Adhesive composition, structure, and golf club

Abstract

To provide an adhesive composition enabling suppression of filler sedimentation.SOLUTION: An adhesive composition including a resin component (A) and a filler (B), characterized in that the absolute value of a difference (ρP-ρF) between the density ρP [g / cm3] of the resin component (A) and the density ρF [g / cm3] of the filler (B) is 0.80 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition, a structure, and a golf club. [Background technology]

[0002] A filler may be blended into the adhesive composition.

[0003] Patent Document 1 discloses an adhesive composition containing at least one thermosetting monomer, a plurality of spacers, and optionally at least one curing initiator, wherein the spacers are composed of one or more organic polymers. Patent Document 1 also describes that the problem to be solved is the need for an effective method for controlling bond line and planarity during packaging of semiconductor devices. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2005-519150 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides an adhesive composition that can suppress filler sedimentation. [Means for solving the problem]

[0006] According to the present invention, there are provided the following adhesive composition, structure, and golf club.

[0007] 1. A composition comprising a resin component (A) and a filler (B), The density ρ of the resin component (A) P [g / cm 3 ] and the density ρ of the filler (B) F [g / cm 3 ] and the difference (ρP -ρ F ) the absolute value of which is 0.80 or less. 2. The adhesive composition according to 1., wherein the filler (B) comprises one or more resins selected from the group consisting of (meth)acrylic resin, polyethylene resin, polypropylene resin, polyvinyl resin, polystyrene resin, polyester resin, polycarbonate resin, poly(meth)acrylonitrile resin, polyamide resin and urethane resin. 3. The adhesive composition according to 2., wherein the filler (B) comprises a (meth)acrylic resin. 4. Density ρ of the resin component (A) P is 0.60g / cm 3 More than 1.40g / cm 3 The adhesive composition according to any one of 1. to 3., which is: 5. Density ρ of the filler (B) F is 0.60g / cm 3 More than 2.20g / cm 3 An adhesive composition according to any one of 1. to 4., which is: 6. The median diameter D of the filler (B) measured by laser diffraction method 50 6. The adhesive composition according to any one of 1. to 5., wherein the particle size is 10 μm or more and 500 μm or less. 7. The adhesive composition according to any one of 1. to 6., wherein the content of the filler (B) is 1 part by mass or more and 50 parts by mass or less when the content of the resin component (A) is 100 parts by mass. 8. The adhesive composition according to any one of 1. to 7., wherein the filler (B) comprises a spherical filler. 9. The adhesive composition according to any one of 1. to 8., wherein the resin component (A) contains a (meth)acrylate. 10. The adhesive composition according to any one of 1. to 9., wherein the resin component (A) contains an elastomer. 11. The adhesive composition according to claim 10, wherein the elastomer comprises one or more elastomers selected from the group consisting of (meth)acrylonitrile-butadiene rubber, methyl(meth)acrylate-butadiene-styrene rubber, and methyl(meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber. 12. The adhesive composition according to 10. or 11., wherein the content of the elastomer is 1% by mass or more and 50% by mass or less when the total amount of the resin component (A) is taken as 100% by mass. 13. The adhesive composition according to any one of 1. to 12., wherein the resin component (A) further contains a radical polymerization initiator. 14. The adhesive composition according to any one of 1. to 13., wherein the resin component (A) further contains a reducing agent. 15. The adhesive composition according to any one of 1. to 14., wherein the total content of the resin component (A) and the filler (B) is 50% by mass or more and 100% by mass or less, when the total amount of the adhesive composition is 100% by mass. 16. The adhesive composition is a two-component adhesive composition comprising a first component and a second component, and the first component and the second component are mixed together for use; the first agent contains a radical polymerization initiator, 16. The adhesive composition according to any one of 1. to 15., wherein the second agent contains a reducing agent. 17. Using a Brookfield viscometer, the temperature was 25°C and the shear rate was 5.5 s -1 16. The adhesive composition according to 16., wherein the viscosity of the first part and the second part measured under the conditions is 2,000 mPa·s or more and 6,500 mPa·s or less. 18. An adhesive composition according to any one of 1. to 17., which is filled between a first member and a second member at least a portion of which is inserted into the first member, and which is capable of fixing at least a portion of the second member within the first member. 19. The adhesive composition according to claim 18, wherein the first member is a golf club sleeve and the second member is a golf club shaft. 20. A first member; a second member at least partially inserted within the first member; a cured product of the adhesive composition according to any one of 1. to 19. between the first member and the second member; A structure containing: 21. A golf club sleeve; a golf club shaft at least partially inserted into the golf club sleeve; a cured product of the adhesive composition according to any one of 1. to 19. between the golf club sleeve and the golf club shaft; Golf clubs including. 22. A composition comprising a resin component (A) and a filler (B); The density ρ of the resin component (A) P [g / cm 3 ] and the density ρ of the filler (B) F [g / cm 3 ] and the difference (ρ P -ρ F ) has an absolute value of 0.80 or less. [Effects of the Invention]

