WO2012043426A1 - 分岐高分子を含有する制振材料用組成物 - Google Patents
分岐高分子を含有する制振材料用組成物 Download PDFInfo
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- WO2012043426A1 WO2012043426A1 PCT/JP2011/071785 JP2011071785W WO2012043426A1 WO 2012043426 A1 WO2012043426 A1 WO 2012043426A1 JP 2011071785 W JP2011071785 W JP 2011071785W WO 2012043426 A1 WO2012043426 A1 WO 2012043426A1
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- branched polymer
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- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NTVDGBKMGBRCKB-UHFFFAOYSA-M sodium;12-hydroxyoctadecanoate Chemical compound [Na+].CCCCCCC(O)CCCCCCCCCCC([O-])=O NTVDGBKMGBRCKB-UHFFFAOYSA-M 0.000 description 1
- VYPDUQYOLCLEGS-UHFFFAOYSA-M sodium;2-ethylhexanoate Chemical compound [Na+].CCCCC(CC)C([O-])=O VYPDUQYOLCLEGS-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
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- 229920003051 synthetic elastomer Polymers 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical group CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- 238000013519 translation Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- FRZSCIVUSFMNBX-UHFFFAOYSA-L zinc;12-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O FRZSCIVUSFMNBX-UHFFFAOYSA-L 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
Definitions
- the present invention relates to a composition for a vibration damping material containing a branched polymer.
- Damping materials are used in a wide range of fields such as acoustic equipment, electrical / electronic equipment, semiconductors, detector ships, automobiles, cameras / office equipment, industrial machinery, railways, etc. for the purpose of reducing noise and vibration.
- the damping material is designed around polymer materials, and base polymers include butyl rubber, EVA, polynorbornene, silicone gel, polyurethane, epoxy resin, various liquid materials, thermoplastic elastomers, polymer design, Materials with excellent damping characteristics have been developed by blending design (Non-Patent Document 1). These damping materials are polymer materials, and a loss tangent tan ⁇ obtained from dynamic viscoelasticity measurement is used as a simple index of damping performance (damping performance).
- the dynamic viscoelastic behavior of the material can be used to dissipate the given mechanical energy as energy such as heat and attenuate the energy. That is, the damping material here is defined as a material that can dissipate the given energy, and the energy is not limited to vibration and sound, and can be applied to any energy.
- the vibration damping material has a relatively high frequency range of about 100 Hz to several thousand Hz.
- it can be an excellent material exhibiting good damping (damping) properties, but provides sufficient damping characteristics at a very low frequency range of several Hz to several tens of Hz at room temperature around 20 ° C. It was difficult.
- Patent Document 1 a rubber damping material containing a polyolefin-based hot melt resin having a softening point in the vicinity of 100 to 200 ° C.
- the hot melt resin is a non-reactive and high molecular weight linear polymer, which is previously melted to crosslink and cure the rubber component to obtain a vibration damping material.
- heating and a large amount of solvent are required to bring the high molecular weight linear polymer into a molten state, which is uneconomical for manufacturing on an industrial scale because of the problem of cost during material molding.
- Patent Document 1 since a solvent or the like is used, there is a possibility of phase separation, and there is a problem in long-term stability such as bleed out (Patent Document 1).
- Patent Document 2 a proposal has been made to use a cured product obtained by combining an ultra-high molecular weight (meth) acrylic acid ester polymer and a monomer having a crosslinkable functional group as a vibration damping material (Patent Document 2).
- an ultrahigh molecular weight (number average) of 200,000 or more is preferable in order to provide sufficient damping characteristics in a very low frequency region number of several Hz to several tens Hz at around room temperature 20 ° C.
- a (meth) acrylic acid ester polymer having a molecular weight of 100,000 or more has a very high viscosity or is a solid.
- Patent Document 2 a problem remains that it is essential to dissolve in a toluene solvent or the like from the viewpoint of workability
- Patent Document 2 a material in which a non-reactive linear polymer having a relatively low molecular weight (about tens of thousands) is confined in a crosslinked rubber network is considered to be the same. It is considered that a material having a high loss tangent tan ⁇ (dynamic viscoelasticity measurement) can be obtained at a temperature higher than the glass transition temperature of the rubber itself.
- these technologies utilize the fact that non-reactive linear polymers diffuse at low speed in the cross-linked network, so that a large amount of non-reactive linear polymers with uniform molecular weight are confined in the cross-linked rubber network.
- a loss tangent tan ⁇ (dynamic viscoelasticity measurement) has a peak, and a vibration damping material capable of arbitrarily controlling the vibration damping performance can be obtained.
- the diffusion rate of the low molecular weight linear polymer is generally faster than that of the high molecular weight (approximately several hundred thousand) linear polymer, it has a relatively high frequency range of about 100 Hz to about several thousand Hz.
- it can be an excellent material exhibiting good damping (damping) properties against vibration sufficient vibration damping characteristics are imparted at a very low frequency range of several Hz around room temperature 20 ° C. It is difficult. From the above, it is considered that there is a limit to the material that confines the non-reactive linear polymer in the crosslinked rubber network when designing the damping material.
- a curable composition for vibration damping materials containing a polymer having one crosslinkable functional group and a polymer having two or more crosslinkable functional groups has been proposed.
- a vibration damping material that is liquid before curing, has a low viscosity and good workability, and has high energy dissipation in a wide temperature range after the curing Patent Document 3
- the amount of the polymer having one crosslinkable functional group is increased, the energy dissipation tends not to increase, but the amount of the polymer charged is limited.
- the content is high, it is apparent that handling becomes difficult, such as extremely low elastic modulus and poor tackiness. Therefore, in reality, the above materials have not yet been satisfactory in terms of characteristics, work, and cost.
- the present invention aims to solve the aforementioned problems.
- vibration suppression is performed for vibrations in a specific temperature range near room temperature ( ⁇ 20 ° C. to 20 ° C.) and over a low frequency range (several Hz).
- An object is to provide a vibration damping material with improved (energy attenuation) properties.
- the vibration control performance can be arbitrarily controlled aiming at a specific frequency region and a specific temperature region which are very low as well as low temperature and high frequency regions, and the degree of freedom in material design.
- the physical properties such as elastic modulus (hardness) can be improved at the same time.
- the present invention contains the branched polymer (A) and the resin (B), and the content of the branched polymer (A) is 100% by weight based on the total amount of the branched polymer (A) and the resin (B). And 15% by weight or more and 85% by weight or less.
- the branched polymer (A) is preferably a (meth) acrylic polymer.
- the branched polymer (A) is preferably a comb polymer or a statistical polymer having irregular branches.
- the weight average molecular weight (Mw) measured in polystyrene conversion by gel permeation chromatography (GPC) of the branched polymer (A) is 10,000 or more.
- Resin (B) is preferably a (meth) acrylic polymer.
- the resin (B) has a crosslinkable functional group.
- the branched polymer (A) is preferably a comb polymer or a statistical polymer having irregular branches.
- the branched polymer (A) is preferably a (meth) acrylic polymer.
- the weight average molecular weight (Mw) measured in polystyrene conversion by gel permeation chromatography (GPC) of the branched polymer (A) is 10,000 or more.
- the vibration damping material of the present invention has high vibration damping (energy attenuation) property against vibrations in a specific temperature range near room temperature ( ⁇ 20 ° C. to 20 ° C.) and a low frequency range (several Hz) or more.
- a composition for a damping material that has a high degree of freedom in material design and can simultaneously improve physical properties such as elastic modulus (hardness).
- the composition for damping material of the present invention contains the branched polymer (A) and the resin (B), and the content of the branched polymer (A) is the total amount of the branched polymer (A) and the resin (B).
- the present invention relates to a composition for damping material, which is 15% by weight or more and 85% by weight or less with respect to 100% by weight. This will be described in detail below.
- the branched polymer (A) in the present invention refers to a polymer having a non-linear polymer form.
- the monomer unit constituting the main chain of the branched polymer (A) according to the present invention is not particularly limited, and an organic polymer polymer or an inorganic polymer polymer can be used.
- Organic polymer used in the present invention examples include a synthetic polymer, a semi-synthetic polymer, and a natural polymer, and are prepared by various polymerization techniques.
- Examples of the synthetic polymer include polystyrene, poly (meth) acryl, polyester, polyamide, polyether, polyurethane, polyvinyl chloride, tetrafluoroethylene, urea resin, phenol resin, and polyolefin.
- N-vinyl lactam (7) vinyl halides such as vinyl chloride and vinylidene chloride, vinylidene halide compounds (8) aryl vinyl and aryl vinylidene compounds such as styrene and vinyl naphthalene, (9) vinyl nitrile and cyano vinylidene compounds such as acrylonitrile, (10) nitrogen heterocyclic compounds such as vinyl pyrrolidone and vinyl pyridine, (11) butadiene , Ethylenically unsaturated compounds such as chloroprene, isoprene, isobutylene, propylene and butylene can be used alone or in combination. A crosslinking agent can also be used.
- semi-synthetic polymers include cellulose polymers such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch polymers such as carboxymethyl starch, and alginic acid polymers such as propylene glycol alginate.
- examples include molecules, chitin, chitosan and the like.
- natural polymer examples include plant polymers such as agar and gum arabic, animal polymers such as gelatin and collagen, natural polysaccharides, polyamino acids and the like.
- a preferable organic polymer is a (meth) acrylic polymer.
- examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid-n- Butyl, (butyl) (meth) acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, to
- the (meth) acrylic polymer main chain is preferably produced mainly by polymerizing at least one monomer selected from the above (meth) acrylic monomers.
- “mainly” means that 50 mol% or more of the monomer units constituting the (meth) acrylic polymer (A) is the above monomer, and preferably 70 mol% or more.
- aromatic (meth) acrylic monomers and (meth) acrylic monomers are preferred in view of the physical properties of the product. More preferred are acrylic ester monomers and / or methacrylic ester monomers, and particularly preferred are acrylic ester monomers. Particularly preferable acrylic ester monomers are ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxybutyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.
- butyl acrylate monomers are more preferred from the viewpoint that physical properties such as low viscosity of the curable composition, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required.
- copolymers based on ethyl acrylate are more preferred.
- This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it.
- the ratio of butyl acrylate is increased, the good oil resistance is impaired, so that the ratio is preferably low for applications requiring oil resistance. It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve the low temperature characteristics without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio is preferably low when heat resistance is required. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics.
- examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40 to 50% / 20-30% / 30-20%).
- a method for synthesizing the (meth) acrylic polymer will be described in detail later.
- the molecular weight distribution of the branched polymer (A) according to the present invention that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is There is no particular limitation.
- the molecular weight of the branched polymer (A) in the present invention is preferably 10,000 or more in terms of weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography (GPC).
- the weight average molecular weight (Mw) is preferably in the range of 10,000 to 1,000,000, more preferably 15,000 to 500,000. If these are the said range, they may be individual and may use 2 or more types together.
- vibrations in a low frequency region severeal Hz or more
- the weight average molecular weight (Mw) of the branched polymer (A) is only less than 10,000, the vibration damping performance of the obtained cured product is lowered. That is, if the weight average molecular weight is too low, the viscosity becomes low and the handling becomes easy, but the damping property tends to deteriorate with respect to the vibration in the low frequency region near the room temperature of the obtained cured product. On the other hand, even if it becomes too high, the branched polymer (A) tends to have a lower viscosity than the linear polymer having the same weight average molecular weight (Mw), and is therefore relatively easy to handle. .
- the weight average molecular weight (Mw) of the precursor of the branched polymer (A) in the present invention is not particularly limited, but is 500 to 1,000,000 in terms of polystyrene when measured by GPC.
- the range is preferably 5000 to 500,000, more preferably 10,000 to 100,000.
- the precursor of the branched polymer (A) becomes a branched chain of the obtained branched polymer (A) and has a great influence on the vibration damping properties.
- the vibration damping property is low, and when this Mw is large, the vibration damping property tends to be greatly improved.
- Mw weight average molecular weight
- the damping performance can be arbitrarily controlled aiming at a specific frequency region and a specific temperature region that are very low as well as low temperature and high frequency region. .
- the branched polymer (A) is relatively easy to handle because it tends to have a lower viscosity than a linear polymer having the same weight average molecular weight (Mw).
- the method for synthesizing the branched polymer (A) in the present invention is not particularly limited, and the branched polymer (A) may be synthesized first and added thereto to obtain a composition for damping material. Further, in the composition containing the precursor of the branched polymer (A), the composition for vibration damping material containing the branched polymer (A) as a result can be synthesized by later synthesis. Good.
- a polymer having a specific functional group can be used as a macromonomer, and a method for obtaining a branched polymer by chain reaction of this macromonomer (precursor of a branched polymer) It is more convenient.
- a macromonomer having a functional group introduced into the polymer terminal with a very high probability is used, a branched polymer can be easily synthesized.
- the branched polymer after polymerizing the macromonomer may or may not have a reactive end.
- a method of synthesizing this macromonomer (branched polymer precursor) there is a method using controlled radical polymerization. Controlled radical polymerization is not limited, but living radical polymerization is preferred, and atom transfer radical polymerization is more preferred. These will be described below.
- the radical polymerization method is a “general radical polymerization method” in which a monomer having a specific functional group and a (meth) acrylic monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator. Can be classified into “controlled radical polymerization methods” in which a specific functional group can be introduced at a controlled position such as a terminal.
- the “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.
- the “controlled radical polymerization method” is a “chain transfer agent method” in which a (meth) acrylic polymer having a functional group at the terminal is obtained by performing polymerization using a chain transfer agent having a specific functional group. It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the polymerization growth terminal without causing a termination reaction or the like.
- chain transfer agent method a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.
- the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
- the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer.
- a manufacturing method of the (meth) acrylic-type polymer which has the said specific functional group it is a more preferable thing.
- a (meth) acrylic polymer having a specific functional group can be used as a macromonomer.
- living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium.
- the definition in the present invention is also the latter.
- “Living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical scavenger such as a nitroxide compound, and “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).
- ARP Atom Transfer Radical Polymerization
- the “atom transfer radical polymerization method” for polymerizing a (meth) acrylic monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”.
- the “radical polymerization method” it has halogens that are relatively advantageous for functional group conversion reactions at the end, and has a high degree of freedom in designing initiators and catalysts, so it has specific functional groups (meta) It is further preferred as a method for producing an acrylic polymer.
- this atom transfer radical polymerization method for example, Matyjazewski et al., Journal of American Chemical Society (J. Am.
- Atom transfer radical polymerization also includes so-called reverse atom transfer radical polymerization.
- Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, a peroxide relative to Cu (II) when Cu (I) is used as a catalyst. And the like, and as a result, an equilibrium state similar to atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).
- Percec et al. Proposed the Single-Electron-Transfer (SET) method, and disclosed in, for example, WO 2008/019100.
- SET Single-Electron-Transfer
- Atom transfer radical polymerization which is one of the preferred methods for synthesizing a macromonomer that is a precursor of a branched polymer in the present invention, will be briefly described below.
- an organic halide particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the ⁇ -position or a compound having a halogen at the benzyl-position), or a sulfonyl halide.
