WO2014188854A1 - Molding material for damping material, and damping material and structural member molded article obtained by molding same - Google Patents
Molding material for damping material, and damping material and structural member molded article obtained by molding same Download PDFInfo
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- WO2014188854A1 WO2014188854A1 PCT/JP2014/061882 JP2014061882W WO2014188854A1 WO 2014188854 A1 WO2014188854 A1 WO 2014188854A1 JP 2014061882 W JP2014061882 W JP 2014061882W WO 2014188854 A1 WO2014188854 A1 WO 2014188854A1
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- 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
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0442—Catalysts
- C08F299/045—Peroxy-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Definitions
- the present invention relates to a damping material molding material, a damping material obtained by molding the damping material, and a molded product for a structural member.
- the present invention relates to a molding material that can obtain a molded article having excellent vibration damping properties or sound insulation properties while maintaining mechanical strength not only at room temperature but also at high temperature, and molding formed by molding the same.
- a molding material that can obtain a molded article having excellent vibration damping properties or sound insulation properties while maintaining mechanical strength not only at room temperature but also at high temperature, and molding formed by molding the same.
- these structural members can be made of damping steel plates, rubber or elastomers can be attached, and metal parts can be used as resin parts. Replacement is generally performed.
- a damping steel plate as a structural member, the cost of itself is high, and it is difficult to process into a fine shape. There were drawbacks.
- the method of attaching rubber or elastomer to the structural member has also been a factor in increasing costs due to an increase in processing steps and the number of parts.
- the present invention provides a molding material that can obtain a molded product having excellent vibration damping properties or soundproofing properties while maintaining mechanical strength not only at room temperature but also at high temperatures, and It aims at providing the molded article formed by shape
- the present invention is shown by the following (1) to (10).
- a molding material for vibration damping material composed of at least one segment (Y) having a temperature equal to or higher than ° C.
- the amount of the elastomer (B) added is 10 to 40 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A-1) or vinyl ester resin (A-2).
- the addition amount of the fiber (C) is 3 to 300 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A-1) or vinyl ester resin (A-2). )
- the damping material molding material according to any one of the above.
- the unsaturated polyester resin (A-1) or the vinyl ester resin (A-2) is composed of two or more resins each having a glass transition temperature of 100 ° C. or higher and lower than 100 ° C. after curing alone.
- the molding material for damping material according to any one of (1) to (4).
- the present invention relates to two or more kinds of unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different Tg after curing, an elastomer (B) which is a block copolymer or a graft copolymer, and fibers.
- a molding material for damping material characterized by containing (C), which has excellent mechanical and damping properties while maintaining mechanical strength not only at room temperature but also at high temperature Can be obtained.
- the Tg of the segment (X) constituting the block copolymer or graft copolymer of the elastomer (B) is 10 ° C. or more and less than 80 ° C., and the Tg of the segment (Y) is 80 ° C. or more.
- the damping material molding material of the present invention comprises two or more unsaturated polyester resins (A-1) or vinyl ester resins (A-2), block copolymers or graft copolymers having different Tg of cured products.
- the component (A) used in the present invention is excellent in mechanical strength even at high temperatures, and a molded product having excellent vibration damping or soundproofing properties can be obtained.
- a combination of the above and two or more unsaturated polyester resins (A-1) and vinyl ester resins (A-2) of less than 100 ° C. is preferable.
- the Tg is more preferably 100 to 300 ° C., and further preferably 150 to 250 ° C.
- the Tg is more preferably 30 to 90 ° C., and further preferably 40 to 80 ° C.
- Tg is obtained from the temperature at which the loss factor (tan ⁇ ) is maximum obtained by the measurement method specified in JIS K7244- (4).
- the measuring method of Tg is as follows, for example. 3 parts by mass of a curing agent (D) (tert-butylbenzoyl peroxide) is added to 100 parts by mass of a single unsaturated polyester resin (A-1) or vinyl ester resin (A-2). Kneading with a double-arm kneader at °C. Next, transfer molding is performed on the obtained molding material using a ⁇ 120 mm disk molding die (fan gate) at an injection time of 60 sec, a curing time of 120 sec, a pressure of 10 MPa, and a molding temperature of 150 ° C. to obtain a molded product.
- D tert-butylbenzoyl peroxide
- a test piece having a length of 45 mm, a width of 3 mm, and a thickness of 3 mm was cut out from the obtained molded product, and the cut out test piece was sinusoidal with a frequency of 1 Hz using a tensile complex modulus measuring device (manufactured by GABO, EPLEXOR100N).
- a loss factor (tan ⁇ ) is obtained by applying a simple tensile force to the test piece and measuring the force applied to the test piece, the amplitude of the displacement cycle, and the phase difference between the two.
- the test piece is installed with a distance between clamps of 30 mm. Further, when measuring the tensile complex elastic modulus, it is possible to measure in the range of 20 to 300 ° C. at intervals of 2 ° C., and to perform a master plot using the frequency-temperature conversion rule.