[0008] According to the present invention, an adhesive composition capable of suppressing filler sedimentation can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described below based on embodiments.

[0010] In the present embodiment, the term "(meth)acrylate" represents a concept that encompasses both acrylate and methacrylate. The same applies to similar terms such as "(meth)acrylic."

[0011] The composition of the present embodiment contains a resin component (A) and a filler (B), and the density ρ P [g / cm 3 ] and the density ρ of the filler (B) F [g / cm 3 ] and the difference (ρ P -ρ F) is less than or equal to 0.80. The composition of the present embodiment is preferably an adhesive composition.

[0012] 1. Adhesive composition The adhesive composition of this embodiment will be described below.

[0013] In this embodiment, the resin component (A) in the adhesive composition refers to monomer components such as (meth)acrylates, polymer components such as elastomers, and components involved in polymerization and curing, such as polymerization initiators and reducing agents, and the resin component (A) does not include filler (B).

[0014] The adhesive composition of the present embodiment contains a resin component (A) and a filler (B), and the density ρ P [g / cm 3 ] and the density ρ of the filler (B) of this embodiment F [g / cm 3 ] and the difference (ρ P -ρ F ) is less than or equal to 0.80.

[0015] It is presumed that the adhesive composition of the present embodiment makes it possible to suppress the settling of the filler by using a resin component and a filler that satisfy specific requirements regarding density.

[0016] The density ρ of the resin component (A) of this embodiment P [g / cm 3 ] and the density ρ of the filler (B) of this embodiment F [g / cm 3 ] and the difference (ρ P -ρ FFrom the viewpoint of further suppressing filler sedimentation, the absolute value of (a) is preferably 0.70 or less, more preferably 0.60 or less, even more preferably 0.50 or less, even more preferably 0.40 or less, even more preferably 0.30 or less, and even more preferably 0.25 or less, and is preferably 0.005 or more, more preferably 0.01 or more, even more preferably 0.015 or more, and even more preferably 0.02 or more, and is preferably 0.005 or more and 0.70 or less, more preferably 0.01 or more and 0.50 or less, even more preferably 0.015 or more and 0.30 or less, and even more preferably 0.02 or more and 0.25 or less.

[0017] The filler (B) of this embodiment preferably comprises one or more resins selected from the group consisting of (meth)acrylic resin, polypropylene resin, polyvinyl resin, polystyrene resin, polyester resin, polycarbonate resin, poly(meth)acrylonitrile resin, polyamide resin, urethane resin and polyolefin resin (preferably polyethylene resin), from the viewpoint of being able to further suppress sedimentation of the filler; and from the viewpoint of being able to improve the holding feeling when the adhesive composition of this embodiment is used to insert a golf club shaft into a sleeve and secure it, the filler (B) more preferably comprises one or more resins selected from the group consisting of (meth)acrylic resin, polyethylene resin, polypropylene resin, polyvinyl resin, polystyrene resin, polyester resin, polycarbonate resin, poly(meth)acrylonitrile resin, polyamide resin and urethane resin, even more preferably a (meth)acrylic resin, and even more preferably a methacrylic resin.

