 was produced in the same manner as in the addition block copolymer TPE-1.
Table 1 shows the materials used and their amounts used.

物 Physical properties of the obtained block copolymers TPE-1 to TPE-3 were measured by the following procedures.

<Physical properties of hydrogenated block copolymer>
(I) Content of Polymer Block (A) The hydrogenated block copolymer was dissolved in CDCl ₃ and subjected to ¹ H-NMR measurement [Apparatus: “ADVANCE 400 Nano bay” (manufactured by Bruker), measurement temperature: 30 ° C. And the content of the polymer block (A) was calculated from the peak intensity derived from styrene.

(Ii) Amount of vinyl bond in polymer block (B) The block copolymer before hydrogenation was dissolved in CDCl ₃ and subjected to ¹ H-NMR measurement [Apparatus: “ADVANCE 400 Nano bay” (manufactured by Bruker), measurement temperature] : 30 ° C]. Ratio of the peak area corresponding to the 3,4-linkage unit and 1,2-linkage unit in the isoprene structural unit and the 1,2-linkage unit in the butadiene structural unit to the total peak area of the structural units derived from isoprene and / or butadiene. The amount of vinyl bond (total content of 3,4-linkage unit and 1,2-linkage unit) was calculated from.

(Iii) Hydrogenation rate of polymer block (B) The hydrogenated block copolymer was dissolved in CDCl ₃ and measured by ¹ H-NMR [apparatus: “ADVANCE 400 Nano bay” (manufactured by Bruker), measurement temperature: 30 ° C], and the hydrogenation rate was calculated from the peak area derived from the residual olefin of isoprene or butadiene and the peak area ratio derived from ethylene, propylene, butylene, 2-methylbutylene, and 3-methylbutylene.

(Iv) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) in terms of polystyrene of the hydrogenated block copolymer was determined by gel permeation chromatography (GPC) measurement under the following conditions.
(GPC measurement device and measurement conditions)
-Equipment: GPC equipment "HLC-8020" (manufactured by Tosoh Corporation)
Separation column: Two “TSKgel G4000HX” manufactured by Tosoh Corporation were connected in series.
・ Eluent: tetrahydrofuran ・ Eluent flow rate: 0.7 mL / min
-Sample concentration: 5mg / 10mL
・ Column temperature: 40 ℃
・ Detector: Differential refractive index (RI) detector ・ Calibration curve: Created using standard polystyrene

(V) Peak temperature of loss tangent tan δ, peak intensity of tan δ, shear storage modulus The obtained block copolymer was subjected to a temperature of 230 ° C. by a press molding apparatus “NF-50T” (manufactured by Shinto Metal Industry Co., Ltd.). A sheet having a thickness of 1.0 mm was prepared by applying pressure at a pressure of 10 MPa for 3 minutes, and the sheet was cut into a disk shape having a diameter of 8 mm to obtain a test piece.
A distortion control dynamic viscoelasticity device “ARES-G2” (manufactured by TA Instruments) based on JIS K7244-10 (2005) was used as a measuring device, and was formed by two flat plates having a diameter of 8 mm. The test piece was sandwiched, vibrated at a strain of 0.1% and a frequency of 1 Hz, and the temperature was raised from −70 ° C. to 100 ° C. at 3 ° C./min for testing.
From the above test, a temperature characteristic curve of tan δ and shear storage elastic modulus G ′ was created, and a peak temperature of tan δ, a peak intensity of tan δ, and a shear storage elastic modulus G ′ at 60 ° C. were determined from the obtained temperature characteristic curves. Was.

