JP6364405B2 - Molding material for damping material, damping material obtained by molding this, and molded product for structural member - Google Patents

Description

  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. In particular, 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. Related to goods.

  Motor parts used in automobiles, industrial equipment, home appliances, and the like cause vibration and noise. As a method of reducing and preventing these vibrations and noises and providing vibration damping and soundproofing, 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. Here, when using 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. In addition, 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.

  On the other hand, it is known that by replacing a metal part with a resin part in a part that requires vibration damping, the vibration damping is significantly improved as compared with the case where a metal part is used. In general, a molding material containing a large amount of an inorganic filler having a high elastic modulus is used for a structural member that is a peripheral component of a vibration source that requires heat resistance, high dimensional accuracy, and dimensional stability.

  On the other hand, it is known that the vibration damping property is better as the elastic modulus of the structural member is lower, and a method of blending a thermoplastic elastomer is disclosed for the purpose of lowering the elastic modulus of the molding material (for example, (See Patent Documents 1, 2, and 3). However, when the elastomer is blended, the elastic modulus of the molded product is lowered when used at a high temperature, so that the use of the product is limited. In addition, in order to give even more vibration control or soundproofing, it is currently necessary to design rubber parts or elastomers on resin parts or to apply vibration control paints. There is a demerit that the number increases and the cost increases. Under these circumstances, a molding material capable of obtaining a molded product having excellent heat resistance, vibration damping properties, and soundproofing properties is desired.

JP 2000-143959 A JP 2000-327894 A Japanese Patent No. 4334630

  In view of the problems of the above-described conventional technology, 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 | molding this.

  This invention is shown by following (1)-(10).

  (1) Two or more types of unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different glass transition temperatures after curing, elastomers that are block copolymers or graft copolymers ( B), the fiber (C) and the curing agent (D), and the elastomer (B) has a glass transition temperature of 10 ° C. or more and less than 80 ° C. and at least one segment (X) and a glass transition temperature of 80 A molding material for vibration damping material composed of at least one segment (Y) having a temperature of not lower than ° C.

  (2) Two or more unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different glass transition temperatures after curing alone, elastomers that are block copolymers or graft copolymers ( B), a fiber (C) and a curing agent (D), and the elastomer (B) is a segment (X) made of a structural unit derived from vinyl acetate, and a segment (Y) made of a structural unit derived from styrene or methyl methacrylate ), A molding material for vibration damping material composed of at least two types of segments.

  (3) Said (1) or (2) whose addition amount of elastomer (B) is 10-40 mass parts with respect to 100 mass parts of unsaturated polyester resin (A-1) or vinyl ester resin (A-2). The molding material for vibration damping materials as described in).

  (4) Said (1)-(3) whose addition amount of fiber (C) is 3-300 mass parts with respect to 100 mass parts of unsaturated polyester resin (A-1) or vinyl ester resin (A-2). ) The damping material molding material according to any one of the above.

  (5) The unsaturated polyester resin (A-1) or the vinyl ester resin (A-2) is composed of two or more kinds of resins whose glass transition temperatures after curing are 100 ° C. or higher and lower than 100 ° C., respectively. The molding material for vibration damping materials according to any one of (1) to (4).

  (6) Any of (1) to (5) above, wherein the molar ratio of the monomer-derived structural unit in segment (X) to the monomer-derived structural unit in segment (Y) is 5: 5 to 3: 7. Molding material for damping material according to any one of the above.

  (7) A damping material obtained by molding the damping material molding material according to any one of (1) to (6).

  (8) The vibration damping material according to (6), wherein a flexural modulus at 130 ° C. is 6 GPa or more.

  (9) The damping material according to (7) or (8), wherein the loss coefficient at 80 ° C. is 0.05 or more and the loss coefficient at 120 ° C. is 0.06 or more.

  (10) A molded product for a structural member obtained by molding the damping material molding material according to any one of (1) to (6).

  The present invention relates to two or more unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different Tg after curing, elastomers (B) and fibers which are block copolymers or graft copolymers. 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. Thus, it is possible to obtain a molding material for damping material having a high loss factor in a wide temperature range.

It is a figure which shows the external appearance of the molded article obtained by transfer-molding the damping material molding material obtained in the Example and the comparative example using a disk molding die. It is a figure which shows the cut-out direction of a test piece in the molded article obtained by carrying out transfer molding of the molding material for damping materials obtained in the Example and the comparative example using a disk molding die.

  The molding material for vibration damping material of the present invention has 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. A segment (X) containing an elastomer (B) that is a coalescence and a fiber (C), the elastomer (B) having a Tg of 10 ° C. or more and less than 80 ° C., and a segment (Tg of 80 ° C. or more) Y) a damping material molding material composed of at least two or more types of segments. Details will be described below.

<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) with different Tg of the cured product, unsaturated polyester resins with different Tg of the cured product (A -1) and a vinyl ester resin (A-2).