[0018] The density ρ of the resin component (A) of this embodiment P is preferably 0.60 g / cm from the viewpoint of further suppressing the settling of the filler. 3 More preferably, 0.70 g / cm 3 More preferably, 0.80 g / cm 3 More preferably, 0.90 g / cm 3 More preferably, 0.95 g / cm 3 and preferably 1.40 g / cm 3or less, more preferably 1.30 g / cm 3 or less, more preferably 1.20 g / cm 3 or less, more preferably 1.15 g / cm 3 or less, more preferably 1.10 g / cm 3 or less, more preferably 1.05 g / cm 3 and preferably 0.60 g / cm 3 More than 1.40g / cm 3 or less, more preferably 0.70 g / cm 3 More than 1.30g / cm 3 or less, more preferably 0.80 g / cm 3 More than 1.20g / cm 3 or less, more preferably 0.90 g / cm 3 More than 1.15g / cm 3 or less, more preferably 0.95 g / cm 3 More than 1.10g / cm 3 or less, more preferably 0.95 g / cm 3 More than 1.05g / cm 3 The following is the result.

[0019] The density ρ of the filler (B) of this embodiment F is preferably 0.60 g / cm from the viewpoint of further suppressing the settling of the filler. 3 More preferably, 0.70 g / cm 3 More preferably, 0.80 g / cm 3 More preferably, 0.90 g / cm 3 More preferably, 1.00 g / cm 3 More preferably, 1.10 g / cm 3 and preferably 2.20 g / cm 3 or less, more preferably 2.00 g / cm 3 or less, more preferably 1.80 g / cm 3 or less, more preferably 1.60 g / cm 3 or less, more preferably 1.50 g / cm 3 or less, more preferably 1.40 g / cm 3 or less, more preferably 1.30 g / cm 3or less, more preferably 1.25 g / cm 3 and preferably 0.60 g / cm 3 More than 2.20g / cm 3 or less, more preferably 0.70 g / cm 3 More than 2.00g / cm 3 or less, more preferably 0.80 g / cm 3 More than 1.80g / cm 3 or less, more preferably 0.90 g / cm 3 More than 1.60g / cm 3 or less, more preferably 0.90 g / cm 3 More than 1.50g / cm 3 or less, more preferably 1.00 g / cm 3 More than 1.40g / cm 3 or less, more preferably 1.00 g / cm 3 More than 1.30g / cm 3 or less, more preferably 1.10 g / cm 3 More than 1.25g / cm 3 The following is the result.

[0020] The median diameter D of the filler (B) of this embodiment measured by laser diffraction method 50 From the viewpoint of improving the holding feeling, is preferably 10 μm or more, more preferably 30 μm or more, even more preferably 50 μm or more, even more preferably 70 μm or more, even more preferably 90 μm or more, and even more preferably 100 μm or more, and is preferably 500 μm or less, more preferably 450 μm or less, even more preferably 400 μm or less, even more preferably 350 μm or less, even more preferably 300 μm or less, and even more preferably 250 μm or less, and is preferably 10 μm or more and 500 μm or less, more preferably 30 μm or more and 450 μm or less, even more preferably 50 μm or more and 400 μm or less, even more preferably 70 μm or more and 350 μm or less, even more preferably 90 μm or more and 300 μm or less, and even more preferably 100 μm or more and 250 μm or less.

[0021] When the content of the resin component (A) of this embodiment is taken as 100 parts by mass, the content of the filler (B) of this embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more, from the viewpoint of improving the grip feeling when the adhesive composition of this embodiment is used to insert and secure a golf club shaft into a sleeve; and from the viewpoint of improving workability, the content is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less; and from the viewpoint of improving the balance between the grip feeling and workability, the content is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, even more preferably 5 parts by mass or more and 30 parts by mass or less, even more preferably 7 parts by mass or more and 25 parts by mass or less, and even more preferably 10 parts by mass or more and 20 parts by mass or less.

[0022] The filler (B) of this embodiment preferably contains a spherical filler from the viewpoint of improving the grip feeling when the adhesive composition of this embodiment is used to insert and fix a golf club shaft into a sleeve.

[0023] The resin component (A) of the present embodiment preferably contains a (meth)acrylate, and more preferably contains a monofunctional (meth)acrylate, from the viewpoint of being able to further suppress sedimentation of the filler and to be able to control the viscosity of the adhesive composition within an appropriate range. Here, the (meth)acrylate of this embodiment does not include the elastomer described below. Furthermore, the monofunctional (meth)acrylate (B) of this embodiment is a compound having one (meth)acryloyl group.

[0024] The monofunctional (meth)acrylate of the present embodiment includes, for example, one or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, ter-butyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylacrylamide, diethyl (meth)acrylamide, and (meth)acryloylmorpholine.