- the temperature at which the obtained loss coefficient (tan ⁇ ) is maximum can be adopted as Tg.
- the unsaturated polyester resin (A-1) used in the present invention is a condensation product (unsaturated polyester) obtained by esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary). Is dissolved in a reactive diluent such as styrene monomer as necessary.
- a reactive diluent such as styrene monomer as necessary.
- the unsaturated polyester used as a raw material for the component (A) those produced by a known method can be used.
- polybasic acids or anhydrides having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid, and fumaric acid, maleic acid, itaconic acid
- a polymerizable unsaturated polybasic acid or an anhydride thereof such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, bisphenol A, hydrogenated bisphenol A , Ethy
- maleic anhydride terephthalic acid, fumaric acid, isophthalic acid, and phthalic anhydride are preferable in terms of cost and physical properties.
- polyhydric alcohol propylene glycol, diethylene glycol, neopentyl glycol, dipropylene glycol, hydrogenated bisphenol A, and ethylene glycol are preferable in terms of price and physical properties.
- the unsaturated polyester preferably has an unsaturated group equivalent (molecular weight per unsaturated group) of 100 to 800. Those having an unsaturated group equivalent of less than 100 tend not to be synthesized, and if the unsaturated group equivalent exceeds 800, a cured product having a high hardness tends to be unable to be obtained.
- the acid value of the unsaturated polyester is preferably 40 mgKOH / g or less, and more preferably 25 mgKOH / g or less.
- the acid value of unsaturated polyester is measured by the method of JIS K6901 5.3.
- the unsaturated polyester resin (A-1) is usually obtained by blending a reactive diluent having an unsaturated group typified by a styrene monomer with the unsaturated polyester as necessary.
- the reactive diluent having an unsaturated group enhances kneadability and impregnation with the fiber (C) and the inorganic filler when producing BMC, and the hardness, strength, chemical resistance, heat resistance, etc. of the molded product Styrene monomer is particularly effective for obtaining a well-balanced physical property.
- the addition amount of the reactive diluent having an unsaturated group is preferably 10 to 250 parts by mass, more preferably 20 to 100 parts by mass, and further preferably 30 to 80 parts by mass with respect to 100 parts by mass of the unsaturated polyester alone. If the addition amount of the reactive diluent is less than 10 parts by mass, workability, impregnation and corrosion resistance tend to deteriorate due to high viscosity. If the addition amount exceeds 250 parts by mass, sufficient strength and heat resistance are obtained. Tend not to be obtained.
- a reactive diluent other than the styrene monomer may be used as the reactive diluent having an unsaturated group.
- examples include styrene monomers such as chlorostyrene, vinyltoluene, and divinylbenzene, other polymerizable monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and ethylene glycol di (meth) acrylate, and other special reactions.
- the diluent include, but are not limited to, diallyl phthalate monomer, diallyl phthalate prepolymer, triallyl isocyanurate, and the like. These may be used alone or in combination.
- the unsaturated polyester resin (A-1) may be a kind of polyester (meth) acrylate resin in which glycidyl (meth) acrylate is added to the terminal carboxyl group.
- the vinyl ester resin (A-2) used in the present invention is also called an epoxy acrylate resin and is generally a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid.
- a compound having a polymerizable unsaturated bond (vinyl ester) produced by a ring-opening reaction with benzene is dissolved in a reactive diluent.
- “Polyester resin handbook” (Eiichiro Takiyama, Nikkan Kogyo Shimbun, 1988) Issue) and “painting glossary” (edited by the Color Material Association, published by Gihodo, published in 1993).
- the vinyl ester used as a raw material for the vinyl ester resin (A-2) (epoxy acrylate resin) is produced by a known method.
- An unsaturated monobasic acid such as acrylic acid is added to the epoxy resin.
- it is epoxy (meth) acrylate obtained by making methacrylic acid react.
- various epoxy resins may be reacted with bisphenol (for example, bisphenol A) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: manufactured by Harima Kasei Co., Ltd.) to impart flexibility. .
- Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolac glycidyl ethers, and the like.
- an epoxy resin a bisphenol A type epoxy resin is preferable in terms of price and physical properties.
- methacrylic acid is preferable in terms of cost and physical properties.
- the vinyl ester preferably has an unsaturated group equivalent (molecular weight per unsaturated group) of 100 to 800. Those having an unsaturated group equivalent of less than 100 tend not to be synthesized, and if the unsaturated group equivalent exceeds 800, a cured product having a high hardness tends to be unable to be obtained.
- unsaturated group equivalent molecular weight per unsaturated group
- the vinyl ester resin (A-2) is usually obtained by blending a reactive diluent having an unsaturated group typified by a styrene monomer with the vinyl ester.
- the reactive diluent having an unsaturated group enhances the kneadability impregnation property with the fiber (C) and the inorganic filler when producing BMC, and improves the hardness, strength, chemical resistance, heat resistance, etc. of the molded product.
- Styrene monomer is particularly effective for improving the properties and obtaining balanced physical properties.