- a compound or the like is preferably used as an initiator.
- an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. It is preferable to use it.
- transition metal complex used as a polymerization catalyst is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0.
- the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like.
- the polymerization reaction can be carried out without solvent, but can also be carried out in various solvents.
- the type of the solvent is not particularly limited, and examples thereof include a solvent described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more.
- Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO 2 as a medium.
- the polymerization temperature is not limited, but can be carried out in the range of 0 to 200 ° C, and preferably in the range of room temperature to 150 ° C.
- the (meth) acrylic polymer synthesized by living radical polymerization can have a crosslinkable functional group at one end, and unlike the conventional case, the functional group is introduced with high probability. As described above, this is a macromonomer.
- the average number of crosslinkable functional groups of the (meth) acrylic polymer per molecule is preferably 0.7 or more, more preferably 0.8 or more in terms of reactivity, and further 0.9 or more. preferable.
- a crosslinkable functional group can be introduced at one end with a high probability, so that a branched polymer (A) can be obtained by post-reacting this macromonomer. Is possible.
- These synthesis methods can be obtained by various polymerization methods and are not particularly limited.
- a reaction catalyst or a curing agent is required.
- Various additives may be used in combination according to the synthesis of the branched polymer (A).
- a macromonomer having at least 1.7 crosslinkable functional groups at the molecular terminals can be used in combination.
- the average is preferably 1.8 or more and 4.0 or less, more preferably 1.9 or more and 3.5 or less per molecule. If the above-mentioned living radical polymerization is used, a crosslinkable functional group can be introduced at both ends with a high probability, so that it can be used as a good crosslinker and / or chain extender.
- the average number of crosslinkable functional groups per molecule refers to the concentration of the crosslinkable functional groups per unit weight obtained from 1 H-NMR measurement value, the molecular weight, copolymerization ratio and GPC measurement. It is a value calculated by dividing by the number of molecules per unit weight obtained from the molecular weight of each copolymerized monomer.
- crosslinkable functional group When synthesizing the branched polymer of the present invention, at least one of the crosslinkable functional groups is preferably at the end of the molecular chain in order to increase the degree of polymerization of the macromonomer that greatly affects the vibration damping properties. More preferably, it has all crosslinkable functional groups at the molecular chain ends.
- a method for producing a (meth) acrylic polymer having at least one crosslinkable functional group at its molecular end is disclosed in JP-B-3-14068, JP-B-4-55444, JP-A-6-211922, and the like. Is disclosed. However, since these methods are free radical polymerization methods using the “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable functional groups at the end of the molecular chain, while Mw / The value of the molecular weight distribution represented by Mn is generally as large as 2 or more, and there is a problem that the viscosity becomes high.
- the above “living radical polymerization method” is used. It is preferable to use it.
- the crosslinkable functional group possessed by the (meth) acrylic polymer is not particularly limited, but includes a crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon double bond or epoxy group. Can be mentioned. Some of these curing catalysts and curing agents are required. Various additives may be added according to the intended physical properties.
- the crosslinkable silyl group of the present invention includes a general formula (1); -[Si (R 1 ) 2-b (Y) b O] m -Si (R 2 ) 3-a (Y) a (1) ⁇ Wherein R 1 and R 2 are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) 3 SiO— (R 'Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and each represents a triorganosiloxy group represented by R 1 or When two or more R 2 are present, they may be the same or different.
- Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different.
- a represents 0, 1, 2, or 3
- b represents 0, 1, or 2.
- m is an integer from 0 to 19. However, it shall be satisfied that a + mb ⁇ 1. ⁇
- hydrolyzable group examples include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
- an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.
- alkoxy groups those having fewer carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.
- Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + ⁇ b) is preferably in the range of 1 to 5.
- two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different.
- the number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.
- a is preferably 2 or more because the curability and the physical properties of the cured product are good.
- a (meth) acrylic polymer (A) having a crosslinkable silyl group a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom may be used.
- a very fast curing rate such as when used at low temperatures, the curing rate is not sufficient, and if it is desired to provide flexibility after curing, it is necessary to reduce the crosslinking density. For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur.
- a is 3 (for example, trimethoxy functional group).
- those having a of 3 cure faster than those having 2 (for example, dimethoxy functional group), but those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.).
- two for example, dimethoxy functional group
- three for example, trimethoxy functional group
- a compound having a of 1 is used as a chain extender mixed with a polymer having a crosslinkable silyl group, specifically, at least one polymer comprising a polysiloxane, polyoxypropylene or polyisobutylene. it can. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding property, and low surface contamination.
- alkenyl group Although the alkenyl group in this invention is not limited, It is preferable that it is what is represented by General formula (3). H 2 C ⁇ C (R 11 ) ⁇ (3) (Wherein R 11 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) In the general formula (3), R 11 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the following groups.
- alkenyl group of the (meth) acrylic polymer (A) and / or the (meth) acrylic polymer (B) is not limited, but a carbonyl group or alkenyl group conjugated with the carbon-carbon double bond. It is preferably not activated by an aromatic ring.
- the bonding mode between the alkenyl group and the main chain of the polymer is not particularly limited, but is preferably bonded via a carbon-carbon bond, an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like.
- amino group in the present invention is not limited, -NR 12 2 (R 12 is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R 12 may be the same or different from each other, and are connected to each other at the other end to form a cyclic structure. You may do it.) Can be mentioned, - (NR 12 3) + X - (R 12 is the same as above. X ⁇ is a counter anion.) There is no problem even if it is the ammonium salt shown.
- R 12 is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, such as hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. And an aralkyl group.
- Two R 12 may be the same as or different from each other. Further, they may be connected to each other at the other end to form an annular structure.
- the group having a polymerizable carbon-carbon double bond is preferably represented by the general formula (4); —OC (O) C (R 13 ) ⁇ CH 2 (4) (In the formula, R 13 represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.) And more preferably a group in which R 13 is hydrogen or a methyl group.
- R 13 is not particularly limited.
- —H, —CH 3 , —CH 2 CH 3 , — (CH 2 ) n CH 3 (n is an integer of 2 to 19) Represents —C 6 H 5 , —CH 2 OH, —CN, etc., with —H and —CH 3 being preferred.
- the epoxy group is preferably a glycidyl group, a glycidyl ether group, a 3,4-epoxycyclohexyl group, or an oxetane group.
- a glycidyl group, a glycidyl ether group, or a 3,4-epoxycyclohexyl group is preferable. More preferred.
- a branched polymer (A) can be obtained by post-reacting a macromonomer having a crosslinkable functional group introduced at one end with high probability using controlled radical polymerization, and easily with high probability. High molecular weight is possible.
- Any polymerization method may be used for the post-reaction polymerization.
- uncontrolled polymerization may be performed, or post-polymerization may be performed by controlled radical polymerization to obtain the branched polymer (A).
- combination of the branched polymer (A) of this invention there exist some which require a reaction catalyst and a hardening
- Various additives may be added according to the intended physical properties.
- condensation catalyst examples include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diester.
- Isooctylmalate dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, etc.
- Tetravalent tin compounds such as tin octylate, tin naphthenate and tin stearate; monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide And monoalkyltin compounds such as monooctyltin compounds; titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate Bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, Carboxylic acid such as cobalt carboxylate,
- Silanol condensation such as silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc., which are derivatives of these modified
- the catalyst include known silanol condensation catalysts such as other acidic catalysts and basic catalysts.
- the amount of the condensation catalyst is preferably about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on a total of 100 parts by weight of the (meth) acrylic polymer having a crosslinkable silyl group. If the amount of the silanol condensation catalyst is less than this range, the reaction rate may be slow, and the reaction may not proceed sufficiently. Although not particularly limited, it is preferable to use a tin-based curing catalyst in order to control the reactivity.
- the silane coupling agent having an amino group as described above should be used as a co-catalyst in the same manner as the amine compound.
- This amino group-containing silane coupling agent is a compound having a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable silicon group) and an amino group, and the groups already exemplified as this hydrolyzable group.
- a methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate.
- the number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.
- the compounding amount of these amine compounds is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer having a crosslinkable silyl group. . If the compounding amount of the amine compound is less than 0.01 parts by weight, the reaction rate may be slow, and the reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 50 parts by weight, it is not preferable from the viewpoint of the environment such as deterioration of hue and strong odor.
- amine compounds may be used alone or in combination of two or more.
- R 49 a Si (OR 50 ) 4-a (5) (In the formula, R 49 and R 50 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Furthermore, a is 0, 1, 2, or 3.) A silicon compound having no amino group or silanol group represented by the above may be added as a promoter.
- Examples of the silicon compound include, but are not limited to, R 49 in the general formula (5) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane.
- R 49 in the general formula (5) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane.
- R 49 in the general formula (5) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxys
- the compounding amount of the silicon compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer having a crosslinkable silyl group.
- the compounding amount of the silicon compound is below this range, the effect of accelerating the reaction may be reduced.
- the hydrosilyl group-containing compound is not particularly limited as long as it is a hydrosilyl group-containing compound that can be branched with a (meth) acrylic polymer having an alkenyl group, and various compounds can be used.
- R 51 and R 52 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group
- R 53 represents an alkyl group having 1 to 10 carbon
- siloxanes from the viewpoint of compatibility with the (meth) acrylic polymer (A) and the (meth) acrylic polymer (B), they are represented by the following general formulas (8) and (9) having a phenyl group. Preferred are chain siloxanes and cyclic siloxanes.
- C 6 H 5 represents a phenyl group.
- the hydrosilyl group-containing compound represented by the general formulas (6) to (9) may be partially converted after the reaction with respect to the low molecular compound having two or more alkenyl groups in the molecule.
- a compound obtained by addition reaction such that a hydrosilyl group remains can also be used.
- Various compounds can be used as the compound having two or more alkenyl groups in the molecule.
- hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A and 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.
- the compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (6) to (9). it can.
- the (meth) acrylic polymer having an alkenyl group and the branching agent can be mixed in an arbitrary ratio.
- the reaction between the (meth) acrylic polymer having an alkenyl group and the branching agent proceeds by mixing and heating these components, but a hydrosilylation catalyst should be added to advance the reaction more rapidly. Can do.
- a hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.
- the radical initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as ⁇ , ⁇ '-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peroxyesters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Such as peroxydicarbon
- the transition metal catalyst is not particularly limited, and for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes.
- platinum compounds RhCl (PPh 3) 3, RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 ⁇ H 2 O, NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more.
- the amount of catalyst, relative to the alkenyl group 1mol precursors branched polymer (A), may employed in the range of 10 -1 to 10 -8 mol, preferably 10 -3 to 10 - It is good to use in the range of 6 mol. If it is less than 10 ⁇ 8 mol, curing does not proceed sufficiently. Further, since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ⁇ 1 mol or more.
- a reaction modifier may be blended in order to balance storage stability and reactivity.
- blended the compound containing an aliphatic unsaturated bond is mentioned.
- acetylene alcohols are exemplified, and examples of acetylene alcohol having a balance between storage stability and curability include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3- And methyl-1-pentyn-3-ol.
- compounds containing aliphatic unsaturated bonds that improve storage stability at high temperatures include ene-in compounds, silane compounds, polysiloxane compounds, olefinic compounds, and fats of olefinic alcohols such as vinyl acetate.
- examples thereof include carboxylic acid esters, tetravinylsiloxane cyclics, nitriles containing an aliphatic unsaturated bond such as 2-pentenenitrile, alkyl acetylenedicarboxylates, maleic acid esters, diorgano fumarate and the like.
- the reactivity modifier may be used alone or in combination of two or more.
- the reaction temperature is not particularly limited, but is generally cured at 0 ° C to 200 ° C, preferably 30 ° C to 150 ° C, more preferably 80 ° C to 150 ° C.
- (meth) acrylic polymer having a hydroxyl group when using the (meth) acrylic-type polymer which has a hydroxyl group, it hardens
- the branching agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and an alkyl etherified product or a low condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof.
- an appropriate reaction catalyst can be used.
- the (meth) acrylic polymer having an amino group according to the present invention reacts uniformly by using a compound having two or more functional groups capable of reacting with an amino group as a branching agent.
- the branching agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and an alkyl etherified product or a low condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof.
- an appropriate reaction catalyst can be used.
- the branching agent for the (meth) acrylic polymer having an epoxy group is not particularly limited, but examples thereof include aliphatic amines, alicyclic amines, aromatic amines; acid anhydrides; polyamides; Amine imides; urea; melamine and its derivatives; polyamine salts; phenolic resins; polymercaptans, polysulfides; aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, etc. Used.
- the (meth) acrylic polymer having a polymerizable carbon-carbon double bond can be crosslinked by a polymerization reaction of the polymerizable carbon-carbon double bond.
- the crosslinking method examples include a method of curing with active energy rays and a method of curing with heat.
- active energy ray curable type it is preferable to use a photoradical initiator or a photoanion initiator as a photopolymerization initiator.
- thermosetting type it is preferable to use a thermal polymerization initiator selected from the group consisting of azo initiators, peroxides, persulfates, and redox initiators.
- the initiators used may be used singly or as a mixture of two or more, but when used as a mixture, the amount of each initiator used is within the respective ranges described below. It is preferable that it exists in.
- a polymerizable monomer and / or oligomer or various additives may be used in combination depending on the purpose.
- a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable.
- radical polymerizable groups examples include acrylic functional groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, vinyl chloride groups, etc. Is mentioned. Especially, what has a (meth) acryl group is preferable.
- the anionic polymerizable group examples include (meth) acryl group, styrene group, acrylonitrile group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group and the like. Among these, those having an acrylic functional group are preferable.
- the above monomers include (meth) acrylate monomers, cyclic acrylates, N-vinyl pyrrolidone, styrene monomers, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and the like. It is done.
- the (meth) acrylate monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and isononyl (meth) acrylate.
- Styrene monomers include styrene and ⁇ -methylstyrene
- acrylamide monomers include acrylamide, N, N-dimethylacrylamide
- conjugated diene monomers include butadiene and isoprene
- vinyl ketone monomers include methyl vinyl ketone. Etc.
- polyfunctional monomers examples include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxy) Ethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetra Bromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1, - nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.
- epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin, polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ⁇ -caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diiso A urethane resin obtained from anate, xylylene diisocyanate, etc.) is reacted with a hydroxyl group-containing (me
- the number average molecular weight of the monomer and / or oligomer having an acrylic functional group is not particularly limited.
- the branched polymer (A) in the curable composition for vibration damping material of the present invention can also be synthesized by active energy rays such as UV and electron beams.
- active energy rays include ultraviolet rays, visible rays, LED rays, electron beams, and radiation.
- ultraviolet rays are preferable from the viewpoints of versatility of the output device, ease of handling, and physical properties of the obtained cured product.
- the photopolymerization initiator used in the present invention is not particularly limited, but a photo radical initiator and a photo anion initiator are preferable, and a photo radical initiator is particularly preferable.
- a compound having a hydroxyl group and a phenyl ketone structure, a compound having a benzophenone structure, and a compound having an acylphosphine oxide structure are preferable.
- 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 , 4-Trimethyl pliers Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are
- initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue are included. It is done.
- amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine
- iodonium salts such as diphenyliodonium chloride
- dyes and amines such as methylene blue
- polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.
- a near infrared light absorbing cationic dye may be used as a near infrared light polymerization initiator.
- Near-infrared light-absorbing cationic dyes are excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light absorption disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use a cationic cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer in combination.
- the addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but it is based on 100 parts by weight of the (meth) acrylic polymer having a polymerizable carbon-carbon double bond. 0.001 to 10 parts by weight is preferable.
- the method for synthesizing the branched polymer (A) of the present invention is not particularly limited, but depending on the properties of the photopolymerization initiator initiator, the high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor Light and electron beam irradiation with a laser or the like can be mentioned.
- Heat-crosslinking system When the branched polymer (A) of the present invention is synthesized by heating, it is preferable to contain a thermal polymerization initiator.
- the thermal polymerization initiator used in the present invention is not particularly limited, and includes azo initiators, peroxides, persulfates, and redox initiators.
- Suitable azo initiators include, but are not limited to, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2′-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2′-azobis (isobutyronitrile) (VAZO 64), 2, 2′-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2′-azobis (2- Cyclopropylpropionitrile), 2,2′-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries), etc. Is mentioned.
- Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Examples include oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.
- Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.
- Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.
- initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.
- Preferred thermal radical initiators are selected from the group consisting of azo initiators and peroxide initiators. Further preferred are 2,2′-azobis (methylisobutylate), t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.
- the thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is typically, but not limited to, a polymerizable carbon-carbon dioxide at at least one end of the present invention.
- a catalytically effective amount typically, but not limited to, a polymerizable carbon-carbon dioxide at at least one end of the present invention.
- the total amount of the (meth) acrylic polymer having a group having a heavy bond and other monomer and oligomer mixture added is 100 parts by weight, it is about 0.01 to 5 parts by weight, more preferably about 0. 0.025 to 2 parts by weight. If a mixture of initiators is used, the total amount of initiator mixture is as if only one initiator was used.
- the method for synthesizing the branched polymer of the present invention is not particularly limited, but the temperature varies depending on the kind of the thermal initiator, (meth) acrylic polymer, compound to be added, etc. It is preferably in the range of 250 ° C, more preferably in the range of 70 ° C to 200 ° C.
- the curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc., but is usually in the range of 1 minute to 10 hours.
- the vibration damping material of the present invention contains a resin (B).
- Resin (B) may be in a resin state, a rubber state, or a gel state.
- the resin state, rubber state, or gel state defined in the present invention refers to a state in which the shape can be maintained for 24 hours at room temperature in an environment where gravity is exerted. Any shape and substance may be used as long as the damping material can maintain such a shape.
- thermoplastic resin As a component constituting the resin state, a thermoplastic resin, a lyotropic liquid crystal resin, a liquid resin, a thermosetting resin, a crosslinked rubber, or the like may be used as long as the performance of the vibration damping material of the present invention is not impaired.
- thermoplastic resin polyolefin resin, aromatic vinyl compound resin, polyvinyl chloride resin, polyacrylic resin, polyether resin, polyamide resin, polyester resin, polycarbonate resin, Polyacetal resin, polyphenylene ether resin, polymethylpentene, ultra high molecular weight polyethylene, polysulfone resin, polysulfide resin, polyimide resin, polyamideimide resin, polyetherimide resin, fluorine resin, thermoplastic polyurethane resin And polyethersulfone resin, polyether ketone resin, thermotropic liquid crystal resin, and lyotropic liquid crystal resin.
- thermoplastic resin polyolefin resin, aromatic vinyl compound resin, polyvinyl chloride resin, polyacrylic resin, polyether resin, polyamide resin, polyester resin, polycarbonate resin, Polyacetal resin, polyphenylene ether resin, polymethylpentene, ultra high molecular weight polyethylene, polysulfone resin, polysulfide resin, polyimide resin, polyamideimide resin, polyetherimide resin, fluorine
- liquid resins examples include silicone resins, modified silicone (MS) resins, polyisobutylene (PIB) resins, polysulfide resins, modified polysulfide resins, polyurethane resins, polyacrylic resins, and polyacrylurethane resins. can give.
- thermosetting resins examples include unsaturated polyester resins, epoxy resins, hydrosilylated crosslinking resins, phenol resins, alkyd resins, diallyl phthalate resins, urea resins, polyurethane resins, melamine resins, and the like. It is done.
- Cross-linked rubbers include natural rubber, polybutadiene rubber (PBD), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, chlorinated butyl rubber, chloroprene rubber, and acrylic. Examples thereof include rubber, urethane rubber, isoprene rubber, ethylene-propylene rubber, fluorine rubber, and silicone rubber.
- PBD polybutadiene rubber
- SBR styrene-butadiene rubber
- hydrogenated styrene-butadiene rubber acrylonitrile-butadiene rubber
- butyl rubber chlorinated butyl rubber
- chloroprene rubber chloroprene rubber
- acrylic acrylic. Examples thereof include rubber, urethane rubber, isoprene rubber, ethylene-propylene rubber, fluorine rubber, and silicone rubber.
- Resin (B) is preferably a (meth) acrylic polymer.
- a chemically crosslinked body and / or a physical crosslinked body may be used as a component constituting the rubber and gel state.
- a chemically crosslinked body is a rubber or gel chemically crosslinked by a covalent bond.
- Such a resin (B) is preferably a polymer having a crosslinkable functional group.
- a physical cross-linked body is a cross-linked body that has a bond energy as weak as thermal energy and in which cross-linking points are generated and disappeared in the course of molecular motion.
- This bond may be a bond between polymer and polymer, between polymer and small molecule, or between small molecule and small molecule.
- the physical crosslinked body includes pseudo-crosslinking that occurs when the polymer chain is temporarily entangled.
- gum and a gel state even if it contains liquid substances, such as a solvent and a plasticizer, it does not need to contain, You may use what is called a low molecular gelling agent.
- the low molecular weight gelling agent examples include isophorone diisocyanate-2-ethylhexylamine adduct, 1,2,3,4-dibenzylidene-D-sorbitol, 12-hydroxystearic acid, N-lauroyl-L-glutamic acid. - ⁇ , ⁇ -bis-n-butyramide, spin-labeled steroid, cholesterol derivative, aluminum dialkyl phosphate, fatty acid aluminum, phenolic cyclic oligomer, 2,3-bis-n-hexadecyloxyanthracene, cyclic depsipeptide, etc. These 1 type may be used independently and may use 2 or more types together.
- the rubber and gel state in the present invention is not limited to the above examples, and may be a state in which the shape can be maintained for 24 hours at room temperature.
- composition for vibration damping materials in the present invention contains a branched polymer (A) and a resin (B).
- the amount of the branched polymer (A) is from 15% by weight to 85% by weight with respect to 100% by weight of the total amount of the branched polymer (A) and the resin (B), but from 20% by weight to 80% by weight. It is preferably 50 wt% or more and 80 wt% or less. If it is less than 15% by weight, it is not preferable because sufficient effects as a damping characteristic and a rheology adjusting agent cannot be obtained.
- composition for damping material in the present invention various additives other than the branched polymer (A) and the resin (B) may be added.
- a silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the composition for vibration damping material of the present invention.
- the adhesion-imparting agent When the adhesion-imparting agent is added, the joint width or the like varies due to an external force, thereby further reducing the risk of the sealing material peeling from the adherend such as a siding board. Further, in some cases, it is not necessary to use a primer used for improving adhesion, and simplification of construction work is expected.
- Specific examples of the silane coupling agent include amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogen and other silane coupling agents.
- Examples include ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, and other isocyanate group-containing silanes; Silane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ - (2-aminoethyl) amino Propyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, ⁇ - (2-aminoethyl)
- amino-modified silyl polymers silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used.
- the silane coupling agent used in the present invention is used in the range of 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the branched polymer (A) and the resin (B). In particular, it is preferably used in the range of 0.5 to 10 parts by weight.
- the effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.
- silane coupling agent examples include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.
- the adhesiveness-imparting agent may be used alone or in combination of two or more. These adhesiveness-imparting agents can improve the adhesion to the adherend when added. Although not particularly limited, 0.1 to 20 parts by weight of a silane coupling agent is used in combination with the above-mentioned adhesion-imparting agent in order to improve adhesion, particularly adhesion to a metal-coated surface such as an oil pan. Is preferred.
- Plasticizers may be used in the composition for damping material of the present invention as necessary.
- a plasticizer is used in combination with a filler described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed. However, it does not necessarily have to be added.
- the plasticizer is not particularly limited, but for purposes such as physical property adjustment and property adjustment, for example, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; Non-aromatic dibasic esters such as adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate, methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, Polyalkylene glycol esters such as pentaerythritol ester; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; polystyrene and poly- ⁇ -methylstyrene Polybutadiene, polybutene, polyisobutylene, but
- the polymer plasticizer which is a polymer having a number average molecular weight of 500 to 100,000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition, Mechanical properties such as elongation can be adjusted, and the initial physical properties can be maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule.
- the drying property (also called paintability) when a paint is applied can be improved. Furthermore, it can be an excellent material exhibiting a good damping (damping) property against vibrations in a relatively high frequency range of about 100 Hz to several 1000 Hz at room temperature.
- the polymer plasticizer may or may not have a functional group.
- the number average molecular weight of the polymer plasticizer is described as 500 to 100,000, but is preferably 800 to 10,000, more preferably 1000 to 60,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, and the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability may not be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability
- acrylic polymers are preferred.
- (meth) acrylic polymers are preferred from the viewpoints of compatibility, weather resistance, and heat resistance.
- acrylic polymers are more preferable.
- Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers.
- the latter acrylic plasticizer is prepared by a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. Therefore, it is more preferable for the purpose of the present invention.
- Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue).
- the living radical polymerization method can also be mentioned as another synthesis method. This method is preferable because the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, but is not limited thereto.
- the molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.
- the molecular weight distribution is narrow, it can be an excellent material exhibiting very good vibration damping (damping) against vibrations in a relatively high frequency range of about 100 Hz to several 1000 Hz at room temperature. It is also possible to design a damping (damping) property that shows a peak in frequency.
- the plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.
- plasticizers can be blended at the time of polymer production.
- the amount of use in the case of using a plasticizer is not limited.
- the plasticizer used in the present invention is used in the range of 0.1 to 500 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). In particular, it is preferably used in the range of 1 to 300 parts by weight.
- ⁇ Filler> Various fillers may be used as necessary in the composition for vibration damping material of the present invention. Although it depends on the type of filler, it is generally useful because it can improve the loss factor (damping characteristics) particularly in a high temperature region of 80 ° C. or higher.
- the filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red pepper, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, Glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber They include fibrous fillers such as is.
- precipitated silica fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.
- silica in the form of ultrafine powder having a specific surface area (according to the BET adsorption method) of 50 m 2 / g or more, usually 50 to 400 m 2 / g, preferably about 100 to 300 m 2 / g is preferable.
- silica whose surface is previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane or the like is more preferable.
- silica-based fillers with high reinforcing properties are not particularly limited, but are those of Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Co., Ltd., which is one of precipitated silica. Nipsil etc. are mentioned.
- a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added.
- the specific surface area of calcium carbonate is small, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient.
- the larger the specific surface area value the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product.
- the calcium carbonate is subjected to a surface treatment using a surface treatment agent.
- a surface treatment agent organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used.
- fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid.
- salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids.
- surfactants include polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, sulfate anion surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, and alkylnaphthalenes.
- the treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate.
- the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weatherability improvement effect may not be sufficient.
- the treatment amount exceeds 20% by weight the storage stability of the composition for vibration damping material May decrease.
- calcium carbonate when used, if it is particularly expected to improve the thixotropy of the composition for vibration damping materials, the breaking strength of the cured product, the breaking elongation, the adhesiveness and the weather resistance adhesiveness, It is preferable to use calcium carbonate.
- heavy calcium carbonate may be added for the purpose of lowering viscosity, increasing the amount of the curable composition, reducing costs, etc.
- this heavy calcium carbonate the following may be added as necessary. Can be used.
- Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. Heavy calcium carbonate becomes products having various average particle sizes by classification.
- the specific surface area has a value of 1.5 m 2 / g or more and 50 m 2 / g or less. , more preferably from 2m 2 / g or more 50 m 2 / g or less, more preferably 2.4 m 2 / g or more 50m 2 / g, 3m 2 / g or more 50 m 2 / g or less is particularly preferred.
- the specific surface area is less than 1.5 m 2 / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply reduced or when the purpose is only to increase the viscosity.
- the value of the specific surface area refers to a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method.
- a measuring instrument it is preferable to use a specific surface area measuring instrument SS-100 manufactured by Shimadzu Corporation.
- fillers may be used alone or in combination of two or more according to the purpose and necessity.
- these fillers may be used alone or in combination of two or more according to the purpose and necessity.
- the viscosity of the composition for damping material is increased moderately. Suppressing and improving the breaking strength, breaking elongation, adhesion and weather resistance of damping material can be greatly expected.
- the filler is used in the range of 5 to 1000 parts by weight with respect to the total of 100 parts by weight of the branched polymer (A) and the resin (B). More preferably, it is used in the range of parts by weight, particularly preferably in the range of 40 to 300 parts by weight.
- the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. Workability may be reduced.
- a filler may be used independently and may be used together 2 or more types.
- fine hollow particles may be used in combination with these reinforcing fillers.
- Such fine hollow particles are not particularly limited, but, as described in “The latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 ⁇ m or less, more preferably Is a hollow body made of an inorganic or organic material of 200 ⁇ m or less.
- CMC functional filler
- the diameter is 1 mm or less, preferably 500 ⁇ m or less, more preferably Is a hollow body made of an inorganic or organic material of 200 ⁇ m or less.
- examples of the inorganic balloons include silicate balloons and non-silicate balloons
- silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc.
- non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons.
- these inorganic balloons include Shirasu balloons made by Idichi Kasei, Sankilite made by Sanki Kogyo Co., Ltd., Nippon Glass Co., Ltd., Caloon made by Sumitomo 3M, Cellstar Z-28 made by Sumitomo 3M, MICRO made by EMERSON & CUMING BALLON, PITTSBURGE CORNING's CELAMIC GLASSMODULES, 3M's GLASS BUBBLES, Asahi Glass's Q-CEL, Taiheiyo Cement's E-SPHERES, PFAMARKETING's CEROSPHERES. S.
- Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon.
- the thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon.
- the thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons.
- a crosslinked thermoplastic balloon can also be used.
- the balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.
- organic balloons include UCAR and PHENOLIC MICROBALLLOONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O from EMERSON & CUMING, and DOWESHALAL made by Saran balloons by Saran Balloon.
- the above balloons may be used alone or in combination of two or more.
- fatty acids fatty acid esters, rosin, rosin lignin, silane coupling agents, titanium coupling agents, aluminum coupling agents, polypropylene glycol, etc.
- silane coupling agents titanium coupling agents, aluminum coupling agents, polypropylene glycol, etc.
- titanium coupling agents aluminum coupling agents
- polypropylene glycol etc.