(Vi) Motility parameter M
First, the relaxation time of the resin component (II) was measured by a pulse NMR method. Specifically, it measured by the following procedures.
・ Pulse NMR system: Minispec MQ20 manufactured by Bruker Biospin
Measurement method: solid echo method Measurement conditions: The obtained resin component (II) was applied for 3 minutes at a temperature of 230 ° C. and a pressure of 10 MPa using a press molding apparatus “NF-50T” (manufactured by Shinto Metal Industry Co., Ltd.). By pressing, a sheet having a thickness of 1.0 mm was produced, and the sheet cut out into a length of 10 mm × a width of 10 mm × was put into a sample tube to obtain a sample. After holding this sample at 60 ° C. for 15 minutes, measurement was performed under the conditions of a pulse width of 7.2 μsec, a pulse interval of 10 μsec, an integration count of 60, a spin echo repetition time of 1.0 sec, four dummy shots, and a measurement temperature of 60 ° C. To prepare a relaxation curve (relaxation strength y with respect to the relaxation time x) in the spin-spin relaxation of the resin component (II) (here, the block copolymer).
Next, the relaxation curve obtained by the above-mentioned pulse NMR method is fitted by the least square method using the following equation [I] to obtain coefficients A ₁ to A ₃ and the spin-spin relaxation time τ _{1 of} each component. ~ Τ ₃ was determined. Here, τ ₁ <τ ₂ . Using these numerical values, a motility parameter M (that is, a value indicating the motility of the block (B) of the block copolymer as the resin component (II)) was calculated based on the following equation [II].
y = A ₁ * exp (−0.5 * (x / τ ₁ ) ² ) + A ₂ * exp (−0.5 * (x / τ ₂ ) ² ) + A ₃ * exp (−x / τ ₃ ) [I]
M = (τ ₂ * A ₂ + τ ₃ * A ₃ ) / (A ₂ + A ₃ ) [II]
The results are shown in Table 2 below.

(Production of powder)
The block copolymer TPE-1 obtained in Production Example 1 was charged into a cryomill (manufactured by Taiyo Nippon Sanso Co., Ltd.) and freeze-pulverized with liquid nitrogen. The obtained pulverized product was sieved to prepare a block copolymer TPE-1 powder (TPE-1 powder) having an average particle diameter (50% volume average diameter) of 70 μm.
With respect to the block copolymers TPE-2 and TPE-2 obtained in Production Examples 2 and 3, powders having an average particle diameter (50% volume average diameter) of 70 μm (TPE-2 powder and TPE-3 powder) were obtained in the same procedure. Produced.
The average particle diameter (50% volume average diameter) of the powder was measured by wet laser diffraction using a sample in which powder was dispersed in water using a Mastersizer 3000 manufactured by Malvern.

(Preparation of resin composition)
A resin composition was prepared using the block copolymers TPE-1 to 3 obtained in Production Examples 1 to 3, a monomer for preparing the resin component (I), other additives, and a catalyst. (Examples 1 to 5, Comparative Example 1). Table 3 below shows the components and the amounts of the components in the examples and comparative examples.
The materials used to prepare the resin composition other than the block copolymers TPE-1 to TPE-3 are as follows.
(Polyol)
-Bifunctional polypropylene glycol (Exenol 2020 manufactured by Asahi Glass Co., Ltd., number average molecular weight 2,000)
・ Trifunctional polypropylene glycol (Exenol 5030 manufactured by Asahi Glass Co., Ltd., number average molecular weight 5,040)
(Plasticizer)
・ Diisononyl phthalate (DINP)
(Isocyanate)
・ Diphenylmethane diisocyanate (MDI)
・ Hexamethylene diisocyanate-biuret (HDI-b)
(filler)
・ Calcium carbonate ・ Carbon black (catalyst)
-Bismuth tris (2-ethylhexanoate) (Neostan U-600 manufactured by Nitto Kasei Co., Ltd.)
・ Dioctyl tin dilaurate (Neostan U-810 manufactured by Nitto Kasei Co., Ltd.)

Specifically, under a nitrogen atmosphere, the polyol, the plasticizer, and the powder of the resin component (II) and the filler shown in Table 3 were charged into a planetary mixer (manufactured by Primix Co., Ltd.), and the pressure was set to 1.2 kPa at 50 ° C. The mixture was then depressurized and dehydrated by mixing at a rotation speed of 40 rpm for 4 hours to obtain a paste mixture.
Next, among the isocyanates shown in Table 3, MDI was put into a planetary mixer, and the paste mixture after the above-mentioned dehydration treatment was added in its entirety. Further, a bismuth-based catalyst was added among the catalysts in Table 3, and at a rotation speed of 40 rpm. And mixed at 50 ° C. for 1 hour. Further, HDI-b among the isocyanates shown in Table 3 and a tin-based catalyst among the catalysts shown in Table 3 were added and mixed at a rotation speed of 40 rpm for 10 minutes to obtain one matrix resin component (I). A resin composition containing a liquid moisture-curable polyurethane composition was obtained.