- the addition amount of the reactive diluent having an unsaturated group is preferably 10 to 250 parts by mass, more preferably 30 to 200 parts by mass, and further preferably 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl ester. If the addition amount of the reactive diluent is less than 10 parts by mass, workability, impregnation and corrosion resistance tend to deteriorate due to high viscosity. If the addition amount exceeds 250 parts by mass, sufficient strength and heat resistance are obtained. Tend not to be obtained.
- a reactive diluent other than the styrene monomer may be used as the reactive diluent having an unsaturated group.
- examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
- Component (A) may be blended with a radical curable resin such as a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, or a diallyl phthalate resin.
- a radical curable resin such as a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, or a diallyl phthalate resin.
- the elastomer (B) used in the present invention is a block copolymer or graft copolymer, a segment (X) having a Tg of 10 ° C. or higher and lower than 80 ° C., and a segment (Y) having a Tg of 80 ° C. or higher. ) At least two types of segments. By being composed of at least two types of segments (X) having a Tg of 10 ° C. or more and less than 80 ° C. and a segment (Y) having a Tg of 80 ° C. or more, not only at normal temperature but also at high temperature Even in such a case, it is possible to obtain a molded product having excellent vibration damping properties and soundproofing properties while maintaining mechanical strength.
- the Tg of the segment (X) is more preferably 10 to 70 ° C., and further preferably 20 to 60 ° C.
- the Tg of the segment (Y) is more preferably 80 to 150 ° C, and further preferably 80 to 130 ° C.
- a homopolymer having each of segment (X) and segment (Y) alone as a constituent unit was synthesized, and the loss was in accordance with JIS K7244- (4).
- the temperature at which the coefficient (tan ⁇ ) is maximized is obtained, or Tg can be calculated for each of the segment (X) and the segment (Y) using the FOX equation.
- the molar ratio of the structural unit derived from the monomer in the segment (X) constituting the elastomer (B) to the structural unit derived from the monomer in the segment (Y) is preferably 5: 5 to 7: 3, and 5: 5 to 6 : 4 is more preferable.
- the elastomer (B) for example, one or more of a block copolymer or a graft copolymer composed of segments such as polystyrene, polymethyl methacrylate, and polyvinyl acetate that are effective as a low shrinkage agent are used. Can do.
- the segment (X) constituting the elastomer (B) include a polyvinyl acetate segment, polyamide, polylactic acid, polybutylene terephthalate, and polyethylene terephthalate.
- the segment (Y) include a polystyrene segment, a polymethyl methacrylate segment, and a poly (ethylene methacrylate) segment.
- the elastomer (B) is preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, and still more preferably 20 to 30 parts by weight with respect to 100 parts by weight of the component (A).
- the blending amount is less than 10 parts by mass, the loss factor tends to be small, and when it exceeds 40 parts by mass, the strength at high temperature tends to be remarkably deteriorated.
- the elastomer (B) is a block copolymer
- the elastomer (B) is, for example, segment (X) -segment (Y), segment (X) -segment (Y) -segment (X), segment (Y)
- a configuration such as a segment (X) and a segment (Y) can be adopted.
- the segment (X) is a main chain
- the segment (Y) is a graft copolymer (side chain)
- the segment (Y) is a main chain. Any of the graft copolymers in which the segment (X) is a graft chain (side chain) can be used.
- the fiber (C) used in the present invention is not particularly limited, but when used for forming with flow such as transfer molding, a fiber (C) cut to a fiber length of about 1.5 to 25 mm is preferable.
- the fiber length of the fiber (C) is more preferably 6 to 25 mm, further preferably 9 to 25 mm.
- organic and inorganic fibers such as glass fiber, carbon fiber, pulp fiber, Tetron (registered trademark) fiber, vinylon fiber, aramid fiber, polyethylene terephthalate fiber, and wollastonite, may be used. it can.
- glass fiber is preferable in terms of price and physical properties.
- chopped strand glass is preferable.
- the blending amount of the fiber (C) is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, and still more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the component (A).
- the blending amount of the fiber (C) is more than 300 parts by mass, problems such as impregnation and fluidity of the damping material molding material occur, and the moldability tends to deteriorate.
- the amount of the fiber (C) is less than 3 parts by mass, the strength tends to be insufficient.
- Curing agents are those classified as well known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates as organic peroxide catalysts. Azo compounds are also effective.
- Specific examples include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, ditertiary butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, Bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, Azobisisobutyronitrile, azo-bis-carboxylic amide can be used
- the curing agent is preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the component (A).
- thickeners in addition to the above components, thickeners, thickeners, pigments, inorganic fillers, curing agents, internal mold release agents, and the like can be used as necessary.
- thickener examples include metal oxides such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, metal hydroxides, and isocyanate compounds. It is not always necessary to use a thickener.