- These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.
- the content of the balloon is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the branched polymer (A) and the resin (B). Can be used in a range of If this amount is less than 0.1 parts by weight, the effect of weight reduction is small, and if it is 50 parts by weight or more, a decrease in tensile strength may be observed among mechanical properties.
- the specific gravity of the balloon is 0.1 or more, it is preferably 3 to 50 parts by weight, and more preferably 5 to 30 parts by weight.
- the physical property modifier is not particularly limited, but examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkylisopropenoxysilanes such as ⁇ -glycidoxypropylmethyldiisopropenoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) aminopropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropy
- the physical property adjusting agent By using the physical property adjusting agent, it is possible to increase the hardness of the vibration damping material obtained by curing the composition for vibration damping material in the present invention, or to reduce the hardness and increase the elongation.
- the said physical property modifier may be used independently and may be used together 2 or more types.
- the content of the physical property modifier is not particularly limited, but is preferably 0.1 to 200 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). Can be used in a range of
- a silanol-containing compound may be added to the composition for vibration damping material of the present invention in order to change the vibration damping properties.
- the silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.
- the compound having one silanol group in the molecule which is one of the silanol-containing compounds is not particularly limited, and the compounds shown below, (CH 3 ) 3 SiOH, (CH 3 CH 2 ) 3 SiOH, (CH 3 CH 2 CH 2 ) 3 SiOH, (n-Bu) 3 SiOH, (sec-Bu) 3 SiOH, (t-Bu) 3 SiOH , (T-Bu) Si (CH 3 ) 2 OH, (C 5 H 11 ) 3 SiOH, (C 6 H 13 ) 3 SiOH, (C 6 H 5 ) 3 SiOH, (C 6 H 5 ) 2 Si ( CH 3) OH, (C 6 H 5) Si (CH 3) 2 OH, (C 6 H 5) 2 Si (C 2 H 5) OH, C 6 H 5 Si (C 2 H 5) 2 OH, C 6 H 5 Si (C 2 H 5) 2 OH, C 6 H 5 CH 2 Si (C 2 H 5 ) 2 OH, C 10 H 7 Si (CH 3 ) 2 OH
- R 58 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- the plurality of R 58 may be the same or different.
- R 58 is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group or a phenyl group, more preferably a methyl group.
- (CH 3 ) 3 SiOH which is easy to obtain and has a low molecular weight, is preferable from the viewpoint of effects.
- the compound having one silanol group in the molecule reacts with a crosslinkable silyl group or a siloxane bond formed by crosslinking when a (meth) acrylic polymer having a crosslinkable silyl group is used. It is estimated that the number of cross-linking points is reduced and the vibration damping material is given flexibility.
- the compound that can be used in the vibration damping material of the present invention and can generate a compound having one silanol group in the molecule by reacting with moisture is not particularly limited. It is preferable that the compound (hydrolysis product) which has one silanol group is a compound represented by the said General formula (10). For example, although not particularly limited, the following compounds may be mentioned in addition to the compound represented by the general formula (11) as described later.
- the compound that can be used in the present invention and can generate a compound having one silanol group in the molecule by reacting with moisture is not particularly limited, but is represented by the following general formula (11) in addition to the above compound.
- ((R 58 ) 3 SiO) n R 59 (11) (In the formula, R 58 is the same as described above. N represents a positive number, and R 59 represents a group obtained by removing some or all of the active hydrogen from the active hydrogen-containing compound.)
- R 58 is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group or a phenyl group, more preferably a methyl group.
- the (R 58 ) 3 Si group is particularly preferably a trimethylsilyl group in which all three R 58 are methyl groups.
- N is preferably 1 to 5.
- the active hydrogen-containing compound from which R 59 is derived is not particularly limited.
- Phenols formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, methacrylic Carboxylic acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; methylamine, Amines such as dimethylamine, ethylamine, diethylamine, n-butylamine and imidazole; acid amides such as acetamide and benzamide; ureas such as urea and N, N′-diphenylurea; acetone, acetylacetone and 2,4-heptadione And ketones.
- Carboxylic acids such as oleic acid, linoleic acid
- the compound capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (11) is, for example, trimethylsilyl chloride or dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with an active hydrogen such as a halogen group together with a (R 58 ) 3 Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R 58 is the same as described above.)
- the compound represented by the general formula (11) include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N— Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trim
- a compound that can be represented by the general formula (((R 60 ) 3 SiO) (R 61 O) s ) t Z, CH 3 O (CH 2 CH (CH 3 ) O) 5 Si (CH 3 ) 3 , CH 2 CHCH 2 (CH 2 CH (CH 3) O) 5 Si (CH 3) 3, (CH 3 ) 3 SiO (CH 2 CH (CH 3 ) O) 5 Si (CH 3 ) 3 , (CH 3 ) 3 SiO (CH 2 CH (CH 3 ) O) 7 Si (CH 3 ) 3
- R 60 is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom
- R 61 is a divalent hydrocarbon group having 1 to 8 carbon atoms
- s and t are positive integers.
- S is 1 to 6
- s ⁇ t is 5 or more
- Z is a 1 to 6-valent organic group
- Etc can also be used suitably.
- the active hydrogen-containing compound generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc.
- the active hydrogen-containing compound generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc.
- the active hydrogen-containing compound generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc.
- phenols, acid amides or alcohols are preferably phenols or alcohols in which the active hydrogen-containing compound is a compound having a hydroxyl group.
- a tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.
- a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, synthesis or after synthesis.
- a compound is produced.
- the compound having one silanol group in the molecule produced in this way was produced by a crosslinkable silyl group or reaction when using a (meth) acrylic polymer having a crosslinkable silyl group as described above. It is presumed that by reacting with the siloxane bond, the number of crosslinking points is reduced and the cured product is given flexibility.
- the amount of silanol-containing compound added can be appropriately adjusted according to the expected physical properties of the damping material.
- timing of adding the silanol-containing compound to the vibration damping material composition is not particularly limited, and may be added during the production of the branched polymer, and may be added in the process of making the resin state, the rubber state, or the gel state. Also good.
- the content of the silanol-containing compound is not particularly limited, but is preferably 0.1 to 200 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). Can be used in a range of
- thixotropic agent anti-sagging agent
- a thixotropic agent may be added to the composition for vibration damping material of the present invention in order to prevent sagging and improve workability.
- the sag prevention agent is not particularly limited, and examples thereof include hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.
- the content of the thixotropic agent is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). Can be used in a range of parts.
- a photoreactive substance is a substance in which the molecular structure undergoes a chemical change in a short time by the action of light, resulting in a change in physical properties such as curing.
- This photoreactive substance it is possible to reduce the adhesiveness (also referred to as residual tack) of the vibration damping material when it is in the resin state, rubber state, or gel state.
- This photo-curable material is a material that can be cured by exposure to light, but a typical photo-curable material is allowed to stand at room temperature for one day, for example, in a place where the sun is exposed to the room (near the window).
- the unsaturated acrylic compound is a monomer, an oligomer or a mixture thereof having an unsaturated group represented by the following general formula (12).
- CH 2 CHR 62 CO (O)-(12) (Wherein R 62 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.)
- Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A, isocyanuric acid, and the like.
- Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.
- Azide resin is known as a photosensitive resin having an azide group as a photosensitive group.
- photosensitive resin published March 17, 1972. , Published by the Printing Society Press, page 93 to page 106 to page 117
- these are detailed examples. These can be used alone or in combination, and a sensitizer can be added if necessary.
- unsaturated acrylic compounds are preferable because they are easy to handle.
- the photoreactive substance is preferably added in an amount of 0.01 to 20 parts by weight with respect to a total of 100 parts by weight of the branched polymer (A) and the resin (B). If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.
- an air oxidation curable material may be added to the vibration damping material of the present invention.
- the air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) on the surface of the damping material can be reduced.
- the air oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air.
- a typical air oxidative curable substance can be cured by, for example, standing in air indoors for one day.
- the air oxidative curable substance examples include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; Polymers and copolymers of 1,2-polybutadiene, 1,4-polybutadiene, and C5 to C8 diene, and various modified products of the polymer and copolymers (maleinized modified products, boiled oil modified products, etc.) A specific example is given. Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.
- liquid diene polymer examples include liquid polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizability with these diene compounds.
- Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled products) Oil-modified products, etc.). These may be used alone or in combination of two or more.
- liquid diene polymers liquid polybutadiene is preferred.
- the air oxidation curable substance may be used alone or in combination of two or more.
- the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance.
- these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.
- the content of the air oxidative curable substance is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts per 100 parts by weight in total of the branched polymer (A) and the resin (B). It can be used in the range of parts by weight.
- antioxidant to the composition for damping materials of this invention as needed.
- Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
- phosphorus antioxidants such as thioethers such as MARK PEP-36 and MARK AO-23 (all of which are manufactured by Adeka Gas Chemical), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all of which are manufactured by Ciba Geigy Japan) Etc.
- thioethers such as MARK PEP-36 and MARK AO-23 (all of which are manufactured by Adeka Gas Chemical)
- Irgafos 38, Irgafos 168, Irgafos P-EPQ all of which are manufactured by Ciba Geigy Japan
- hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and mono (or di or tri).
- ( ⁇ -methylbenzyl) phenol 2,2′-methylenebis (4ethyl-6-tert-butylphenol), 2,2′-methylenebis (4methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tri Ethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4hydroxyphenyl) propylene Nate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-
- the antioxidant may be used in combination with the light stabilizer described later, and is particularly preferable because the effect is further exhibited and the weather resistance may be improved.
- Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which an antioxidant and a light stabilizer are mixed in advance may be used.
- the amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight as the total of the branched polymer (A) and the resin (B). If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.
- ⁇ Light stabilizer> You may add a light stabilizer to the composition for damping materials of this invention as needed.
- Various types of light stabilizers are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) published by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
- an ultraviolet absorber is preferable, and specifically, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of these are manufactured by Ciba Geigy Japan) Benzotriazole compounds such as TINUVIN 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as TINUVIN 120 (manufactured by Ciba Geigy Japan).
- a hindered amine compound is also preferable, and examples of such a compound include dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ N, N′-bis (3aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro -1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) Esters etc. Is mentioned.
- the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effects, it is not particularly limited, but may be used in combination, and may be preferably used in combination.
- the light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved.
- Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.
- the amount of the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.
- the damping material of the present invention may further contain a release agent (metal soap) as necessary.
- the metal soap is not particularly limited and any one can be used.
- Metal soap is generally a combination of long-chain fatty acids and metal ions, and has a nonpolar or low polarity part based on fatty acids and a polar part based on the part bound to metal in one molecule. Can be used.
- long chain fatty acids examples include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids.
- saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of availability, and saturated fatty acids having 6 to 18 carbon atoms are particularly preferable from the viewpoint of releasing effect.
- metal ions examples include alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium, barium), zinc, lead, cobalt, aluminum, manganese, strontium, and the like.
- metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, barium ricinoleate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate Zinc 2-ethylhexan
- metal stearates are preferable from the viewpoint of availability and safety, and particularly from the viewpoint of economy, one or more selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate. Is most preferred. There is no restriction
- the content of the release agent is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total of the branched polymer (A) and the resin (B). Can be used in a range of
- additives may be added to the composition for vibration damping material of the present invention as needed for the purpose of adjusting various physical properties of the curable composition or the cured product.
- additives include, for example, flame retardants, anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, etc. Can be given. These various additives may be used alone or in combination of two or more.
- the method for preparing the vibration damping material of the present invention is not particularly limited, but may be prepared as a one-component type in which all the compounding components are preliminarily compounded and stored and cured by moisture in the air after construction.
- components such as a curing catalyst, a filler, a plasticizer, and water may be added separately as a curing agent, and the two-component type may be prepared by mixing the compounding material and the polymer composition before use.
- a colorant can be added at the time of mixing the two components, and the colorant is easy to work if, for example, a pigment and a plasticizer, and in some cases, a paste obtained by mixing a filler is used.
- the curing rate can be finely adjusted at the work site by adding a retarder during mixing of the two components.
- the damping material obtained by curing the composition for damping material containing the branched polymer (A) and the resin (B) of the present invention can be used as an excellent damping material. That is, the vibration damping material that becomes a resin state, rubber state, or gel state substance is particularly resistant to vibrations in a low frequency range (several Hz or more) in a temperature range near room temperature (-20 ° C to 20 ° C). And high vibration damping (tan ⁇ is 0.2 or more).
- the rheology modifier of the present invention is a branched polymer (A).
- This feature is the structure of the branched polymer (A). Since the ends on one side of all branches are bonded, the diffusion rate of the branched polymer (branch) chain is very slow due to the bonding point. is there. Therefore, a high vibration damping property can be expressed even at a low frequency in a temperature region near room temperature.
- the higher the molecular weight of a branched polymer (branch) chain the slower the chain diffusion rate. Therefore, high vibration damping properties against vibrations in a lower frequency region (several Hz or more). Can be designed.
- the branched polymer it is not caused by the main chain structure of the branched polymer, and can be an excellent damping material by the branched structure. Furthermore, when it is necessary to maintain the shape, it may be in a resin state, a rubber state, or a gel state, and these may be completely different from the above-described branched polymer (A). That is, there is no limitation as long as the material can realize a resin state, a rubber state, or a gel state. Further, when the branched polymer (A) is used as a rheology modifier, there is no limitation on the shape. . Therefore, there is a great advantage that the vibration damping property and other physical properties can be designed separately.
- the damping material according to the present invention does not use the glass-rubber transition temperature.
- the glass-rubber transition temperature of the obtained material is around ⁇ 45 ° C.
- high vibration damping property (tan ⁇ is 0.2 or more in the temperature range around ⁇ 20 ° C. to 20 ° C.) ) Does not utilize the glass-rubber transition temperature.
- vibration damping material and the rheology adjusting agent of the present invention can be used for various uses because of its high degree of design freedom.
- shock absorbing material, shock absorbing material, vibration absorbing material, vibration insulating material, vibration transmitting material, displacement absorbing material, displacement transmitting material, stress absorbing material, stress relaxing material, stress transmitting material, pressure dispersion material, vibration damping material, Damping materials, packing materials, soundproof materials, sound absorbing materials, sound insulating materials, insulating materials, moistureproof materials, anticorrosive materials, rustproof materials and the like can be mentioned.
- Sports equipment such as shoes and protectors
- health care equipment such as bedding, pillows, cushions, mattresses, and pads for prevention of injury
- watches, mobile phones, cameras, scanners, computers, printers Information storage device (memory), game machine, electronic dictionary, music player, TV, video, DVD player / recorder, Blu-ray disc player / recorder, projector, video player, stepping motor, magnetic disk, hard disk, microphone, recording Machine, telephone, refrigerator, rice cooker, oven, microwave oven, electromagnetic cooker, dishwasher, air conditioner, fan, air purifier, humidifier, dehumidifier, vacuum cleaner, dryer, washing machine, iron, fan heater, Sewing machine, warm water flush toilet seat, lighting device, scale, blood pressure , Thermometers, pedometers, hearing aids, barber and beauty appliances, vending machines, speaker frames, BS antennas, VTRs, and other electrical and electronic devices; roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls , Stairs,
- weight average molecular weight and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; Showa Denko) and chloroform as a GPC solvent were used. The number of functional groups introduced per molecule of the polymer was calculated based on the concentration analysis by 1 H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.