[0025] The monofunctional (meth)acrylate of the present embodiment includes, for example, an alkyl monofunctional-containing (meth)acrylate having an alkyl group, and the alkyl-containing monofunctional (meth)acrylate includes, for example, one or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, ter-butyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc., and preferably includes methyl (meth)acrylate, and more preferably includes methyl methacrylate.

[0026] The monofunctional (meth)acrylate of the present embodiment includes, for example, a hydroxyl group-containing monofunctional (meth)acrylate. The hydroxyl group-containing monofunctional (meth)acrylate includes, for example, one or more selected from the group consisting of 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, and 1,4-butanediol mono(meth)acrylate, and preferably includes 2-hydroxyethyl (meth)acrylate, and more preferably includes 2-hydroxyethyl methacrylate.

[0027] The monofunctional (meth)acrylate of the present embodiment includes, for example, a monofunctional (meth)acrylate having a cyclic structure. The monofunctional (meth)acrylate having a cyclic structure includes, for example, one or more selected from the group consisting of dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and cyclohexyl (meth)acrylate, and preferably includes dicyclopentenyloxyethyl (meth)acrylate, and more preferably includes dicyclopentenyloxyethyl methacrylate. The monofunctional (meth)acrylate having a cyclic structure includes, for example, a monofunctional (meth)acrylate having an alicyclic structure, and the monofunctional (meth)acrylate having an alicyclic structure preferably includes, for example, dicyclopentenyloxyethyl methacrylate. The monofunctional (meth)acrylate of the present embodiment includes, for example, one or more selected from the group consisting of alkyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, and monofunctional (meth)acrylates having a cyclic structure, and preferably includes alkyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, and monofunctional (meth)acrylates having a cyclic structure. When an alkyl group-containing (meth)acrylate, a hydroxyl group-containing (meth)acrylate, and a monofunctional (meth)acrylate having a cyclic structure are used in combination, the ratio of the alkyl group-containing (meth)acrylate, the hydroxyl group-containing (meth)acrylate, and the monofunctional (meth)acrylate having a cyclic structure to be used in combination is preferably alkyl group-containing (meth)acrylate:hydroxyl group-containing (meth)acrylate:monofunctional (meth)acrylate having a cyclic structure=20-95:1-60:1-60, more preferably 35-85:5-45:5-45, and even more preferably 50-70:10-30:10-30, in terms of mass ratio, relative to a total of 100 mass% of the alkyl group-containing (meth)acrylate, the hydroxyl group-containing (meth)acrylate, and the monofunctional (meth)acrylate having a cyclic structure.

[0028] When the total amount of resin component (A) of this embodiment is taken as 100% by mass, the content of the (meth)acrylate of this embodiment is, from the viewpoint of being able to further suppress filler sedimentation and being able to control the viscosity of the adhesive composition within an appropriate range, preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and preferably 20% by mass or more and 99% by mass or less, more preferably 40% by mass or more and 95% by mass or less, even more preferably 60% by mass or more and 95% by mass or less, even more preferably 70% by mass or more and 90% by mass or less, even more preferably 80% by mass or more and 90% by mass or less.

[0029] The resin component (A) of the present embodiment preferably contains an elastomer from the viewpoint of being able to further suppress sedimentation of the filler and being able to control the viscosity of the adhesive composition within an appropriate range. The elastomer of this embodiment preferably has a soft segment unit, which preferably contains one or more structures selected from the group consisting of a diene structure, an ethylene structure, a propylene structure, an isoprene structure, a urethane structure, an ethylene glycol structure, a propylene glycol structure, a silicone structure, and a chloroprene structure, and more preferably contains a diene structure such as a butadiene structure.

[0030] The elastomer of this embodiment may have hard segments in addition to soft segment units. The "soft segment" refers to a flexible portion that exhibits rubber elasticity. The "hard segment" refers to a molecular restraint portion that serves as a crosslinking point of the crosslinked rubber to prevent plastic deformation. The content of the soft segment unit in the elastomer of this embodiment is preferably 15% by mass or more and 90% by mass or less, and more preferably 25% by mass or more and 85% by mass or less, of the entire elastomer of this embodiment.