- the inorganic filler calcium carbonate and aluminum hydroxide are mainly used, but other known fillers such as glass powder, glass beads, silica, talc, clay, alumina, barium sulfate, and titanium oxide can be used. These inorganic fillers may be used individually by 1 type, and can also be used in combination of 2 or more type.
- the blending amount of the inorganic filler is preferably 100 to 500 parts by mass, more preferably 200 to 450 parts by mass, and further preferably 200 to 300 parts by mass with respect to 100 parts by mass of the component (A).
- the blending amount of the inorganic filler When the blending amount of the inorganic filler is more than 500 parts by mass, the viscosity of the damping material molding material becomes high, and problems such as impregnation and fluidity are impaired, and physical properties tend to be lowered. When the blending amount of the inorganic filler is less than 100 parts by mass, the fluidity is too large, and physical properties such as hot strength tend to decrease.
- the shape of the inorganic filler is not particularly limited, but preferably has a weight average particle size of 0.5 ⁇ m to 50 ⁇ m, more preferably 0.5 ⁇ m to 30 ⁇ m, and even more preferably 1 ⁇ m to 20 ⁇ m.
- the average particle size is less than 0.5 ⁇ m, the viscosity tends to be high, and there is a tendency that a molded product cannot be produced.
- the average particle size is more than 50 ⁇ m, the fluidity of the damping material is poor and the moldability tends to be poor.
- Examples of the internal mold release agent include stearic acid, zinc stearate, calcium stearate, aluminum stearate, stearates such as magnesium stearate, carnauba wax, and the like, and these can be used or used in appropriate ratios. .
- the molding material for vibration damping material of the present invention constituted by the components as described above can be obtained by kneading the components (A) to (D) and the like using a usual method, for example, a kneader. .
- the method is not particularly limited. For example, compression molding, transfer molding, injection molding, or the like is adopted, and a cured product having a cured product having a phase separation structure is obtained. It has vibration-damping properties and can obtain a high-strength molded product.
- the damping material obtained by molding the molding material for damping material of the present invention preferably has a flexural modulus at 130 ° C. of 6 GPa or more, more preferably 7 GPa or more, and 8 GPa or more. Further preferred.
- the flexural modulus in this case is measured based on JIS K6911.
- the damping elastic modulus of the damping material at 130 ° C. is 6 GPa or more, the resulting molded product tends to be able to maintain the mechanical strength at a high temperature.
- the method for measuring the flexural modulus is as follows. Measurement was performed based on JIS K6911 using a molded product obtained by compression molding at a molding temperature of 150 ° C., a molding pressure of 10 MPa, and a curing time of 3 minutes. Specifically, a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was formed, and the thickness direction of the obtained test piece was perpendicular to the ground so that the distance between supporting points was 64 mm below the test piece. A fulcrum was established so that Using a bending tester (manufactured by Shimadzu Corporation, Autograph AG-X plus) under the conditions of 23 ° C.
- a bending tester manufactured by Shimadzu Corporation, Autograph AG-X plus
- a pressure wedge of 2 mm / min is applied to the center of the test piece from above the test piece.
- a load was applied at a load speed, the change in the deflection of the central part of the test piece due to the load was measured, and a load-deflection curve was drawn.
- a bending elastic modulus is computed using the following formula
- the vibration damping material of the present invention preferably has a loss coefficient at 80 ° C. of 0.05 or more and a loss coefficient at 120 ° C. of 0.06 or more.
- the loss factor in this case is measured based on JIS K7244- (4).
- the loss factor at 80 ° C. of the damping material is 0.05 or more, and the loss factor at 120 ° C. is 0.06 or more, so that the loss factor is high in a wide temperature range and the damping property is good. There is a tendency.
- the obtained molding material is subjected to transfer molding at an injection time of 60 sec, a curing time of 120 sec, a pressure of 10 MPa, and a molding temperature of 150 ° C.
- test piece having a length of 45 mm, a width of 3 mm, and a thickness of 3 mm was cut out from the obtained molded product, and the cut out test piece was sinusoidal with a frequency of 1 Hz using a tensile complex modulus measuring device (manufactured by GABO, EPLEXOR100N).
- a loss factor (tan ⁇ ) is obtained by applying a simple tensile force to the test piece and measuring the force applied to the test piece, the amplitude of the displacement cycle, and the phase difference between the two.
- the test piece is installed with a distance between clamps of 30 mm. Further, when measuring the tensile complex elastic modulus, it is possible to measure in the range of 20 to 130 ° C. at intervals of 2 ° C., and to perform a master plot using the frequency-temperature conversion rule.
- ⁇ Unsaturated polyester resin (Tg: 190 ° C.)> A blended composition consisting of 80 mol of propylene glycol, 20 mol of hydrogenated bisphenol A, and 100 mol of maleic anhydride was condensed at 200 ° C. under an inert gas to obtain an unsaturated polyester. 60 parts by mass of the obtained unsaturated polyester was dissolved in 40 parts by mass of a styrene monomer to prepare an unsaturated polyester resin.