- an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
- Butyl acetate was used as a diluent solvent for the polymer. It diluted with about 100 weight part butyl acetate with respect to the said polymer, the filter aid was added, it heat-processed, and it filtered. Further, an adsorbent (KYOWARD 700SEN, KYOWARD 500SH) was added to the filtrate and filtered to obtain a clarified liquid. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
- DMAC was distilled off under reduced pressure
- the polymer concentrate was diluted with about 100 parts by weight of butyl acetate with respect to the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated,
- a polymer [P1] having an acryloyl group as an ultraviolet crosslinking group was obtained.
- the obtained polymer [P1] had a weight average molecular weight Mw of 12,760 and a molecular weight distribution of 1.10.
- the average number of acryloyl groups introduced per molecule of the polymer was determined by 1 H NMR analysis, it was about 1.0 (that is, the introduction rate of acryloyl groups at one end was almost 100%).
- DSC differential scanning calorimetry
- Tg glass-rubber transition temperature
- an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
- Butyl acetate was used as a diluent solvent for the polymer. It diluted with about 100 weight part butyl acetate with respect to the said polymer, the filter aid was added, it heat-processed, and it filtered. Further, an adsorbent (KYOWARD 700SEN, KYOWARD 500SH) was added to the filtrate and filtered to obtain a clarified liquid. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
- DMAC was distilled off under reduced pressure
- the polymer concentrate was diluted with about 100 parts by weight of butyl acetate with respect to the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated,
- a polymer [P2] having an acryloyl group as an ultraviolet crosslinking group was obtained.
- the obtained polymer [P2] had a weight average molecular weight Mw of 25430 and a molecular weight distribution of 1.10.
- the average number of acryloyl groups introduced per molecule of the polymer was determined by 1 H NMR analysis, it was about 1.0 (that is, the introduction rate of acryloyl groups at one end was almost 100%).
- DSC differential scanning calorimetry
- Tg glass-rubber transition temperature
- an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
- Butyl acetate was used as a diluent solvent for the polymer. It diluted with about 100 weight part butyl acetate with respect to the said polymer, the filter aid was added, it heat-processed, and it filtered. Further, an adsorbent (KYOWARD 700SEN, KYOWARD 500SH) was added to the filtrate and filtered to obtain a clarified liquid. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
- Step of introducing a non-reactive functional group at the terminal The obtained polymer is dissolved in about 100 parts by weight of N, N-dimethylacetamide (DMAC), and potassium acetate (with respect to the terminal Br group) is dissolved. About 2 molar equivalents), heat stabilizer (H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), adsorbent (Kyoward 700SEN), and about 70 ° C. And stirred for several hours.
- DMAC N, N-dimethylacetamide
- H-TEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl
- adsorbent Kyoward 700SEN
- the polymer [P3] was a (meth) acrylic polymer that does not react even when the above-described various reaction catalysts are used and has a simple linear polymer form.
- an ultraviolet irradiation device (light hammer) 6: to yield Fusion UV system Japan KK) peak irradiance 1300 mW / cm 2 using a polymer corresponding to the branch polymer (a) by the irradiation of the integrated quantity of light 3000 mJ / cm 2 to [P4].
- the obtained polymer [P4] had a weight average molecular weight Mw of 135882 and a molecular weight distribution of 3.41. Since the weight average molecular weight Mw of the precursor of the branched polymer (A) (polymer [P1]) was 12760, the average number of branches of the polymer [P4] was about 10.6. From differential scanning calorimetry (DSC), the glass-rubber transition temperature (Tg) of the polymer [P4] was ⁇ 45 ° C.
- an ultraviolet irradiation device (light hammer) 6: to yield Fusion UV system Japan KK) peak irradiance 1300 mW / cm 2 using a polymer corresponding to the branch polymer (a) by the irradiation of the integrated quantity of light 3000 mJ / cm 2 to [P5].
- the average number of acryloyl groups remaining per molecule of the polymer was determined by 1 H NMR analysis, it was not detected (that is, the radical polymerization rate of the polymer [P1] was almost 100%).
- the glass-rubber transition temperature (Tg) of the polymer [P5] was -45 ° C.
- the obtained polymer [P5] had a weight average molecular weight Mw of 4,49719 and a molecular weight distribution of 7.16. Since the weight average molecular weight Mw of the precursor of the branched polymer (A) (polymer [P2]) was 25430, the average number of branches of the polymer [P5] was about 17.6.
- Butyl acetate was used as a diluent solvent for the polymer. It diluted with about 100 weight part butyl acetate with respect to the said polymer, the filter aid was added, it heat-processed, and it filtered. Further, an adsorbent (KYOWARD 700SEN, KYOWARD 500SH) was added to the filtrate and filtered to obtain a clarified liquid. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
- DMAC was distilled off under reduced pressure
- the polymer concentrate was diluted with about 100 parts by weight of butyl acetate with respect to the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and both ends were concentrated.
- a polymer [P6] having an acryloyl group as an ultraviolet crosslinking group was obtained.
- the obtained polymer [P6] had a weight average molecular weight Mw of about 14101 and a molecular weight distribution of 1.19. When the average number of acryloyl groups introduced per molecule of the polymer was determined by 1 H NMR analysis, it was about 1.9. From differential scanning calorimetry (DSC), the glass-rubber transition temperature (Tg) of the polymer [P6] was -45 ° C.
- DVA-200 Dynamic viscoelasticity measuring device
- the test piece was in the shape of a sample having a thickness of about 2 mm, a length of about 6.5 mm, and a width of 5.5 mm. From the measurement, a change in loss tangent (tan ⁇ ) with respect to temperature can be obtained and used as an index of damping performance (damping performance). If the loss tangent tan ⁇ is high, the dynamic viscoelastic behavior of the material can be used to dissipate the given mechanical energy as energy such as heat and attenuate the energy.
- DSC Differential scanning calorimetry
- DSC-50 manufactured by Shimadzu Corporation
- the heating rate was 5 ° C./min, and the temperature range was ⁇ 80 ° C. to 80 ° C.
- the glass-rubber transition temperature (Tg) was determined by DSC measurement.
- Example 1 20 parts of the branched polymer [P4] obtained in Production Example 4 and 80 parts of the polymer [P6] obtained in Production Example 6 were combined with 1 part of the antioxidant IRGANOX 1010 and 2-hydroxyl as a photo radical initiator.
- DAROCURE1173 -2-Methyl-1-phenyl-propan-1-one
- IRGACURE819 0.1 part, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- IRGACURE819 made by Specialty Chemicals
- Example 2 50 parts of the branched polymer [P4] obtained in Production Example 4 and 50 parts of the polymer [P6] obtained in Production Example 6 were combined with 1 part of the antioxidant IRGANOX1010 and 2-hydroxyl as a photo radical initiator.
- DAROCURE1173 -2-Methyl-1-phenyl-propan-1-one
- IRGACURE819 0.1 part, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- IRGACURE819 made by Specialty Chemicals
- Example 3 80 parts of the branched polymer [P4] obtained in Production Example 4 and 20 parts of the polymer [P6] obtained in Production Example 6 were combined with 1 part of the antioxidant IRGANOX1010 and 2-hydroxyl as a photo radical initiator.
- DAROCURE1173 -2-Methyl-1-phenyl-propan-1-one
- IRGACURE819 0.1 part, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- IRGACURE819 made by Specialty Chemicals
- Example 4 50 parts of the branched polymer [P5] obtained in Production Example 5 and 50 parts of the polymer [P6] obtained in Production Example 6 were mixed with 1 part of the antioxidant IRGANOX1010 and 2-radical photoinitiator.
- Hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCURE1173; manufactured by Ciba Specialty Chemicals) 0.1 part, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819; Ciba (Specialty Chemicals) 0.05 part was added, and after sufficient dissolution and mixing, heating and defoaming were performed at 60 ° C. for 1 hour.
- DAROCURE1173 Hydroxy-2-methyl-1-phenyl-propan-1-one
- IRGACURE819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- Example 5 75 parts of the branched polymer [P5] obtained in Production Example 5 and 25 parts of the polymer [P6] obtained in Production Example 6 were mixed with 1 part of the antioxidant IRGANOX1010 and 2-radical photoinitiator.
- Hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCURE1173; manufactured by Ciba Specialty Chemicals) 0.05 parts, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819; Ciba (Specialty Chemicals) 0.025 part was added and sufficiently dissolved and mixed, and then heated and degassed at 60 ° C. for 1 hour.
- DAROCURE1173 Hydroxy-2-methyl-1-phenyl-propan-1-one
- IRGACURE819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
- the damping materials containing the branched polymers of Examples 1 to 5 are vibrations in a particularly low frequency range (here, 5 Hz) in a temperature range near room temperature ( ⁇ 20 ° C. to 20 ° C.).
- the vibration damping is remarkably excellent (tangent loss tan ⁇ is 0.25 or more).
- the tangent loss tan ⁇ of the comparative example is less than 0.2, whereas in Examples 1 to 5, it is 0.25 or more, which is clearly suitable for the damping material.
- the molecular weights of the branches of the branched polymer used in Examples 1, 2, 3 and 4, 5 are different.
- Example 2 and Comparative Example 2 are compared.
- 50 parts of the branched polymer component was included, and in Comparative Example 2, 50 parts of the component corresponding to the free hanging chain in the crosslinked network was included.
- the second embodiment is particularly effective for vibration in a low frequency region (here, 5 Hz) in a temperature region near room temperature ( ⁇ 20 ° C. to 20 ° C.). It can be seen that is superior in vibration damping (the value of tangent loss tan ⁇ is large). This means that the material in the rubber state, the gel state, or the resin state exhibits significant vibration damping properties by simply containing the branched polymer. It does not matter whether the branched polymer is bonded to the crosslinked network or not. Therefore, there is no need to select a reaction system for making a rubber state, a gel state, or a resin state. The same applies to Example 4 and Comparative Example 3.
- the composition for a vibration damping material containing the (meth) acrylic polymer of the present invention provides a material having the excellent weather resistance of the (meth) acrylic polymer and exhibiting the required excellent viscoelastic behavior. sell.
- the cured material in the resin state, rubber state, or gel state which is the vibration damping material of the present invention, has a specific temperature range near room temperature ( ⁇ 20 ° C. to 20 ° C.) and a low frequency range (several High vibration suppression (energy attenuation) property against vibrations of Hz) or higher. Therefore, such a cured material can control vibration damping properties in a low frequency region and at room temperature or higher, which has been difficult in the past, and is suitable for a vibration damping material that requires higher performance.
- the vibration damping performance improvement effect of this embodiment not only the vibration damping performance improvement effect of this embodiment, but also branched polymers can be added to various base materials in each application, and physical properties such as shock relaxation properties and vibration damping properties can be designed with a high degree of freedom. Therefore, it can be suitably used for rheology adjusting agents, shock absorbing materials, pressure dispersion materials, vibration damping materials, vibration damping materials, packing materials, sound insulation materials, sound absorbing materials, sound insulation materials, and the like.