[0031] From the viewpoint of further suppressing the settling of the filler and controlling the viscosity of the adhesive composition within an appropriate range, the elastomer of the present embodiment preferably contains one or more rubbers selected from the group consisting of butadiene rubber, styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, methyl(meth)acrylate-butadiene-styrene rubber, and methyl(meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber, and more preferably contains one or more rubbers selected from the group consisting of (meth)acrylonitrile-butadiene rubber, methyl(meth)acrylate-butadiene rubber, and methyl(meth)acrylate-butadiene rubber. The rubber composition preferably contains one or more selected from the group consisting of (meth)acrylonitrile-butadiene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber, and more preferably contains one or more selected from the group consisting of (meth)acrylonitrile-butadiene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber, and even more preferably contains both (meth)acrylonitrile-butadiene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber. When the (meth)acrylonitrile-butadiene rubber and the methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber are used in combination, the ratio of the combined use, in mass ratio, is preferably the former:the latter=0.5:9.5 to 9.5:0.5, more preferably the former:the latter=1:9 to 9:1, and even more preferably the former:the latter=3:7 to 7:3.

[0032] When the total amount of the resin component (A) of the present embodiment is taken as 100% by mass, the content of the elastomer of the present embodiment is, from the viewpoint of being able to further suppress sedimentation of the filler and being able to control the viscosity of the adhesive composition within an appropriate range, preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, even more preferably 10% by mass or more and 30% by mass or less, even more preferably 10% by mass or more and 20% by mass or less.

[0033] The resin component (A) of this embodiment preferably further contains a radical polymerization initiator, which can promote the reaction of carbon-carbon double bonds, thereby improving adhesive strength in a short period of time.

[0034] The radical polymerization initiator of the present embodiment preferably contains a thermal radical polymerization initiator, and from the viewpoint of improving reactivity, the thermal radical polymerization initiator of the present embodiment preferably contains an organic peroxide, more preferably contains one or more selected from the group consisting of cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate, and still more preferably contains cumene hydroperoxide.

[0035] The content of the radical polymerization initiator in this embodiment, when the total amount of resin component (A) in this example is taken as 100 parts by mass, is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, and even more preferably 1.2 parts by mass or more, from the viewpoint of improving reactivity, and may be, for example, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 8.0 parts by mass or less, and is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 8.0 parts by mass or less, even more preferably 1.0 parts by mass or more and 5.0 parts by mass or less, and even more preferably 1.2 parts by mass or more and 4.0 parts by mass or less.

[0036] The resin component (A) of this embodiment preferably further contains a reducing agent. In the adhesive composition of this embodiment, the use of a radical polymerization initiator and a reducing agent in combination can promote the generation of radicals by the polymerization initiator, thereby further promoting the reaction of carbon-carbon double bonds, thereby improving adhesive strength in a short period of time.

[0037] The reducing agent of the present embodiment preferably includes one or more types selected from the group consisting of a tertiary amine, a thiourea derivative, and a transition metal salt, more preferably includes one or two types selected from the group consisting of a tertiary amine and a transition metal salt, and more preferably includes a transition metal salt. Examples of the tertiary amine include one or more selected from the group consisting of triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of the thiourea derivative include one or more selected from the group consisting of 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, ethylenethiourea, acetyl-2-thiourea, benzoylthiourea, N,N-diphenylthiourea, N,N-diethylthiourea, N,N-dibutylthiourea, and tetramethylthiourea. Examples of the transition metal salt include one or more selected from the group consisting of cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, etc. The transition metal salt more preferably includes vanadyl acetylacetonate.

[0038] The content of the reducing agent in this embodiment, when the total amount of the resin component (A) in this embodiment is taken as 100 parts by mass, is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.12 parts by mass or more, even more preferably 0.15 parts by mass or more, and even more preferably 0.20 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 5.0 parts by mass or less, even more preferably 3.0 parts by mass or less, even more preferably 1.0 parts by mass or less, and even more preferably 0.80 parts by mass or less, and is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 8.0 parts by mass or less, even more preferably 0.10 parts by mass or more and 5.0 parts by mass or less, even more preferably 0.12 parts by mass or more and 3.0 parts by mass or less, even more preferably 0.15 parts by mass or more and 1.0 parts by mass or less, and even more preferably 0.20 parts by mass or more and 0.80 parts by mass or less.