- ⁇ Vinyl ester resin (Tg: 130 ° C.)> A compound composed of 1.0 equivalent of bisphenol A type epoxy resin (AER-2603, manufactured by Asahi Kasei Corporation) and 1.0 equivalent of methacrylic acid was reacted at 140 ° C. to obtain a vinyl ester. 50 parts by mass of the obtained vinyl ester was dissolved in 50 parts by mass of a styrene monomer to prepare a vinyl ester resin.
- Table 1 shows the Tg of a cast plate (manufacturing method is described below) prepared only with each unsaturated polyester resin or vinyl ester resin.
- Tg was measured by the following method. 3 parts by mass of tert-butylbenzoyl peroxide was added to 100 parts by mass of the unsaturated polyester resin or vinyl ester resin obtained above, and these were kneaded at 30 ° C. using a double-arm kneader. Next, the obtained molding material was subjected to transfer molding at an injection time of 60 sec, a curing time of 120 sec, a pressure of 10 MPa, and a molding temperature of 150 ° C. using a ⁇ 120 mm disk molding die (fan gate) to obtain a molded product. .
- a test piece having a length of 45 mm, a width of 3 mm, and a thickness of 3 mm was cut out from the obtained molded product, and the cut out test piece was sinusoidal with a frequency of 1 Hz using a tensile complex modulus measuring device (manufactured by GABO, EPLEXOR100N).
- a loss factor (tan ⁇ ) was determined by applying a simple tensile force to the test piece and measuring the force applied to the test piece, the amplitude of the displacement cycle, and the phase difference between the two.
- the test piece was installed with the distance between clamps of 30 mm.
- measurement of the tensile complex elastic modulus measurement was performed in the range of 20 to 300 ° C. at intervals of 2 ° C., and a master plot was performed using a frequency-temperature conversion rule. The temperature at which the obtained loss coefficient (tan ⁇ ) was maximized was adopted as Tg.
- each compounding component with the compounding composition shown in Tables 1 and 2 was kneaded at 30 ° C using a double-arm kneader.
- the molding materials for vibration damping materials of Examples 1 to 11 and Comparative Examples 1 to 12 were obtained.
- Each of the damping material molding materials was transfer molded using a ⁇ 120 mm disk molding die (fan gate) at an injection time of 60 sec, a curing time of 120 sec, a pressure of 10 MPa, and a molding temperature of 150 ° C.
- FIG. 1 is a view showing an appearance of a molded product obtained by transfer molding of the damping material molding materials obtained in Examples 1 to 11 and Comparative Examples 1 to 12 using a disk molding die.
- FIG. 1A is a top view of the obtained molded product
- FIG. 1B is a left side view of the obtained molded product.
- the molded product 1 includes a disk-shaped molded product main body 2 having a diameter of 120 mm and a thickness of 3 mm, and a gate portion 3 having a thickness of 2 mm fixed on the circumference of the molded product main body 2.
- the maximum width of the gate portion 3 is 30 mm, and the width becomes narrower as it goes away from the center direction of the molded product body 2.
- a test piece 4 having a length of 45 mm and a width of 3 mm is formed from the molded product 1 obtained by transfer molding in a direction parallel to the glass fiber orientation (hereinafter referred to as the orientation direction) and the glass fiber. Each was cut out so as to be in a direction perpendicular to the orientation (hereinafter referred to as non-orientation direction).
- the loss factor (tan ⁇ ) was measured based on JIS K7244- (4), and the average values of the test pieces in the orientation direction and the non-orientation direction are shown in Tables 1 and 2.
- . 2A is a top view of the disk molding die
- FIG. 2B is a left side view of the disk molding die.
- the loss factor was measured by the following method. About the cut-out test piece, a sinusoidal tensile force with a frequency of 1 Hz was applied to the test piece at 40 ° C., 80 ° C., and 120 ° C. using a tensile complex elastic modulus measuring device (manufactured by GABO, EPLEXOR100N). The loss factor (tan ⁇ ) at each temperature was determined by measuring the force applied to the above, the amplitude of the displacement cycle, and the phase difference between the two. In addition, the test piece was installed with the distance between clamps of 30 mm.
- the bending strength, flexural modulus, and molding shrinkage were measured based on JIS K6911 using a molded product obtained by compression molding at a molding temperature of 150 ° C., a molding pressure of 10 MPa, and a curing time of 3 minutes. Specifically, a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was formed, and the thickness direction of the obtained test piece was perpendicular to the ground so that the distance between supporting points was 64 mm below the test piece. A fulcrum was established so that Using a bending tester (manufactured by Shimadzu Corporation, Autograph AG-X plus) under the conditions of 23 ° C.
- the present invention can be used as a molding material for obtaining a molded article for a structural member that requires vibration damping.