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Abstract
Description
本発明における分岐高分子(A)とは、非線状の高分子形態を持つ重合体を指す。1つの中心から3本以上の枝が出ている星型高分子、1本の幹に分岐していない枝が複数ついた櫛型高分子、不規則に枝分かれのある統計的高分子(ケーリーの樹木と呼ばれることもある)などに分かれる。分岐は、様々な主合成過程で生じる。付加重合過程で起こったり、単官能または/および多官能性(3官能以上)モノマー単位を重合または縮合させても生じる。
本発明に係る分岐高分子(A)の主鎖を構成するモノマー単位としては特に限定されず、有機系高分子重合体、無機系高分子重合体のものを用いることができる。
本発明に使用される有機系高分子重合体には、合成高分子重合体、半合成高分子重合体、天然高分子重合体があげられ種々の重合技術により調製される。
本発明における、分岐高分子(A)の合成法は、特に制限されず、分岐高分子(A)を先に合成し、それを添加して制振材料用組成物としても良い。また、分岐高分子(A)の前駆体を含有している組成物中において、後で合成させることで、結果的に分岐高分子(A)を含有する制振材料用組成物となってもよい。
ラジカル重合法は、重合開始剤としてアゾ系化合物、過酸化物などを用いて、特定の官能基を有するモノマーと(メタ)アクリル系モノマーとを単に共重合させる「一般的なラジカル重合法」と、末端などの制御された位置に特定の官能基を導入することが可能な「制御ラジカル重合法」に分類できる。
(架橋性官能基の数)
リビングラジカル重合により合成された(メタ)アクリル系重合体は、片末端に架橋性官能基を持つことができ、従来とは異なり、高確率で官能基が導入されている。上述のように、これがマクロモノマーとなる。(メタ)アクリル系重合体が有する架橋性官能基の1分子当たり平均した個数としては0.7以上が好ましく、反応性の点で0.8個以上がより好ましく、0.9個以上がさらに好ましい。上記、リビングラジカル重合を用いれば、高確率で架橋性官能基を片末端に導入できるため、このマクロモノマーを後反応させることにより分岐高分子(A)が得られ、高確率で容易に高分子量化が可能である。これらの合成方法は、種々の重合法により得ることができ、特に限定されない。また、必要があれば反応触媒や硬化剤が必要になるものがある。また、分岐高分子(A)の合成に応じて、各種の添加剤を併用しても構わない。
本発明の分岐高分子を合成する際、制振性に大きな影響を与えるマクロモノマーの重合度を高くするため、架橋性官能基の少なくとも1個は分子鎖の末端にあることが好ましい。より好ましくは、全ての架橋性官能基を分子鎖末端に有するものである。
(メタ)アクリル系重合体が有する架橋性官能基としては、特に限定するわけではないが、架橋性シリル基、アルケニル基、水酸基、アミノ基、重合性の炭素-炭素二重結合またはエポキシ基が挙げられる。これら硬化触媒や硬化剤が必要になるものがある。また、目的とする物性に応じて、各種の添加剤を添加しても構わない。
本発明の架橋性シリル基としては、一般式(1);
-[Si(R1)2-b(Y)bO]m-Si(R2)3-a(Y)a (1)
{式中、R1、R2は、いずれも炭素数1~20のアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、または(R')3SiO-(R'は炭素数1~20の1価の炭化水素基であって、3個のR'は同一であってもよく、異なっていてもよい)で示されるトリオルガノシロキシ基を示し、R1またはR2が2個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Yは水酸基または加水分解性基を示し、Yが2個以上存在するときそれらは同一であってもよく、異なっていてもよい。aは0,1,2,または3を、また、bは0,1,または2を示す。mは0~19の整数である。ただし、a+mb≧1であることを満足するものとする。}
で表される基があげられる。
-Si(R2)3-a(Y)a (2)
(式中、R2、Yは前記と同じ、aは1~3の整数)で表される架橋性シリル基が、入手が容易である点で好ましい。
本発明におけるアルケニル基は、限定はされないが、一般式(3)で表されるものであることが好ましい。
H2C=C(R11)- (3)
(式中、R11は水素原子あるいは炭素数1~20の炭化水素基である)
一般式(3)において、R11は水素原子あるいは炭素数1~20の炭化水素基であり、具体的には以下のような基が例示される。
-(CH2)n-CH3、
-CH(CH3)-(CH2)n-CH3、
-CH(CH2CH3)-(CH2)n-CH3、
-CH(CH2CH3)2、
-C(CH3)2-(CH2)n-CH3、
-C(CH3)(CH2CH3)-(CH2)n-CH3、
-C6H5、
-C6H5(CH3)、
-C6H5(CH3)2、
-(CH2)n-C6H5、
-(CH2)n-C6H5(CH3)、
-(CH2)n-C6H5(CH3)2
(nは0以上の整数で、各基の合計炭素数は20以下)
これらの内では、水素原子が好ましい。
本発明におけるアミノ基としては、限定はされないが、
-NR12 2
(R12は水素または炭素数1~20の1価の有機基であり、2個のR12は互いに同一でもよく異なっていてもよく、また、他端において相互に連結し、環状構造を形成していてもよい。)
が挙げられるが、
-(NR12 3)+X-
(R12は上記と同じ。X-は対アニオン。)
に示されるアンモニウム塩であっても何ら問題はない。
重合性の炭素-炭素二重結合を有する基としては、好ましくは、一般式(4);
-OC(O)C(R13)=CH2 (4)
(式中、R13は水素、または、炭素数1~20の一価の有機基を表す。)
で表される基であり、更に好ましくは、R13が、水素、または、メチル基である基である。
エポキシ基としては、好ましくは、グリシジル基、グリシジルエーテル基、3,4-エポキシシクロヘキシル基、オキセタン基が挙げられるが、反応性の点でグリシジル基、グリシジルエーテル基、3,4-エポキシシクロヘキシル基がより好ましい。
上述のように、制御ラジカル重合を駆使して、高確率で架橋性官能基が片末端に導入されたマクロモノマーを後反応させることにより分岐高分子(A)が得られ、高確率で容易に高分子量化が可能である。この後反応の重合方法は、いかなる方法でもよい。例えば、制御されていない重合でも構わないし、制御ラジカル重合で後重合をして、分岐高分子(A)を得ても良い。また、本発明の分岐高分子(A)の合成においては、反応触媒や硬化剤が必要になるものがある。また、目的とする物性に応じて、各種の添加剤を添加しても構わない。
〔架橋性シリル基を有する(メタ)アクリル系重合体の場合〕
架橋性シリル基を有する(メタ)アクリル系重合体は、従来公知の各種縮合触媒の存在下、あるいは非存在下にシロキサン結合を形成することにより縮合、多分岐化し、分岐高分子(A)が得られる。分岐高分子の性状としては、(メタ)アクリル系重合体の分子量と主鎖骨格に応じて、ゲル状、ゴム状のものから樹脂状のものまで幅広く作成することができる。
R49 aSi(OR50)4-a (5)
(式中、R49およびR50は、それぞれ独立に、炭素数1~20の置換あるいは非置換の炭化水素基である。さらに、aは0、1、2、3のいずれかである。)で示されるアミノ基やシラノール基をもたないケイ素化合物を助触媒として添加しても構わない。
アルケニル基を用いて架橋させる場合は、限定はされないが、ヒドロシリル基含有化合物を分岐剤とし、ヒドロシリル化触媒を用いてヒドロシリル化反応により多分岐化させることが好ましい。
R51 3SiO-[Si(R51)2O]a-[Si(H)(R52)O]b-[Si(R52)(R53)O]c-SiR51 3 (6)
HR51 2SiO-[Si(R51)2O]a-[Si(H)(R52)O]b-[Si(R52)(R53)O]c-SiR51 2H (7)
(式中、R51およびR52は炭素数1~6のアルキル基、または、フェニル基、R53は炭素数1~10のアルキル基またはアラルキル基を示す。aは0≦a≦100、bは2≦b≦100、cは0≦c≦100を満たす整数を示す。)、環状シロキサン等の化合物を用いることができる。
(CH3)3SiO-[Si(H)(CH3)O]g-[Si(C6H5)2O]h-Si(CH3)3 (8)
(CH3)3SiO-[Si(H)(CH3)O]g-[Si(CH3){CH2C(H)(R57)C6H5}O]h-Si(CH3)3 (9)
(式中、R57は水素またはメチル基を示す。gは2≦g≦100、hは0≦h≦100の整数を示す。C6H5はフェニル基を示す。)
ヒドロシリル基含有化合物としてはさらに、分子中に2個以上のアルケニル基を有する低分子化合物に対し、一般式(6)から(9)に表されるヒドロシリル基含有化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。分子中に2個以上のアルケニル基を有する化合物としては、各種のものを用いることができる。例示するならば、1,4-ペンタジエン、1,5-ヘキサジエン、1,6-ヘプタジエン、1,7-オクタジエン、1,8-ノナジエン、1,9-デカジエン等の炭化水素系化合物、O,O'-ジアリルビスフェノールA、3,3'-ジアリルビスフェノールA等のエーテル系化合物、ジアリルフタレート、ジアリルイソフタレート、トリアリルトリメリテート、テトラアリルピロメリテート等のエステル系化合物、ジエチレングリコールジアリルカーボネート等のカーボネート系化合物が挙げられる。
本発明において、水酸基を有する(メタ)アクリル系重合体を使用する場合は、水酸基と反応し得る官能基を2個以上有する化合物を分岐剤として用いることにより、均一に硬化する。分岐剤の具体例としては、たとえば、1分子中に2個以上のイソシアネート基を有する多価イソシアネート化合物、メチロール化メラミンおよびそのアルキルエーテル化物または低縮合化物等のアミノプラスト樹脂、多官能カルボン酸およびそのハロゲン化物等が挙げられる。これらの分岐剤を使用して分岐高分子を作成する際には、それぞれ適当な反応触媒を使用することができる。
本発明に係るアミノ基を有する(メタ)アクリル系重合体は、アミノ基と反応し得る官能基を2個以上有する化合物を分岐剤として用いることにより、均一に反応する。分岐剤の具体例としては、たとえば、1分子中に2個以上のイソシアネート基を有する多価イソシアネート化合物、メチロール化メラミンおよびそのアルキルエーテル化物または低縮合化物等のアミノプラスト樹脂、多官能カルボン酸およびそのハロゲン化物等が挙げられる。これらの分岐剤を使用して分岐高分子を作成する際には、それぞれ適当な反応触媒を使用することができる。
本発明に係るエポキシ基を有する(メタ)アクリル系重合体の分岐剤としては特に限定されないが、たとえば、脂肪族アミン類、脂環族アミン類、芳香族アミン類;酸無水物;ポリアミド;イミダゾール類;アミンイミド;ユリア;メラミンとその誘導体;ポリアミンの塩;フェノール樹脂;ポリメルカプタン、ポリスルフィド;芳香族ジアゾニウム塩、ジアリルヨードニウム塩、トリアリルスルホニウム塩、トリアリルセレニウム塩等の光・紫外線硬化剤等が用いられる。
重合性の炭素-炭素二重結合を有する(メタ)アクリル系重合体は、その重合性の炭素-炭素二重結合の重合反応により架橋させることができる。
本発明の制振材用硬化性組成物中の分岐高分子(A)は、UVや電子線などの活性エネルギー線によっても合成することができる。活性エネルギー線としては、紫外線、可視光線、LED光線、電子線、放射線等が挙げられる。このうち、出力装置の汎用性や取り扱いのしやすさ、得られる硬化物の物性などの観点から、紫外線が好ましい。活性エネルギー線により多分岐化させる場合には、光重合開始剤を含有させることが好ましい。
本発明の分岐高分子(A)を加熱合成させる場合には、熱重合開始剤を含有させることが好ましい。
本発明の制振材は、樹脂(B)を含む。
また、本発明における制振材料用組成物は、分岐高分子(A)および樹脂(B)を含有する。
本発明の制振材料用組成物には、シランカップリング剤や、シランカップリング剤以外の接着性付与剤を添加することができる。接着付与剤を添加すると、外力により目地幅等が変動することによって、シーリング材がサイディングボード等の被着体から剥離する危険性をより低減することができる。また、場合によっては接着性向上の為に用いるプライマーの使用の必要性がなくなり、施工作業の簡略化が期待される。シランカップリング剤の具体例としては、アミノ基や、メルカプト基、エポキシ基、カルボキシル基、ビニル基、イソシアネート基、イソシアヌレート、ハロゲン等の官能基をもったシランカップリング剤が例示でき、その具体例としては、γ-イソシアネートプロピルトリメトキシシラン、γ-イソシアネートプロピルトリエトキシシラン、γ-イソシアネートプロピルメチルジエトキシシラン、γ-イソシアネートプロピルメチルジメトキシシラン等のイソシアネート基含有シラン類;γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリイソプロポキシシラン、γ-アミノプロピルメチルジメトキシシラン、γ-アミノプロピルメチルジエトキシシラン、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリエトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジエトキシシラン、γ-(2-アミノエチル)アミノプロピルトリイソプロポキシシラン、γ-ウレイドプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、N-ベンジル-γ-アミノプロピルトリメトキシシラン、N-ビニルベンジル-γ-アミノプロピルトリエトキシシラン等のアミノ基含有シラン類;γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、γ-メルカプトプロピルメチルジエトキシシラン等のメルカプト基含有シラン類;γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン等のエポキシ基含有シラン類;β-カルボキシエチルトリエトキシシラン、β-カルボキシエチルフェニルビス(2-メトキシエトキシ)シラン、N-β-(カルボキシメチル)アミノエチル-γ-アミノプロピルトリメトキシシラン等のカルボキシシラン類;ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-メタクリロイルオキシプロピルメチルジメトキシシラン、γ-アクロイルオキシプロピルメチルトリエトキシシラン等のビニル型不飽和基含有シラン類;γ-クロロプロピルトリメトキシシラン等のハロゲン含有シラン類;トリス(トリメトキシシリル)イソシアヌレート等のイソシアヌレートシラン類等を挙げることができる。また、これらを変性した誘導体である、アミノ変性シリルポリマー、シリル化アミノポリマー、不飽和アミノシラン錯体、フェニルアミノ長鎖アルキルシラン、アミノシリル化シリコーン、ブロックイソシアネートシラン、シリル化ポリエステル等もシランカップリング剤として用いることができる。
本発明の制振材料用組成物には、各種可塑剤を必要に応じて用いても良い。可塑剤を後述する充填材と併用して使用すると硬化物の伸びを大きくできたり、多量の充填材を混合できたりするためより有利となる。しかし、必ずしも添加しなければならないものではない。可塑剤としては、特に限定されないが、物性の調整、性状の調節等の目的により、たとえば、ジブチルフタレート、ジヘプチルフタレート、ジ(2-エチルヘキシル)フタレート、ブチルベンジルフタレート等のフタル酸エステル類;ジオクチルアジペート、ジオクチルセバケート、ジブチルセバケート、コハク酸イソデシル等の非芳香族二塩基酸エステル類;オレイン酸ブチル、アセチルリシリノール酸メチル等の脂肪族エステル類;ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、ペンタエリスリトールエステル等のポリアルキレングリコールのエステル類;トリクレジルホスフェート、トリブチルホスフェート等のリン酸エステル類;トリメリット酸エステル類;ポリスチレンやポリ-α-メチルスチレン等のポリスチレン類;ポリブタジエン、ポリブテン、ポリイソブチレン、ブタジエン-アクリロニトリル、ポリクロロプレン;塩素化パラフィン類;アルキルジフェニル、部分水添ターフェニル、等の炭化水素系油;プロセスオイル類;ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテルポリオールとこれらポリエーテルポリオールの水酸基をエステル基、エーテル基などに変換した誘導体等のポリエーテル類;エポキシ化大豆油、エポキシステアリン酸ベンジル等のエポキシ可塑剤類;セバシン酸、アジピン酸、アゼライン酸、フタル酸等の2塩基酸とエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール等の2価アルコールから得られるポリエステル系可塑剤類;アクリル系可塑剤を始めとするビニル系モノマーを種々の方法で重合して得られる(メタ)アクリル系重合体類等が挙げられる。
本発明の制振材料用組成物には、各種充填材を必要に応じて用いても良い。充填材種によっても異なるが、一般的には特に80℃以上の高温領域の損失係数(制振特性)の低下を改善できることから有用である。充填材としては、特に限定されないが、木粉、パルプ、木綿チップ、アスベスト、ガラス繊維、炭素繊維、マイカ、クルミ殻粉、もみ殻粉、グラファイト、ケイソウ土、白土、シリカ(フュームドシリカ、沈降性シリカ、結晶性シリカ、溶融シリカ、ドロマイト、無水ケイ酸、含水ケイ酸等)、カーボンブラックのような補強性充填材;重質炭酸カルシウム、膠質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、べんがら、アルミニウム微粉末、フリント粉末、酸化亜鉛、活性亜鉛華、亜鉛末、炭酸亜鉛およびシラスバルーンなどのような充填材;石綿、ガラス繊維およびガラスフィラメント、炭素繊維、ケブラー繊維、ポリエチレンファイバー等のような繊維状充填材等が挙げられる。
また、さらに、物性の大きな低下を起こすことなく軽量化、低コスト化を図ることを目的として、微小中空粒子をこれら補強性充填材と併用しても良い。
本発明の制振材料用組成物には、必要に応じて、引張特性を調整する物性調整剤を添加しても良い。