(Evaluation of resin composition)
The physical properties of the resin compositions obtained in Examples 1 to 5 and Comparative Example 1 were evaluated according to the following measurement methods.
<Dynamic viscoelasticity measurement (DMA)>
The measurement was performed according to JIS K 7244-4 (1999). Specifically, the obtained resin composition was applied on a polypropylene (PP) film using a glass rod having a 1 mm spacer wound at both ends, and cured at 23 ° C. and 50% RH for 2 days. Using a cured product obtained in this manner, a test piece of 50 mm long × 10 mm wide was punched out, and a dynamic viscoelasticity measuring device manufactured by Hitachi High-Tech Science Co., Ltd. was used at a measurement temperature of −80 to + 100 ° C. and a frequency of 10 Hz. A temperature characteristic curve of tan δ was prepared by measurement, and the presence or absence of a tan δ peak at −10 to + 40 ° C. was confirmed, and the tan δ peak temperature, tan δ peak intensity, and tan δ intensity at 20 ° C. were measured.

<Tensile test>
The following items were all measured according to JIS K6251 (2010). Specifically, the obtained resin composition is applied on a PP film using a glass rod with a 2 mm spacer wound on both ends, and cured for 2 days in an atmosphere of 23 ° C. and 50% RH. No. 5 dumbbell-shaped test piece was punched out from the cured product, and the tensile strength [MPa] and rupture were measured by measuring the test piece at a test speed of 500 mm / min using a universal material tester Model 5966 manufactured by Instron. The elongation [%] was measured.
<Tear test>
The tear strength [kN / m] was measured according to JIS K7128-1 (1998). Specifically, the obtained resin composition is applied on a PP film using a glass rod with a 2 mm spacer wound on both ends, and cured for 2 days in an atmosphere of 23 ° C. and 50% RH. A trouser-type test piece of JIS-K7128-1 was prepared from the cured product, and the tear strength was measured at a test speed of 100 mm / min using a universal material tester 5966 manufactured by Instron. It was measured.
<Adhesion test (steel plate)>
Tensile shear adhesive strength [MPa] was measured according to JIS K6850 (1999). Specifically, two SPCC SD (25 mm × 100 mm × 2 mm thick) steel plates were used, and these were degreased with acetone and faced like a tensile-shear adhesive test piece, and PTFE of 25 mm × 10 mm × 5 mm thickness was used. The three spacers made were sandwiched and fixed with masking tape. Thereafter, the spacer at the center was extracted, and a resin composition to be measured was filled therein to prepare a sample. With respect to this sample, tensile shear strength was measured at a test speed of 2 mm / min using a universal material tester Model 5966 manufactured by Instron. At this time, it was visually confirmed whether the failure mode was cohesive failure or adhesive failure.

<Hardness>
Using the resin compositions obtained in Examples and Comparative Examples, test pieces for measuring hardness having a size of 30 mm × 25 mm × thickness of 5 mm were prepared, and after the resin compositions were cured, JIS K 6253 (2012) ), A durometer hardness test was performed using a durometer hardness meter type A GS-619R-G (manufactured by Teclock Corporation) to measure Shore A hardness.

<Average dispersion diameter of component (II)>
The obtained resin composition was applied on a PP film using a glass rod having a 1 mm spacer wound on both ends, and cured for 2 days in an atmosphere of 23 ° C. and 50% RH to obtain a cured product. The sample in which the component (II) was dissolved was obtained by immersing the obtained cured product in cyclohexane for 5 minutes. The surface of the sample was observed with a polarization microscope ECLIPSE E600POL manufactured by Nikon Corporation, the size of 30 randomly selected components (II) was measured, their arithmetic average was calculated, and the obtained value was calculated as the component (II). ).

<Weather resistance test>
Using the resin compositions obtained in Examples and Comparative Examples, test pieces having a size of 30 mm × 25 mm × 5 mm in thickness were prepared, and a weather resistance tester (Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd.) was used. Then, a weather resistance test was carried out by exposing for 200 hours under the conditions of irradiance 180 W / m ² , black panel temperature 60 ° C. and relative humidity 50%. If there was no difference in appearance between before and after the weather resistance test, 〇, if there was a difference but the level was not problematic for practical use, △ if there was a difference of a level that was not suitable for practical use, then × evaluated.