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Abstract
Description
その硬化物のTgが異なる、2種以上の不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)(以下、成分(A)ということがある)は、その硬化物のTgの異なる2種類の不飽和ポリエステル樹脂(A-1)の組み合わせ、その硬化物のTgの異なる2種類のビニルエステル樹脂(A-2)の組み合わせ、その硬化物のTgの異なる不飽和ポリエステル樹脂(A-1)とビニルエステル樹脂(A-2)の組み合わせとすることができる。 <Unsaturated polyester resin (A-1), vinyl ester resin (A-2)>
Two or more kinds of unsaturated polyester resins (A-1) or vinyl ester resins (A-2) (hereinafter sometimes referred to as component (A)) having different Tg of the cured product are those of Tg of the cured product. Combination of two different types of unsaturated polyester resins (A-1), combination of two types of vinyl ester resins (A-2) having different Tg of the cured product, unsaturated polyester resins having different Tg of the cured product (A -1) and vinyl ester resin (A-2).
本発明に用いられるエラストマー(B)は、ブロック共重合体又はグラフト共重合体であり、Tgが10℃以上で80℃未満であるセグメント(X)、及びTgが80℃以上であるセグメント(Y)の少なくとも2種以上のセグメントから構成される。Tgが10℃以上で80℃未満であるセグメント(X)、及びTgが80℃以上であるセグメント(Y)の少なくとも2種以上のセグメントから構成されることで、常温時だけでなく高温時であっても機械的強度を保持しつつ、制振性あるいは防音性に優れた成形品を得る事ができる。 <Elastomer (B)>
The elastomer (B) used in the present invention is a block copolymer or graft copolymer, a segment (X) having a Tg of 10 ° C. or higher and lower than 80 ° C., and a segment (Y) having a Tg of 80 ° C. or higher. ) At least two types of segments. By being composed of at least two types of segments (X) having a Tg of 10 ° C. or more and less than 80 ° C. and a segment (Y) having a Tg of 80 ° C. or more, not only at normal temperature but also at high temperature Even in such a case, it is possible to obtain a molded product having excellent vibration damping properties and soundproofing properties while maintaining mechanical strength.
本発明で使用する繊維(C)としては、特に限定はないが、トランスファー成形など流動をともなう成形に用いる場合には、繊維長1.5~25mm程度に切断した繊維(C)が好ましい。繊維(C)の繊維長は6~25mmがより好ましく、9~25mmがさらに好ましい。また繊維(C)の種類としては、ガラス繊維、カーボン繊維、パルプ繊維、テトロン(登録商標)繊維、ビニロン繊維、アラミド繊維、ポリエチレンテレフタレート繊維、ワラストナイト等の有機、無機繊維を使用することができる。これらの中でもガラス繊維が価格、物性の点で好ましい。さらには、チョップドストランドガラスが好ましい。繊維(C)の配合量は、成分(A)100質量部に対して3~300質量部が好ましく、5~200質量部がより好ましく、50~150質量部がさらに好ましい。繊維(C)の配合量が300質量部よりも多い場合には制振材用成形材料の含浸性、流動性を損なうなどの問題が発生し、成形性が悪化するなどの傾向にある。繊維(C)の配合量が3質量部よりも少ない場合には、強度が不十分となる傾向にある。 <Fiber (C)>
The fiber (C) used in the present invention is not particularly limited, but when used for forming with flow such as transfer molding, a fiber (C) cut to a fiber length of about 1.5 to 25 mm is preferable. The fiber length of the fiber (C) is more preferably 6 to 25 mm, further preferably 9 to 25 mm. Moreover, as a kind of fiber (C), organic and inorganic fibers, such as glass fiber, carbon fiber, pulp fiber, Tetron (registered trademark) fiber, vinylon fiber, aramid fiber, polyethylene terephthalate fiber, and wollastonite, may be used. it can. Among these, glass fiber is preferable in terms of price and physical properties. Furthermore, chopped strand glass is preferable. The blending amount of the fiber (C) is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, and still more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the fiber (C) is more than 300 parts by mass, problems such as impregnation and fluidity of the damping material molding material occur, and the moldability tends to deteriorate. When the amount of the fiber (C) is less than 3 parts by mass, the strength tends to be insufficient.
硬化剤は、有機過酸化物系触媒として、公知のケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネートに分類されるものがあり、またアゾ化合物も有効である。具体例としては、例えばベンゾイルパーオキサイド、ジクミルパーオキサイド、ジイソプロピルパーオキサイド、ジターシャリーブチルパーオキサイド、t-ブチルパーオキシベンゾエート、1,1ービス(t-ブチルパーオキシ)ー3,3,5ートリメチルシクロヘキサン、2,5ージメチルー2,5ービス(t-ブチルパーオキシ)ヘキシンー3、3ーイソプロピルヒドロパーオキサイド、t-ブチルヒドロパーオキサイド、ジクミルパーオキサイド、ジクミルヒドロパーオキサイド、アセチルパーオキサイド、ビス(4ーt-ブチルシクロヘキシル)パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソブチルパーオキサイド、3,3,5ートリメチルヘキサノイルパーオキサイド、ラウリルパーオキサイド、アゾビスイソブチロニトリル、アゾビスカルボンアミドなどが使用できる。保存安定性が良好でジクミルパーオキサイド、ジターシャリーブチルパーオキサイド、t-ブチルハイドロパーオキサイドなどは特に有効である。硬化剤は、成分(A)100質量部に対して、1~10質量部であることが好ましく、2~5質量部であることがより好ましい。 <Curing agent (D)>
Curing agents are those classified as well known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates as organic peroxide catalysts. Azo compounds are also effective. Specific examples include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, ditertiary butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, Bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, Azobisisobutyronitrile, azo-bis-carboxylic amide can be used. Dicumyl peroxide, ditertiary butyl peroxide, t-butyl hydroperoxide and the like are particularly effective because of good storage stability. The curing agent is preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the component (A).