本発明の制振材料用組成物には、制振物性を変える等のために、必要に応じてシラノール含有化合物を添加しても良い。シラノール含有化合物とは、分子内に1個のシラノール基を有する化合物、および/または、水分と反応することにより分子内に1個のシラノール基を有する化合物を生成し得る化合物のことをいう。これらは一方のみを用いてもよいし、両化合物を同時に用いてもよい。
(CH3)3SiOH、(CH3CH2)3SiOH、(CH3CH2CH2)3SiOH、(n-Bu)3SiOH、(sec-Bu)3SiOH、(t-Bu)3SiOH、(t-Bu)Si(CH3)2OH、(C5H11)3SiOH、(C6H13)3SiOH、(C6H5)3SiOH、(C6H5)2Si(CH3)OH、(C6H5)Si(CH3)2OH、(C6H5)2Si(C2H5)OH、C6H5Si(C2H5)2OH、C6H5CH2Si(C2H5)2OH、C10H7Si(CH3)2OH
(ただし、上記式中C6H5はフェニル基を、C10H7はナフチル基を示す。)
等のような(R")3SiOH(ただし式中R"は同一または異種の置換もしくは非置換のアルキル基またはアリール基)で表わすことができる化合物等が例示できる。このうち下記一般式(10)で表される化合物が好ましい。
(R58)3SiOH (10)
(式中、R58は炭素数1~20の1価の炭化水素基を示す。複数のR58は同一であってもよく又は異なっていてもよい。)
R58は、メチル基、エチル基、ビニル基、t-ブチル基、フェニル基が好ましく、さらにメチル基が好ましい。
((R58)3SiO)nR59 (11)
(式中、R58は上述したものと同様である。nは正数を、R59は活性水素含有化合物から一部あるいは全ての活性水素を除いた基を示す。)
R58は、メチル基、エチル基、ビニル基、t-ブチル基、フェニル基が好ましく、さらにメチル基が好ましい。
CH3O(CH2CH(CH3)O)5Si(CH3)3、
CH2=CHCH2(CH2CH(CH3)O)5Si(CH3)3、
(CH3)3SiO(CH2CH(CH3)O)5Si(CH3)3、
(CH3)3SiO(CH2CH(CH3)O)7Si(CH3)3
(式中、R60は同一または異種の置換もしくは非置換の1価の炭化水素基または水素原子、R61は炭素数1~8の2価の炭化水素基、s、tは正の整数で、sは1~6、s×tは5以上、Zは1~6価の有機基)
等も好適に使用できる。これらは単独で用いてもよく、2種以上を併用してもよい。
本発明の制振材料用組成物には、必要に応じて垂れを防止し、作業性を良くするためにチクソ性付与剤(垂れ防止剤)を添加しても良い。
本発明の制振材料用組成物には、必要に応じて光反応性物質を添加しても良い。光反応性物質とは、光の作用によって短時間に、分子構造が化学変化をおこし、硬化などの物性的変化を生ずるものである。この光反応性物質を添加することにより、樹脂状態、ゴム状態、またはゲル状態にした際の制振材の粘着性(残留タックともいう)を低減できる。この光硬化性物質は、光をあてることにより硬化し得る物質であるが、代表的な光硬化性物質は、たとえば、室内の日の当たる位置(窓付近)に1日間、室温で静置することにより硬化させることができる物質である。この種の化合物には、有機単量体、オリゴマー、樹脂あるいはそれらを含む組成物など多くのものが知られており、その種類は特に限定されないが、たとえば、不飽和アクリル系化合物、ポリケイ皮酸ビニル類あるいはアジド化樹脂等が挙げられる。
CH2=CHR62CO(O)- (12)
(式中、R62は水素、炭素数1~10のアルキル基、炭素数6~10のアリール基または炭素数7~10のアラルキル基を示す。)
不飽和アクリル系化合物としては、具体的には、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ネオペンチルアルコール等の低分子量アルコール類の(メタ)アクリル酸エステル類;ビスフェノールA、イソシアヌル酸等の酸あるいは上記低分子量アルコール等をエチレンオキシドやプロピレンオキシドで変性したアルコール類の(メタ)アクリル酸エステル類;主鎖がポリエーテルで末端に水酸基を有するポリエーテルポリオール、主鎖がポリエーテルであるポリオール中でビニル系モノマーをラジカル重合することにより得られるポリマーポリオール、主鎖がポリエステルで末端に水酸基を有するポリエステルポリオール、主鎖がビニル系あるいは(メタ)アクリル系重合体であり、主鎖中に水酸基を有するポリオール等の(メタ)アクリル酸エステル類;ビスフェノールA型やノボラック型等のエポキシ樹脂と(メタ)アクリル酸を反応させることにより得られるエポキシアクリレート系オリゴマー類;ポリオール、ポリイソシアネートおよび水酸基含有(メタ)アクリレート等を反応させることにより得られる分子鎖中にウレタン結合および(メタ)アクリル基を有するウレタンアクリレート系オリゴマー等が挙げられる。
本発明の制振材には、必要に応じて空気酸化硬化性物質を添加しても良い。空気酸化硬化性物質とは、空気中の酸素により架橋硬化できる不飽和基を有する化合物である。この空気酸化硬化性物質を添加することにより、制振材表面の粘着性(残留タックともいう)を低減できる。本発明における空気酸化硬化性物質は、空気と接触させることにより硬化し得る物質であり、より具体的には、空気中の酸素と反応して硬化する性質を有するものである。代表的な空気酸化硬化性物質は、たとえば空気中で室内に1日間静置することにより硬化させることができる。
本発明の制振材料用組成物には、必要に応じて酸化防止剤を添加しても良い。酸化防止剤は各種のものが知られており、たとえば大成社発行の「酸化防止剤ハンドブック」、シーエムシー化学発行の「高分子材料の劣化と安定化」(235~242)等に記載された種々のものが挙げられるが、これらに限定されるわけではない。
本発明の制振材料用組成物には、必要に応じて光安定剤を添加しても良い。光安定剤は各種のものが知られており、例えば大成社発行の「酸化防止剤ハンドブック」、シーエムシー化学発行の「高分子材料の劣化と安定化」(235~242)等に記載された種々のものが挙げられるが、これらに限定されるわけではない。
本発明の制振材には、必要に応じて離型剤(金属石鹸)をさらに含有させることができる。
この金属石鹸の添加量としては特に制限はない。
本発明の制振材料用組成物には、当該硬化性組成物または硬化物の諸物性の調整を目的として、必要に応じて各種添加剤を添加してもよい。このような添加物の例としては、たとえば、難燃剤、老化防止剤、ラジカル禁止剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、発泡剤、などがあげられる。これらの各種添加剤は単独で用いてもよく、2種類以上を併用してもよい。
本発明の分岐高分子(A)および樹脂(B)を含有する制振材料用組成物を硬化させてなる制振材は、優れた制振材として利用できる。すなわち、この樹脂状態、ゴム状態、またはゲル状態の物質となる制振材は、室温付近の温度領域(-20℃~20℃)において、特に低い周波数領域(数Hz以上)の振動に対して、高い制振性(tanδが0.2以上)を持つ。
本発明のレオロジー調整剤は、分岐高分子(A)であることを特徴とする。この特徴は、分岐高分子(A)の構造であり、すべての枝の片側の末端が結合しているため、その結合点ゆえに、分岐したポリマー(枝)鎖の拡散速度が非常に遅いことである。よって、室温付近の温度領域において、低い周波数でも高い制振性を発現できる。また、上述したように、分岐したポリマー(枝)鎖の分子量が高ければ高いほど、鎖の拡散速度が遅くなるため、さらに低い周波数領域(数Hz以上)の振動に対して、高い制振性を設計できる。分岐高分子の主鎖構造には起因せず、分岐構造によって優れた制振材となり得る。さらに、形状を保持する必要がある場合、樹脂状態、ゴム状態、またはゲル状態であればよく、これらは、上述の分岐高分子(A)とは全く別の物質であってよい。すなわち、樹脂状態、ゴム状態、またはゲル状態を実現できる材料であれば、制限がない。さらに、分岐高分子(A)をレオロジー調整剤として用いる場合は、形状にも制限がない。。そのため、制振性と他の諸物性を別々に設計できるという大きな利点がある。また、本発明による制振材は、ガラス-ゴム転移温度を利用していないことがポイントである。実施例でも述べるが、得られる材料のガラス-ゴム転移温度は、-45℃付近であるため、室温付近の温度領域(-20℃~20℃)における高い制振性(tanδが0.2以上)は、ガラス-ゴム転移温度を利用したものではない。
本発明の制振材およびレオロジー調整剤の用途としては、その設計自由度の高さより様々な用途へ使用可能である。例えば、衝撃吸収材、衝撃緩和材、振動吸収材、振動絶縁材、振動伝達材、変位吸収材、変位伝達材、応力吸収材、応力緩和材、応力伝達材、圧力分散材、防振材、制振材、梱包材、防音材、吸音材、遮音材、絶縁材、防湿材、防食材、防錆材などが挙げられる。これら材料が用いられる用途としては、例えば、シューズ、プロテクターなどのスポーツ用品;寝具、枕、クッション、マットレス、けが防止用パッドなどの健康医療介護用品;時計、携帯電話、カメラ、スキャナ、パソコン、プリンタ、情報記憶素子(メモリ)、ゲーム機器、電子辞書、音楽再生器、テレビ、ビデオ、DVDプレイヤー/レコーダー、ブルーレイディスクプレイヤー/レコーダー、プロジェクター、映像再生器、ステッピングモーター、磁気ディスク、ハードディスク、マイク、録音機、電話機、冷蔵庫、炊飯器、オーブン、電子レンジ、電磁調理器、食器洗浄機、エアコン、扇風機、空気清浄機、加湿器、除湿機、掃除機、乾燥機、洗濯機、アイロン、ファンヒーター、ミシン、温水洗浄便座、照明装置、体重計、血圧計、体温計、歩数計、補聴器、理美容家電、自動販売機、スピーカフレーム、BSアンテナ、VTR等の電気・電子機器用途;ルーフ、フロア、シャッタ、カーテンレール、床、配管ダクト、デッキプレート、カーテンウォール、階段、ドア、免振アイソレーター、構造材等の建築用途;エンジンルーム、計測ルーム等の船舶用途;エンジン(オイルパン、フロントカバー、ロッカーカバー)、車体(ダッシュ、フロア、ドア、ルーフ、パネル、ホイルハウス)、トランスミッション、パーキングブレーキカバー、シートバック、シーリング材、車載電子部品の保護材、カーテレビ、カーオーディオ、カーナビゲーション等の自動車用途;TVカメラ、複写機、電算機、プリンタ、レジスタ、キャビネット等のカメラ・事務機器用途;電動工具、シュータ、エレベータ、エスカレータ、コンベア、トラクタ、ブルドーザ、発電機、コンプレッサ、コンテナ、ホッパ、防音ボックス、草刈り機のモータカバー等の産業機械関係用途;鉄道車両ルーフ、側板、ドア、アンダーフロア、各種補機カバー、橋梁等の鉄道用途;半導体用途等の精密除振装置;可聴域しきい値近傍の低周波音及び高周波音に対応する等の防音材がある。
(片末端にアクリロイル基を有するポリアクリル酸n-ブチルの合成)
(1)重合工程
アクリル酸n-ブチル100部を脱酸素した。攪拌機付ステンレス製反応容器の内部を脱酸素し、臭化第一銅0.42部、脱酸素したアクリル酸n-ブチルのうち20部を仕込み、加熱攪拌した。アセトニトリル4.4部、開始剤としてα-ブロモ酪酸エチル1.9部を添加、混合し、混合液の温度を約80℃に調節した段階でペンタメチルジエチレントリアミン(以下、トリアミンと略す)0.018部を添加し、重合反応を開始した。残りのアクリル酸n-ブチル80部を逐次添加し、重合反応を進めた。重合途中、適宜トリアミンを追加し、重合速度を調整した。重合時に使用したトリアミンの総量は0.06部であった。重合が進行すると重合熱により内温が上昇するので内温を約80℃~約90℃に調整しながら重合を進行させた。モノマー転化率(重合反応率)が約95%以上の時点で反応容器気相部に酸素‐窒素混合ガスを導入した。内温を約80℃~約90℃に保ちながらしながら反応液を数時間加熱攪拌して反応液中の重合触媒と酸素を接触させた。アセトニトリル及び未反応のモノマーを減圧脱揮して除去し、重合体を含有する濃縮物を得た。濃縮物は著しく着色していた。
酢酸ブチルを重合体の希釈溶媒として使用した。上記重合体に対して100重量部程度の酢酸ブチルで希釈し、ろ過助剤を加えて加熱処理し、ろ過した。またろ液に対して吸着剤(キョーワード700SEN、キョーワード500SH)を添加し、濾過して清澄液を得た。ろ液を濃縮し、ほぼ無色透明の重合体を得た。
得られた重合体に対して約100重量部のN,N-ジメチルアセトアミド(DMAC)に溶解させて、アクリル酸カリウム(末端Br基に対して約2モル当量)、熱安定剤(H-TEMPO:4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-n-オキシル)、吸着剤(キョーワード700SEN)、を添加し、約70℃で数時間加熱攪拌した。DMACを減圧留去し、重合体濃縮物を重合体に対して約100重量部の酢酸ブチルで希釈し、ろ過助剤を添加して固形分をろ別し、ろ液を濃縮し、片末端に紫外線架橋基としてアクリロイル基を有する重合体[P1]を得た。得られた重合体[P1]の重量平均分子量Mwは12760、分子量分布は1.10であった。重合体1分子当たりに導入された平均のアクリロイル基の数を1H NMR分析により求めたところ、約1.0個(すなわち、片末端へのアクリロイル基の導入率はほぼ100%)であった。示差走査熱量測定(DSC)から重合体[P1]のガラス-ゴム転移温度(Tg)は、-45℃であった。
(片末端にアクリロイル基を有するポリアクリル酸n-ブチルの合成)
(1)重合工程
アクリル酸n-ブチル100部を脱酸素した。攪拌機付ステンレス製反応容器の内部を脱酸素し、臭化第一銅0.95部、脱酸素したアクリル酸n-ブチルのうち20部を仕込み、加熱攪拌した。アセトニトリル8.8部、開始剤としてα-ブロモ酪酸エチル1.9部を添加、混合し、混合液の温度を約80℃に調節した段階でペンタメチルジエチレントリアミン(以下、トリアミンと略す)0.018部を添加し、重合反応を開始した。残りのアクリル酸n-ブチル80部を逐次添加し、重合反応を進めた。重合途中、適宜トリアミンを追加し、重合速度を調整した。重合時に使用したトリアミンの総量は0.17部であった。重合が進行すると重合熱により内温が上昇するので内温を約80℃~約90℃に調整しながら重合を進行させた。モノマー転化率(重合反応率)が約95%以上の時点で反応容器気相部に酸素‐窒素混合ガスを導入した。内温を約80℃~約90℃に保ちながらしながら反応液を数時間加熱攪拌して反応液中の重合触媒と酸素を接触させた。アセトニトリル及び未反応のモノマーを減圧脱揮して除去し、重合体を含有する濃縮物を得た。濃縮物は著しく着色していた。
酢酸ブチルを重合体の希釈溶媒として使用した。上記重合体に対して100重量部程度の酢酸ブチルで希釈し、ろ過助剤を加えて加熱処理し、ろ過した。またろ液に対して吸着剤(キョーワード700SEN、キョーワード500SH)を添加し、濾過して清澄液を得た。ろ液を濃縮し、ほぼ無色透明の重合体を得た。
得られた重合体に対して約100重量部のN,N-ジメチルアセトアミド(DMAC)に溶解させて、アクリル酸カリウム(末端Br基に対して約2モル当量)、熱安定剤(H-TEMPO:4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-n-オキシル)、吸着剤(キョーワード700SEN)、を添加し、約70℃で数時間加熱攪拌した。DMACを減圧留去し、重合体濃縮物を重合体に対して約100重量部の酢酸ブチルで希釈し、ろ過助剤を添加して固形分をろ別し、ろ液を濃縮し、片末端に紫外線架橋基としてアクリロイル基を有する重合体[P2]を得た。得られた重合体[P2]の重量平均分子量Mwは25430、分子量分布は1.10であった。重合体1分子当たりに導入された平均のアクリロイル基の数を1H NMR分析により求めたところ、約1.0個(すなわち、片末端へのアクリロイル基の導入率はほぼ100%)であった。示差走査熱量測定(DSC)から重合体[P2]のガラス-ゴム転移温度(Tg)は、-45℃であった。
(末端に反応性官能基を持たないポリアクリル酸n-ブチルの合成)
(1)重合工程
アクリル酸n-ブチル100部を脱酸素した。攪拌機付ステンレス製反応容器の内部を脱酸素し、臭化第一銅0.95部、脱酸素したアクリル酸n-ブチルのうち20部を仕込み、加熱攪拌した。アセトニトリル8.8部、開始剤としてα-ブロモ酪酸エチル1.9部を添加、混合し、混合液の温度を約80℃に調節した段階でペンタメチルジエチレントリアミン(以下、トリアミンと略す)0.018部を添加し、重合反応を開始した。残りのアクリル酸n-ブチル80部を逐次添加し、重合反応を進めた。重合途中、適宜トリアミンを追加し、重合速度を調整した。重合時に使用したトリアミンの総量は0.17部であった。重合が進行すると重合熱により内温が上昇するので内温を約80℃~約90℃に調整しながら重合を進行させた。モノマー転化率(重合反応率)が約95%以上の時点で反応容器気相部に酸素‐窒素混合ガスを導入した。内温を約80℃~約90℃に保ちながらしながら反応液を数時間加熱攪拌して反応液中の重合触媒と酸素を接触させた。アセトニトリル及び未反応のモノマーを減圧脱揮して除去し、重合体を含有する濃縮物を得た。濃縮物は著しく着色していた。
酢酸ブチルを重合体の希釈溶媒として使用した。上記重合体に対して100重量部程度の酢酸ブチルで希釈し、ろ過助剤を加えて加熱処理し、ろ過した。またろ液に対して吸着剤(キョーワード700SEN、キョーワード500SH)を添加し、濾過して清澄液を得た。ろ液を濃縮し、ほぼ無色透明の重合体を得た。
得られた重合体に対して約100重量部のN,N-ジメチルアセトアミド(DMAC)に溶解させて、酢酸カリウム(末端Br基に対して約2モル当量)、熱安定剤(H-TEMPO:4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-n-オキシル)、吸着剤(キョーワード700SEN)、を添加し、約70℃で数時間加熱攪拌した。DMACを減圧留去し、重合体濃縮物を重合体に対して約100重量部の酢酸ブチルで希釈し、ろ過助剤を添加して固形分をろ別し、ろ液を濃縮し、末端に非反応性官能基としてカルボニル基を有する重合体[P3]を得た。得られた重合体[P3]の重量平均分子量Mwは25850、分子量分布は1.14であった。重合体[P3]は、上述の各種反応触媒を用いても、反応せず、単なる線状高分子の形態を持つ(メタ)アクリル系重合体である。重合体1分子当たりに導入された平均のカルボニル基の数を1H NMR分析により求めたところ、約1.0個(すなわち、片末端への非反応性官能基の導入率はほぼ100%)であった。示差走査熱量測定(DSC)から重合体[P3]のガラス-ゴム転移温度(Tg)は、-45℃であった。