<Sound transmission loss>
The center of a steel plate having a size of 900 mm x 600 mm x a thickness of 6 mm was cut into a size of 770 mm x 470 mm, and the edge of the cut steel plate was obtained in Examples and Comparative Examples so that the width was 1 cm and the thickness was 5 mm. The resin composition was applied.
Thereafter, a single glass sheet having a size of 800 mm x 500 mm x a thickness of 5 mm was brought into close contact with the applied resin composition, and the resin composition was cured to obtain a test piece. Using the obtained test piece, the sound transmission loss (STL) of a reverberation room and an anechoic room based on JIS A 1416 (2000) was measured.

The results are shown in Table 4 below and FIG. FIG. 1 is a graph showing the temperature characteristics of the loss tangent tan δ of the resin compositions of Examples 1 to 4 and Comparative Example 1.

明らか As is clear from the results in Table 4, the resin compositions of Examples 1 to 5 have higher values of tear strength, tensile shear bond strength, and hardness than Comparative Example 1. In particular, Example 1 shows that the failure mode in the adhesive strength test is a cohesive failure type, and the adhesive strength of the adhesive is extremely high. Further, as shown in FIG. 1, the resin compositions of Examples 1 to 3 had a peak of tan δ in the range of −10 to + 40 ° C., and did not contain the resin component (II). It shows that the composition has higher damping properties than the composition. Furthermore, it can be seen that the resin compositions of Examples 1 to 5 have higher sound transmission loss than the resin composition of Comparative Example 1 at any frequency, and are excellent in sound insulation.

Since the block copolymer has low polarity and low compatibility with the adhesive, it may aggregate without mixing (decrease in mechanical strength and adhesive strength). By mixing the powder (fine particles) obtained by the above with an adhesive before curing and dispersing it with an appropriate dispersion diameter, the tear strength and the hardness are improved while maintaining the adhesiveness to the steel sheet, and further, the mobility parameter is determined by a predetermined value. By using the resin component (II) in the range, the vibration damping property can be improved.
Further, by using a block copolymer having a high peak temperature of tan δ, the elongation at break, the tear strength, and the adhesion are improved due to the high material strength of the elastomer.
Furthermore, the resin component (II) constituting the powder used in Examples 1 to 4 is a block copolymer, and since the polymer block (B) is hydrogenated, the resin component (II) is high as is apparent from Table 1. It shows weather resistance and can be expected to improve heat resistance.

On the other hand, the resin composition of Comparative Example 1 was inferior to the resin compositions of Examples 1 to 5 in evaluation of elongation at break, tensile shear bond strength, hardness and the like. In the resin composition of Comparative Example 1, no tan δ peak was observed in the range of −10 to + 40 ° C.

The resin composition of the present invention can be used for a DG adhesive for automobiles. In applications other than the DG adhesive, for example, by giving the adhesive an anti-vibration property, by replacing the existing adhesive used for the member for which vibration is to be suppressed with the adhesive of the present invention, It can be expected to reduce vibration and noise while maintaining adhesiveness.