プロピレングリコール80モル、水素化ビスフェノールA20モル、無水マレイン酸100モルからなる配合組成物を不活性ガス下に200℃で縮合することでエステル化をし、不飽和ポリエステルを得た。この得られた不飽和ポリエステル60質量部を、スチレンモノマー40質量部に溶解し、不飽和ポリエステル樹脂を作製した。 <Unsaturated polyester resin (Tg: 190 ° C.)>
A blended composition consisting of 80 mol of propylene glycol, 20 mol of hydrogenated bisphenol A, and 100 mol of maleic anhydride was condensed at 200 ° C. under an inert gas to obtain an unsaturated polyester. 60 parts by mass of the obtained unsaturated polyester was dissolved in 40 parts by mass of a styrene monomer to prepare an unsaturated polyester resin.
ジエチレングリコール100モル、テレフタル酸50モルからなる配合組成物を不活性ガス下に200℃で、酸価5mgKOH/g以下になるまで1次反応させた後、無水マレイン酸20モル、無水フタル酸30モルを加え、反応温度200℃で酸価40mgKOH/g以下になるまで二次反応させる事により不飽和ポリエステルを得た。この得られた不飽和ポリエステル70質量部を、スチレンモノマー30質量部に溶解し、不飽和ポリエステル樹脂を作製した。なお、酸価は、JIS K6901 5.3により測定した。 <Unsaturated polyester resin (Tg: 60 ° C.)>
A blended composition consisting of 100 moles of diethylene glycol and 50 moles of terephthalic acid was subjected to a primary reaction under an inert gas at 200 ° C. until an acid value of 5 mgKOH / g or less, and then 20 moles of maleic anhydride and 30 moles of phthalic anhydride. Was added to carry out a secondary reaction until the acid value reached 40 mgKOH / g or less at a reaction temperature of 200 ° C. to obtain an unsaturated polyester. 70 parts by mass of the obtained unsaturated polyester was dissolved in 30 parts by mass of a styrene monomer to prepare an unsaturated polyester resin. The acid value was measured according to JIS K6901 5.3.
ビスフェノールA型エポキシ樹脂1.0当量(旭化成株式会社製、AER-2603)及びメタクリル酸1.0当量からなる配合組成物を140℃で反応させ、ビニルエステルを得た。この得られたビニルエステル50質量部を、スチレンモノマー50質量部に溶解し、ビニルエステル樹脂を作製した。 <Vinyl ester resin (Tg: 130 ° C.)>
A compound composed of 1.0 equivalent of bisphenol A type epoxy resin (AER-2603, manufactured by Asahi Kasei Corporation) and 1.0 equivalent of methacrylic acid was reacted at 140 ° C. to obtain a vinyl ester. 50 parts by mass of the obtained vinyl ester was dissolved in 50 parts by mass of a styrene monomer to prepare a vinyl ester resin.
上記の方法により得られた不飽和ポリエステル樹脂およびビニルエステル樹脂を用いて、表1及び2に示す配合組成でそれぞれの配合成分を、30℃で双腕型ニーダーを用いて混練することで、実施例1~11及び比較例1~12の制振材用成形材料を得た。この各制振材用成形材料を、φ120mmの円盤成形金型(ファンゲート)を用いて、射出時間60sec、硬化時間120sec、圧力10MPa、成形温度150℃でトランスファー成形した。 <Production of damping material molding material and damping material>
Using the unsaturated polyester resin and vinyl ester resin obtained by the above method, each compounding component with the compounding composition shown in Tables 1 and 2 was kneaded at 30 ° C using a double-arm kneader. The molding materials for vibration damping materials of Examples 1 to 11 and Comparative Examples 1 to 12 were obtained. Each of the damping material molding materials was transfer molded using a φ120 mm disk molding die (fan gate) at an injection time of 60 sec, a curing time of 120 sec, a pressure of 10 MPa, and a molding temperature of 150 ° C.
Regarding the molding compression ratio, after molding, each of the test piece and the mold was allowed to stand for 24 hours at a temperature of 23 ° C. and a humidity of 50%, and the dimensions of the test piece and the mold were measured. Shrinkage was calculated. The results are shown in Tables 1 and 2.