製造例1で得られた重合体[P1]100部に、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.2部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.1部を加え、十分に溶解・混合後、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより分岐高分子(A)に相当する重合体[P4]を得た。重合体1分子当たりに残存している平均のアクリロイル基の数を1H NMR分析により求めたところ、検出されなかった(すなわち、重合体[P1]のラジカル重合率はほぼ100%)。得られた重合体[P4]の重量平均分子量Mwは135882、分子量分布は3.41であった。分岐高分子(A)の前駆体(重合体[P1])の重量平均分子量Mwは12760であるため、重合体[P4]の平均の分岐数は約10.6個であった。示差走査熱量測定(DSC)から重合体[P4]のガラス-ゴム転移温度(Tg)は、-45℃であった。
製造例2で得られた重合体[P2]100部に、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.2部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.1部を加え、十分に溶解・混合後、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより分岐高分子(A)に相当する重合体[P5]を得た。重合体1分子当たりに残存している平均のアクリロイル基の数を1H NMR分析により求めたところ、検出されなかった(すなわち、重合体[P1]のラジカル重合率はほぼ100%)。示差走査熱量測定(DSC)から重合体[P5]のガラス-ゴム転移温度(Tg)は、-45℃であった。得られた重合体[P5]の重量平均分子量Mwは449719、分子量分布は7.16であった。分岐高分子(A)の前駆体(重合体[P2])の重量平均分子量Mwは25430であるため、重合体[P5]の平均の分岐数は約17.6個であった。
(両末端にアクリロイル基を有するアクリル酸n-ブチル重合体の製造方法)
(1)重合工程
アクリル酸n-ブチル100部を脱酸素した。攪拌機付ステンレス製反応容器の内部を脱酸素し、臭化第一銅0.17部、脱酸素したアクリル酸n-ブチルのうち20部を仕込み、加熱攪拌した。アセトニトリル4.4部、開始剤としてジエチル2,5-ジブロモアジペート3.5部を添加、混合し、混合液の温度を約80℃に調節した段階でペンタメチルジエチレントリアミン(以下、トリアミンと略す)0.018部を添加し、重合反応を開始した。残りのアクリル酸n-ブチル80部を逐次添加し、重合反応を進めた。重合途中、適宜トリアミンを追加し、重合速度を調整した。重合時に使用したトリアミンの総量は0.09部であった。重合が進行すると重合熱により内温が上昇するので内温を約80℃~約90℃に調整しながら重合を進行させた。モノマー転化率(重合反応率)が約95%以上の時点で反応容器気相部に酸素‐窒素混合ガスを導入した。内温を約80℃~約90℃に保ちながらしながら反応液を数時間加熱攪拌して反応液中の重合触媒と酸素を接触させた。アセトニトリル及び未反応のモノマーを減圧脱揮して除去し、重合体を含有する濃縮物を得た。濃縮物は著しく着色していた。
酢酸ブチルを重合体の希釈溶媒として使用した。上記重合体に対して100重量部程度の酢酸ブチルで希釈し、ろ過助剤を加えて加熱処理し、ろ過した。またろ液に対して吸着剤(キョーワード700SEN、キョーワード500SH)を添加し、濾過して清澄液を得た。ろ液を濃縮し、ほぼ無色透明の重合体を得た。
重合体を重合体に対して約100重量部のN,N-ジメチルアセトアミド(DMAC)に溶解させて、アクリル酸カリウム(末端Br基に対して約2モル当量)、熱安定剤(H-TEMPO:4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-n-オキシル)、吸着剤(キョーワード700SEN)、を添加し、約70℃で数時間加熱攪拌した。DMACを減圧留去し、重合体濃縮物を重合体に対して約100重量部の酢酸ブチルで希釈し、ろ過助剤を添加して固形分をろ別し、ろ液を濃縮し、両末端に紫外線架橋基としてアクリロイル基を有する重合体[P6]を得た。得られた重合体[P6]の重量平均分子量Mwは約14101、分子量分布は1.19であった。重合体1分子当たりに導入された平均のアクリロイル基の数を1H NMR分析により求めたところ、約1.9個であった。示差走査熱量測定(DSC)から重合体[P6]のガラス-ゴム転移温度(Tg)は、-45℃であった。
実施例及び比較例で作製された硬化物(試験片)の物性測定は、以下の方法、条件に従って実施した。
動的粘弾性測定装置DVA-200(アスティ計測制御社製)を使用して、測定することができる。-80℃~40℃まで温度範囲、角速度=5(1/sec)、引張ひずみ0.05%の条件で、温度分散測定を行った。
試験片は、厚み約2mm、長さ約6.5mm、幅5.5mmのサンプルの形状とした。測定から、温度に対する損失正接(tanδ)の変化を得ることができ、制振性能(ダンピング性能)の指標とした。損失正接tanδが高ければ、その材料の動的粘弾性挙動を利用して、与えられた力学的エネルギーを熱等のエネルギーとして散逸させ、エネルギーを減衰させることができる。
示差走査熱量測定(DSC)は、DSC-50(島津製作所社製)を使用して、測定することができる。昇温速度は5℃/分、温度範囲は-80℃~80℃とした。DSC測定により、ガラス-ゴム転移温度(Tg)を決定した。
製造例4で得られた分岐高分子重合体[P4]20部および製造例6で得られた重合体[P6]80部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.1部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.05部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。このゴム状硬化物シートは、分岐高分子重合体[P4]を単に含有するものであり、分岐高分子重合体[P4]が重合体[P6]由来の架橋網目に結合されたものでない。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例4で得られた分岐高分子重合体[P4]50部および製造例6で得られた重合体[P6]50部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.1部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.05部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。このゴム状硬化物シートは、分岐高分子重合体[P4]を単に含有するものであり、分岐高分子重合体[P4]が重合体[P6]由来の架橋網目に結合されたものでない。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例4で得られた分岐高分子重合体[P4]80部および製造例6で得られた重合体[P6]20部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.1部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.05部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。このゴム状硬化物シートは、分岐高分子重合体[P4]を単に含有するものであり、分岐高分子重合体[P4]が重合体[P6]由来の架橋網目に結合されたものでない。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例5で得られた分岐高分子重合体[P5]50部および、製造例6で得られた重合体[P6]50部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.1部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.05部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。このゴム状硬化物シートは、分岐高分子重合体[P5]を単に含有するものであり、分岐高分子重合体[P5]が重合体[P6]由来の架橋網目に結合されたものでない。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例5で得られた分岐高分子重合体[P5]75部および、製造例6で得られた重合体[P6]25部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.05部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.025部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。このゴム状硬化物シートは、分岐高分子重合体[P5]を単に含有するものであり、分岐高分子重合体[P5]が重合体[P6]由来の架橋網目に結合されたものでない。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例6で得られた重合体[P6]100部に、酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.2部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.1部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚のゴム状硬化物シートを得た。
得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例1で得られた重合体[P1]50部および製造例6で得られた重合体[P6]50部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.2部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.1部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚の硬化物シートを得た。このゴム状硬化物シートのミクロ構造は、重合体[P6]が架橋網目を作り、その網目に重合体[P1]由来の自由ぶらさがり鎖(いわゆるダングリング鎖)が架橋網目に結合されたものである。
得られたゴム状硬化物を用いて、剪断モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例2で得られた重合体[P2]50部および製造例6で得られた重合体[P6]50部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.2部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.1部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚の硬化物シートを得た。このゴム状硬化物シートのミクロ構造は、重合体[P6]が架橋網目を作り、その網目に重合体[P2]由来の自由ぶらさがり鎖(いわゆるダングリング鎖)が架橋網目に結合されたものである。
得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例3で得られた非反応性官能基を末端に持つ重合体[P3]60部および製造例6で得られた重合体[P6]40部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.08部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.04部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚の硬化物シートを得た。この硬化物シートは、非反応性線状高分子に相当する重合体[P3]を、重合体[P6]由来の架橋ゴム網目に閉じ込めた材料である。
得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
製造例3で得られた非反応性官能基を末端に持つ重合体[P3]75部および製造例6で得られた重合体[P6]25部に酸化防止剤IRGANOX1010を1部、光ラジカル開始剤として、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(DAROCURE1173;チバ・スペシャルティ・ケミカルズ製)0.05部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(IRGACURE819;チバ・スペシャルティ・ケミカルズ製)0.025部を加え、十分に溶解・混合後、60℃で1時間加熱脱泡を行なった。さらに型枠に流し込んで、紫外線照射装置(ライトハンマー6:Fusion UV system Japan社製)を用いてピーク照度1300mW/cm2、積算光量3000mJ/cm2の照射をすることにより2mm厚の硬化物シートを得た。この硬化物シートは、非反応性線状高分子に相当する重合体[P3]を、重合体[P6]由来の架橋ゴム網目に閉じ込めた材料である。得られたゴム状硬化物を用いて、引張モードにて動的粘弾性測定を行い、温度分散データを得た。結果を表1に示す。
これは、分岐高分子を単に含有させるだけで、ゴム状態、ゲル状態または樹脂状態の材料が著しく制振性を示すことを表している。分岐高分子が架橋網目に結合しているか、結合していないかは問題ではない。よって、ゴム状態、ゲル状態または樹脂状態にするための反応系を選択する必要もなく、任意であり、材料設計の自由度は非常に高い。また、実施例4および比較例3でも同様である。
Claims (10)
- 分岐高分子(A)および樹脂(B)を含有し、分岐高分子(A)の含有量が、分岐高分子(A)と樹脂(B)の総量100重量%に対し、15重量%以上85重量%以下である、制振材料用組成物。
- 分岐高分子(A)が(メタ)アクリル系重合体である請求項1に記載の制振材料用組成物。
- 分岐高分子(A)が櫛型高分子、又は不規則に枝分かれのある統計的高分子である請求項1または2に記載の制振材料用組成物。
- 分岐高分子(A)のゲルパーミエーションクロマトグラフィー(GPC)によりポリスチレン換算で測定した重量平均分子量(Mw)が10000以上である請求項1~3のいずれか一項に記載の制振材料用組成物。
- 樹脂(B)が(メタ)アクリル系重合体である請求項1~4のいずれか一項に記載の制振材料用組成物。
- 樹脂(B)が架橋性の官能基を有する請求項1~5のいずれか一項に記載の制振材料用組成物。
- 分岐高分子(A)からなるレオロジー調整剤。
- 分岐高分子(A)が櫛型高分子、又は不規則に枝分かれのある統計的高分子である請求項7に記載のレオロジー調整剤。
- 分岐高分子(A)が(メタ)アクリル系重合体である請求項7または8に記載のレオロジー調整剤。
- 分岐高分子(A)のゲルパーミエーションクロマトグラフィー(GPC)によりポリスチレン換算で測定した重量平均分子量(Mw)が10000以上である請求項7~9に記載のレオロジー調整剤。
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JP2015047827A (ja) * | 2013-09-04 | 2015-03-16 | 日東電工株式会社 | 制振材 |
WO2018221719A1 (ja) * | 2017-06-02 | 2018-12-06 | 北川工業株式会社 | 熱伝導材用組成物、及び熱伝導材 |
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JP2015047827A (ja) * | 2013-09-04 | 2015-03-16 | 日東電工株式会社 | 制振材 |
WO2018221719A1 (ja) * | 2017-06-02 | 2018-12-06 | 北川工業株式会社 | 熱伝導材用組成物、及び熱伝導材 |
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CN111574643A (zh) * | 2020-06-18 | 2020-08-25 | 中国热带农业科学院农产品加工研究所 | 提高天然橡胶阻尼温域的方法和橡胶 |
CN116120800A (zh) * | 2023-02-21 | 2023-05-16 | 中国人民解放军陆军工程大学 | 一种耐低温水性阻尼涂料及其制备方法 |
CN116120800B (zh) * | 2023-02-21 | 2023-10-20 | 中国人民解放军陆军工程大学 | 一种耐低温水性阻尼涂料及其制备方法 |
Also Published As
Publication number | Publication date |
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CN103140522B (zh) | 2015-07-01 |
CN103140522A (zh) | 2013-06-05 |
EP2623531B1 (en) | 2016-11-16 |
EP2623531A4 (en) | 2015-02-25 |
EP2623531A1 (en) | 2013-08-07 |
JPWO2012043426A1 (ja) | 2014-02-06 |
JP5809633B2 (ja) | 2015-11-11 |
US20130253143A1 (en) | 2013-09-26 |
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