[0039] When the total amount of the adhesive composition of this embodiment is taken as 100% by mass, the total content of the resin component (A) of this embodiment and the filler (B) of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and is preferably 100% by mass or less, more preferably 99% by mass or less, even more preferably 97% by mass or less.

[0040] The adhesive composition of the present embodiment may or may not contain other components in addition to those described above.

[0041] The adhesive composition of the present embodiment is a two-component adhesive composition that comprises a first agent and a second agent, and that is used by mixing the first agent of the present embodiment with the second agent of the present embodiment. It is preferable that the first agent of the present embodiment contains a radical polymerization initiator, and the second agent of the present embodiment contains a reducing agent.

[0042] It is preferable to adjust the amount of each component in the first and second parts so that the adhesive composition after mixing the first and second parts contains each component within the above-mentioned preferred content range.

[0043] Using a B-type viscometer, the temperature was 25°C and the shear rate was 5.5 s -1 From the viewpoint of improving workability, the viscosity of the first part of the present embodiment and the viscosity of the second part of the present embodiment measured under the above conditions are each preferably 2,000 mPa·s or more, more preferably 2,500 mPa·s or more, even more preferably 3,000 mPa·s or more, and preferably 6,500 mPa·s or less, more preferably 6,200 mPa·s or less, even more preferably 6,000 mPa·s or less, and even more preferably 5,500 mPa·s or less.

[0044] The adhesive composition of this embodiment is preferably filled between a first member and a second member at least a portion of which is inserted into the first member of this embodiment, and is capable of fixing at least a portion of the second member of this embodiment within the first member of this embodiment, and more preferably the first member of this embodiment is a golf club sleeve and the second member of this embodiment is a golf club shaft.

[0045] 2. Structure The structure of this embodiment will be described below.

[0046] The structure of this embodiment includes a first member, a second member at least partially inserted within the first member of this embodiment, and a cured body of the adhesive composition of this embodiment between the first member of this embodiment and the second member of this embodiment.

[0047] 3. Golf clubs The golf club of this embodiment will be described below.

[0048] The golf club of this embodiment includes a golf club sleeve, a golf club shaft at least a portion of which is inserted into the golf club sleeve of this embodiment, and a cured body of the adhesive composition of this embodiment between the golf club sleeve of this embodiment and the golf club shaft of this embodiment. The golf club of this embodiment has an improved grip on the golf club shaft inserted into the golf club sleeve of this embodiment.

[0049] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0050] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0051] <Preparation of Adhesive Composition> Table 1 shows the composition of resin component (A). Table 2 shows the content of filler (B) per 100 parts by mass of resin component (A). Each component was prepared according to Tables 1 and 2, and thoroughly mixed using a stirring device equipped with stirring blades to prepare a first part and a second part, respectively. In preparing the first part and the second part, each (meth)acrylate component was thoroughly and uniformly mixed at 50 to 80°C to form a mixture. Next, the other components were added to the mixture and stirred, followed by a degassing treatment to prepare the first part and the second part, respectively. The first and second parts were then mixed in a mass ratio of 1:1 to obtain an adhesive composition. The adhesive composition was evaluated for the following properties. The results are shown in Table 2.

[0052] Additional information regarding some of the information listed in Tables 1 and 2 is provided below. MBAS resin: methyl methacrylate-butadiene-acrylonitrile-styrene rubber (manufactured by Denka Co., Ltd., product name: BL-20, methyl methacrylate content 15% by mass, butadiene content 46% by mass, acrylonitrile content 3% by mass, styrene content 36% by mass, soft segment unit content 46% by mass) NBR: Acrylonitrile butadiene rubber (manufactured by ENEOS Materials Corporation, product name: N220S, acrylonitrile content 41.5% by mass, butadiene content 58.5% by mass, soft segment unit content 58.5% by mass) Methyl methacrylate (Mitsubishi Chemical Corporation, product name: Acrylic Ester M) 2-Hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, product name: Acrylate Ester HO) Dicyclopentenyloxyethyl methacrylate (manufactured by Resonac, product name: DH600) Cumene hydroperoxide (NOF Corporation, product name: PH-80) Vanadyl acetylacetonate (manufactured by Shinko Chemical Industry Co., Ltd., product name: VOAA2) Filler 1 (manufactured by Negami Chemical Industrial Co., Ltd., product name: 2100JPD, material: polyethylene) Filler 2 (manufactured by Sekisui Chemical Co., Ltd., product name: MBX-100, material: PMMA) Filler 3 (manufactured by Sekisui Chemical Co., Ltd., product name: MBX-200, material: PMMA) Filler 4 (Prime Polymer Co., Ltd., product name: SE-090T, material: PMMA) Filler 5 (manufactured by Sansho Abrasives Co., Ltd., product name: GP105P, material: glass)