2 成形品本体
3 ゲート部
4 試験片 DESCRIPTION OF
Claims (10)
- それぞれ単独で硬化後のガラス転移温度が異なる2種以上の不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)、ブロック共重合体又はグラフト共重合体であるエラストマー(B)、繊維(C)及び硬化剤(D)を含有し、エラストマー(B)が、ガラス転移温度が10℃以上で80℃未満であるセグメント(X)の少なくとも1種及びガラス転移温度が80℃以上であるセグメント(Y)の少なくとも1種から構成される制振材用成形材料。 Two or more unsaturated polyester resins (A-1) or vinyl ester resins (A-2) each having a different glass transition temperature after curing, an elastomer (B) that is a block copolymer or a graft copolymer, The fiber (C) and the curing agent (D) are contained, and the elastomer (B) has a glass transition temperature of 10 ° C. or higher and lower than 80 ° C. and at least one segment (X) and a glass transition temperature of 80 ° C. or higher. A molding material for vibration damping material comprising at least one kind of a certain segment (Y).
- それぞれ単独で硬化後のガラス転移温度が異なる2種以上の不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)、ブロック共重合体又はグラフト共重合体であるエラストマー(B)、繊維(C)及び硬化剤(D)を含有し、エラストマー(B)が、酢酸ビニル由来の構成単位からなるセグメント(X)、及びスチレン又はメチルメタクリレート由来の構成単位からなるセグメント(Y)の少なくとも2種以上のセグメントから構成される制振材用成形材料。 Two or more unsaturated polyester resins (A-1) or vinyl ester resins (A-2) each having a different glass transition temperature after curing, an elastomer (B) that is a block copolymer or a graft copolymer, A segment (X) comprising a fiber (C) and a curing agent (D), the elastomer (B) comprising a structural unit derived from vinyl acetate, and a segment (Y) comprising a structural unit derived from styrene or methyl methacrylate; Molding material for damping material composed of two or more types of segments.
- エラストマー(B)の添加量が、不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)100質量部に対して10~40質量部である請求項1又は2に記載の制振材用成形材料。 The vibration damping according to claim 1 or 2, wherein the addition amount of the elastomer (B) is 10 to 40 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A-1) or the vinyl ester resin (A-2). Molding material for materials.
- 繊維(C)の添加量が、不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)100質量部に対して3~300質量部である請求項1~3のいずれかに記載の制振材用成形材料。 The amount of the fiber (C) added is 3 to 300 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A-1) or vinyl ester resin (A-2). Molding material for damping material.
- 前記不飽和ポリエステル樹脂(A-1)又はビニルエステル樹脂(A-2)が、それぞれ単独で硬化後のガラス転移温度が100℃以上と100℃未満である2種以上の樹脂からなる、請求項1~4のいずれかに記載の制振材用成形材料。 The unsaturated polyester resin (A-1) or the vinyl ester resin (A-2) is composed of two or more resins each having a glass transition temperature of 100 ° C. or higher and lower than 100 ° C. after being cured alone. 5. A molding material for damping material according to any one of 1 to 4.
- 前記セグメント(X)におけるモノマー由来の構成単位と前記セグメント(Y)におけるモノマー由来の構成単位とのモル比が5:5~3:7である請求項1~5のいずれかに記載の制振材用成形材料。 6. The vibration damping according to claim 1, wherein the molar ratio of the monomer-derived structural unit in the segment (X) to the monomer-derived structural unit in the segment (Y) is 5: 5 to 3: 7. Molding material for materials.
- 請求項1~6のいずれかに記載の制振材用成形材料を成形して得られる制振材。 A damping material obtained by molding the damping material molding material according to any one of claims 1 to 6.
- 130℃における曲げ弾性率が6GPa以上である請求項6に記載の制振材。 The vibration damping material according to claim 6, wherein the bending elastic modulus at 130 ° C is 6 GPa or more.
- 80℃における損失係数が0.05以上であり、120℃における損失係数が0.06以上である請求項7又は8に記載の制振材。 The damping material according to claim 7 or 8, wherein a loss coefficient at 80 ° C is 0.05 or more and a loss coefficient at 120 ° C is 0.06 or more.
- 請求項1~6のいずれかに記載の制振材用成形材料を成形してなる構造部材用成形品。 A molded article for a structural member obtained by molding the damping material molding material according to any one of claims 1 to 6.
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CN201480029483.6A CN105283476B (en) | 2013-05-21 | 2014-04-28 | Damping material damping material and structural elements products formed with moulding material and obtained from being molded |
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2014
- 2014-04-28 CN CN201480029483.6A patent/CN105283476B/en not_active Expired - Fee Related
- 2014-04-28 WO PCT/JP2014/061882 patent/WO2014188854A1/en active Application Filing
- 2014-04-28 JP JP2015518176A patent/JP6364405B2/en active Active
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JPH08301998A (en) * | 1995-05-01 | 1996-11-19 | Mitsubishi Motors Corp | Vibration damping resin composition and structural vibration damping resin molding made from the same |
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JP6364405B2 (en) | 2018-07-25 |
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