Claims

A matrix resin component (I) having a monomer unit containing a hetero atom, and a block copolymer having a polymer block (A) derived from an aromatic vinyl compound and a polymer block (B) derived from a conjugated diene compound A resin composition comprising at least one resin component (II) selected from the group consisting of styrene-based resin, conjugated diene polymer, and olefin-based resin, wherein the resin component ( A resin composition wherein the average dispersion diameter of II) is from 10 μm to 5,000 μm.
The resin composition according to claim 1, wherein the resin component (II) satisfies the following condition (1).
Condition (1): Coefficients A 1 to A 3 determined by performing fitting of the following equation [I] on a relaxation curve represented by a relaxation strength y with respect to a relaxation time x measured using a pulse NMR apparatus, and The motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ 1 to τ 3 of each component is 0.01 to 0.25 seconds.
y = A 1 * exp (−0.5 * (x / τ 1 ) 2 ) + A 2 * exp (−0.5 * (x / τ 2 ) 2 ) + A 3 * exp (−x / τ 3 ) [I]
M = (τ 2 * A 2 + τ 3 * A 3 ) / (A 2 + A 3 ) [II]
樹脂 The resin composition according to claim 1 or 2, wherein the resin component (I) is a polyurethane.
樹脂 The resin composition according to any one of claims 1 to 3, wherein the resin component (I) is a moisture-curable polyurethane.
樹脂 The resin composition according to any one of claims 1 to 4, wherein the resin component (I) is a one-pack moisture-curable polyurethane comprising a polyol compound and an isocyanate compound.
(6) The resin composition according to any one of (1) to (5), wherein the resin component (II) is a powdery frozen and pulverized product.
(7) The resin composition according to (6), wherein the 50% volume average diameter of the resin component (II), which is the powder-like freeze-ground product, is 0.01 mm to 1.0 mm.
The resin composition according to claim 2, wherein the mobility parameter M of the resin component (II) is 0.01 to 0.10 seconds.
9. The resin composition according to claim 1, wherein the resin component (II) satisfies the following condition (2).
Condition (2): 60 ° C. measured based on JIS K7244-10 (2005) under the conditions of a distortion amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to + 100 ° C., and a heating rate of 3 ° C./min. Has a shear storage modulus G ′ of 0.10 to 0.58 MPa and a peak temperature of loss tangent tan δ of −5 to + 40 ° C.
The resin component (II) has a polymer block (A) containing more than 70 mol% of a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing 30 mol% or more of a structural unit derived from a conjugated diene compound. The resin composition according to any one of claims 1 to 9, which is a block copolymer having:
The resin composition according to any one of claims 1 to 10, wherein the content of the polymer block (A) in the block copolymer is 6 to 22% by mass.
The resin composition according to any one of claims 1 to 11, wherein the hydrogenation ratio of the polymer block (B) in the block copolymer is 10 to 99 mol%.
The resin composition according to any one of claims 1 to 12, wherein the strength of the loss tangent tan δ at 20 ° C is 0.15 or more.
A block that satisfies the following condition (1) and has a polymer block (A) derived from an aromatic vinyl compound and a polymer block (B) having a hydrogenation rate of 10 to 99 mol% and derived from a conjugated diene compound. A powder comprising at least one resin component (II) selected from the group consisting of a copolymer, a styrene resin, a conjugated diene polymer, and an olefin resin.
Condition (1): Coefficients A 1 to A 3 determined by performing fitting of the following equation [I] on a relaxation curve represented by a relaxation strength y with respect to a relaxation time x measured using a pulse NMR apparatus, and The motility parameter M obtained by the following equation [II] using the spin-spin relaxation times τ 1 to τ 3 of each component is 0.01 to 0.25 seconds.
y = A 1 * exp (−0.5 * (x / τ 1 ) 2 ) + A 2 * exp (−0.5 * (x / τ 2 ) 2 ) + A 3 * exp (−x / τ 3 ) [I]
M = (τ 2 * A 2 + τ 3 * A 3 ) / (A 2 + A 3 ) [II]
The powder according to claim 14, which is a freeze-ground product of the resin component (II).
16. The powder according to claim 14, wherein the 50% volume average diameter is 0.01 mm to 1.0 mm.
The powder according to any one of claims 14 to 16, wherein the mobility parameter M of the resin component (II) is 0.01 to 0.10 seconds.
18. The powder according to claim 14, wherein the resin component (II) satisfies the following condition (2).
Condition (2): 60 ° C. measured based on JIS K7244-10 (2005) under the conditions of a distortion amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to + 100 ° C., and a heating rate of 3 ° C./min. Has a shear storage modulus G ′ of 0.10 to 0.58 MPa and a peak temperature of loss tangent tan δ of −5 to + 40 ° C.
The resin component (II) has a polymer block (A) containing a structural unit derived from an aromatic vinyl compound exceeding 70 mol% and a polymer block (B) containing a structural unit derived from a conjugated diene compound in an amount of 30 mol% or more. The powder according to any one of claims 14 to 18, which is a block copolymer having:
20. The powder according to any one of claims 14 to 19, wherein the content of the polymer block (A) in the block copolymer is 6 to 22% by mass.
An adhesive containing the resin composition according to any one of claims 1 to 13.
A direct glazing adhesive for automobiles, comprising the resin composition according to any one of claims 1 to 13.