[0053] <Measurement of resin component density> The (meth)acrylate components shown in Table 1 were mixed thoroughly and uniformly using a stirrer equipped with a stirring blade at 50 to 80°C to prepare a mixture. Next, the components other than the (meth)acrylate shown in Table 1 were added to the mixture, stirred using a stirrer equipped with a stirring blade, and then degassed to prepare a first resin component (first part) and a second resin component (second part), respectively. The densities of the obtained first and second resin components were measured by the Archimedes method using a Harvard-type pycnometer (inner diameter 22 mm × height 70 mm). The density of the first resin component was 1.0 g / cm 3 and the density of the second resin component is 1.0 g / cm 3 That is, the density of the resin component (A) was 1.0 g / cm 3 It was.

[0054] <Measurement of filler density> The density of the filler was measured at room temperature (23°C) in accordance with JIS K 7112 Plastics - Measurement method for density and specific gravity of non-foamed plastics (Method B, pycnometer method).

[0055] < Median diameter of filler D 50 Measurement of Filler median diameter D 50 was measured from the volumetric particle size distribution in accordance with JIS Z 8825:2022 Particle size analysis - Laser diffraction and scattering method using a particle size distribution measuring device that uses laser diffraction and scattering method.

[0056] <Prevention of filler settling> The filler settling suppression was evaluated under the following conditions. First, the first and second agents were prepared by the above-mentioned method. Next, the prepared first and second parts were left to stand in a thermostatic chamber at room temperature (23°C) for two months, and then a stirring rod was used to check whether the filler had settled to the bottom, compared with the state immediately after preparation. The evaluation results were categorized into four levels: A+, A, B, and C. The results are shown in Table 2. The evaluation criteria were as follows: A+: No difference from immediately after preparation A: Compared to immediately after preparation, there was a small amount of filler at the bottom. B: There was clearly more filler at the bottom compared to immediately after preparation. C: A large amount of filler was present at the bottom

[0057] <Grip grip on the golf head> The feeling of holding the golf head was evaluated under the following conditions. First, the first and second agents were prepared by the above-mentioned method. The prepared first and second parts were then mixed together in a mass ratio of 1:1 and applied to a shaft. The adhesive-coated shaft was inserted into a sleeve, and the grip of the golf club head was evaluated. The evaluation results were categorized into four levels: A+, A, B, and C. The results are shown in Table 2. The evaluation criteria were as follows: A+: A similar holding sensation to that achieved with glass beads was obtained. A: The holding feeling was inferior to when glass beads were used, but it was acceptable. B: The holding feeling was clearly inferior to that when glass beads were used and was unacceptable C: Not much different from when no filler was added

[0058] <Workability> The workability was evaluated under the following conditions. First, the first and second agents were prepared by the above-mentioned method. Next, the prepared first and second parts were mixed together in a mass ratio of 1:1, and the ease of application of the adhesive when applied to the shaft was evaluated. The evaluation results were categorized into four levels: A+, A, B, and C. The results are shown in Table 2. The evaluation criteria were as follows: A+: Ease of application was the same as when glass beads were used. A: Although it was less easy to apply than when glass beads were used, it was still at an acceptable level of ease of application. B: The ease of application was less than when glass beads were used and was unacceptable. C: The ease of application was clearly poor and it was not possible to apply it evenly.

[0059] <Viscosity> The first and second parts of the adhesive composition of each example were measured using a Brookfield viscometer (manufactured by Brookfield, model name: RVDV2T) at a temperature of 25°C and a shear rate of 5.5 s -1 The viscosity was measured at 100°C, and the results are shown in Table 2.

[0060] [Table 1]

[0061] [Table 2]

[0062] In the adhesive compositions of Examples, filler sedimentation was suppressed compared to the adhesive compositions of Comparative Examples. This demonstrates that the adhesive composition of the present embodiment can suppress filler sedimentation.

Claims

1. Contains a resin component (A) and a filler (B), The density ρ of the resin component (A) Ｐ [g / cm ３ ] and the density ρ of the filler (B) Ｆ [g / cm ３ ] and the difference (ρ Ｐ -ρ Ｆ ) has an absolute value of 0.80 or less.

2. 2. The adhesive composition according to claim 1, wherein the filler (B) comprises one or more resins selected from the group consisting of (meth)acrylic resins, polyethylene resins, polypropylene resins, polyvinyl resins, polystyrene resins, polyester resins, polycarbonate resins, poly(meth)acrylonitrile resins, polyamide resins, and urethane resins.

3. The adhesive composition according to claim 2 , wherein the filler (B) comprises a (meth)acrylic resin.

4. The density ρ of the resin component (A) Ｐ is 0.60 g / cm ３ 1.40g / cm or more ３ 3. The adhesive composition according to claim 1 or 2, wherein:

5. The density ρ of the filler (B) Ｆ is 0.60 g / cm ３ 2.20g / cm or more ３ 3. The adhesive composition according to claim 1 or 2, wherein:

6. The median diameter D of the filler (B) measured by a laser diffraction method ５０ The adhesive composition according to claim 1 or 2, wherein the particle size is 10 μm or more and 500 μm or less.

7. 3. The adhesive composition according to claim 1, wherein the content of the filler (B) is 1 part by mass or more and 50 parts by mass or less when the content of the resin component (A) is 100 parts by mass.

8. The adhesive composition according to claim 1 or 2, wherein the filler (B) comprises a spherical filler.

9. The adhesive composition according to claim 1 or 2, wherein the resin component (A) comprises a (meth)acrylate.

10. The adhesive composition according to claim 1 or 2, wherein the resin component (A) comprises an elastomer.

11. 11. The adhesive composition according to claim 10, wherein the elastomer comprises one or more elastomers selected from the group consisting of (meth)acrylonitrile-butadiene rubber, methyl(meth)acrylate-butadiene-styrene rubber, and methyl(meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber.

12. The adhesive composition according to claim 10 , wherein the content of the elastomer is 1% by mass or more and 50% by mass or less when the total amount of the resin component (A) is taken as 100% by mass.

13. The adhesive composition according to claim 1 or 2, wherein the resin component (A) further comprises a radical polymerization initiator.

14. The adhesive composition according to claim 1 or 2, wherein the resin component (A) further comprises a reducing agent.

15. 3. The adhesive composition according to claim 1, wherein the total content of the resin component (A) and the filler (B) is 50% by mass or more and 100% by mass or less, when the total amount of the adhesive composition is 100% by mass.

16. the adhesive composition is a two-component adhesive composition comprising a first component and a second component, and the first component and the second component are mixed together for use; the first agent contains a radical polymerization initiator, The adhesive composition according to claim 1 or 2, wherein the second agent comprises a reducing agent.

17. Using a Brookfield viscometer, the temperature was 25°C and the shear rate was 5.5 s －１ 17. The adhesive composition according to claim 16, wherein the viscosity of the first part and the viscosity of the second part measured under the conditions of (a) to (c) are each 2,000 mPa·s or more and 6,500 mPa·s or less.

18. 3. The adhesive composition according to claim 1, which is filled between a first member and a second member at least a portion of which is inserted into the first member, and which is capable of fixing at least a portion of the second member within the first member.

19. 20. The adhesive composition of claim 18, wherein the first component is a sleeve for a golf club and the second component is a shaft for a golf club.

20. A first member; a second member at least partially inserted within the first member; a cured product of the adhesive composition according to claim 1 or 2 between the first member and the second member; A structure containing:

21. a golf club sleeve; a golf club shaft at least partially inserted into the golf club sleeve; a cured product of the adhesive composition according to claim 1 or 2 between the golf club sleeve and the golf club shaft; Golf clubs including.

22. Contains a resin component (A) and a filler (B), The density ρ of the resin component (A) Ｐ [g / cm ３ ] and the density ρ of the filler (B) Ｆ [g / cm ３ ] and the difference (ρ Ｐ -ρ Ｆ ) has an absolute value of 0.80 or less.

Images