  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. What consists of a combination of the above and 2 or more types of unsaturated polyester resin (A-1) and vinyl ester resin (A-2) below 100 degreeC is preferable. Here, about resin with Tg of 100 degreeC or more, it is more preferable that Tg is 100-300 degreeC, and it is further more preferable that it is 150-250 degreeC. Moreover, about resin whose Tg is less than 100 degreeC, it is more preferable that Tg is 30-90 degreeC, and it is further more preferable that it is 40-80 degreeC. In addition, Tg is calculated | required from the temperature in which the loss coefficient (tan-delta) shows the maximum obtained by the measuring method prescribed | regulated to JISK7244- (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 ℃. Next, transfer molding is performed on the obtained molding material 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. 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 δ) 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. Moreover, in the measurement of a tensile complex elastic modulus, it can measure in the range of 20-300 degreeC at intervals of 2 degreeC, and can perform the master plot using a frequency-temperature conversion rule. The temperature at which the obtained loss coefficient (tan δ) is maximum can be adopted as Tg.

  The unsaturated polyester resin (A-1) used in the present invention is a condensation product (unsaturated polyester) by an esterification reaction between 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. The "Polyester Resin Handbook" (Eiichiro Takiyama, Nikkan Kogyo Shimbun, published in 1988) and "Dictionary of Paint Glossary" (Color Material Association) Edit, Gihodo Publishing, published in 1993).

  As the unsaturated polyester used as a raw material for the component (A), those produced by a known method can be used. Specifically, 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 , Ethylene oxide adduct of bisphenol A, propylene oxide of bisphenol A Polyalcohols id adducts are those prepared by reacting as the alcohol component. As the acid component, maleic anhydride, terephthalic acid, fumaric acid, isophthalic acid, and phthalic anhydride are preferable in terms of cost and physical properties. As the 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. When the acid value exceeds 40 mgKOH / g, the phase separation structure of the cured product becomes insufficient, and the vibration damping property and strength of the obtained molded product tend to be insufficient. In addition, the acid value of unsaturated polyester is measured by the method of JISK6901 5.3.

  The unsaturated polyester resin (A-1) is usually one obtained by blending a reactive diluent having an unsaturated group represented 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. 10-250 mass parts is preferable with respect to 100 mass parts of unsaturated polyester single-piece | units, 20-100 mass parts is more preferable, and, as for the addition amount of the reactive diluent which has an unsaturated group, 30-80 mass parts is more preferable. 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.

  You may use reactive diluents other than a styrene monomer as a reactive diluent which has 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. Examples of 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).

  Moreover, as vinyl ester used as a raw material of vinyl ester resin (A-2) (epoxy acrylate resin), it is manufactured by a well-known method, and unsaturated monobasic acid, for example, acrylic acid, is used for epoxy resin. Or it is epoxy (meth) acrylate obtained by making methacrylic acid react. Further, 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. Among these, as an epoxy resin, a bisphenol A type epoxy resin is preferable in terms of price and physical properties. As the unsaturated monobasic acid, 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.

  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 above 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. 10-250 mass parts is preferable with respect to 100 mass parts of vinyl esters, as for the addition amount of the reactive diluent which has an unsaturated group, 30-200 mass parts is more preferable, and 50-150 mass parts is more preferable. 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.

  You may use reactive diluents other than a styrene monomer as a reactive diluent which has 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-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-acryl Iroxypropyl (meth) acrylate, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, methoxytriethylene glycol (meth) acrylate , Butoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, allyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Examples thereof include, but are not limited to, cyclopentenyloxyethyl (meth) acrylate. These may be used alone or in combination.

  The 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.

<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.

  Here, 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. For Tg of segment (X) and segment (Y), 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 δ) 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) and 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.

  As 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. Examples of the segment (X) constituting the elastomer (B) include a polyvinyl acetate segment, polyamide, polylactic acid, polybutylene terephthalate, and polyethylene terephthalate. Examples of the segment (Y) include a polystyrene segment, a polymethyl methacrylate segment, and a poly (ethylene methacrylate) segment. Examples include vinyl chloride, polycarbonate, polyphenylene sulfide, polyphenylene oxide, and polyacrylonitrile. The elastomer (B) is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, and still more preferably 20 to 30 parts by mass with respect to 100 parts by mass of the component (A). When 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.

  When 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. When the elastomer (B) is a graft copolymer, the segment (X) is a main chain, the segment (Y) is a graft copolymer (side chain), and 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.

<Fiber (C)>
Although it does not specifically limit as fiber (C) used by this invention, When using for shaping | molding with flows, such as transfer shaping | molding, the fiber (C) cut | disconnected by about 1.5-25 mm in fiber length 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. As for the compounding quantity of a fiber (C), 3-300 mass parts is preferable with respect to 100 mass parts of components (A), 5-200 mass parts is more preferable, 50-150 mass parts is more preferable. 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.

<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. It is preferable that it is 1-10 mass parts with respect to 100 mass parts of components (A), and, as for a hardening | curing agent, it is more preferable that it is 2-5 mass parts.

  In the present invention, in addition to the above components, a thickener, a thickener, a pigment, an inorganic filler, a curing agent, an internal mold release agent, and the like can be used as necessary.

  Examples of the thickener 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.

  As 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. 100-500 mass parts is preferable with respect to 100 mass parts of components (A), and, as for the compounding quantity of an inorganic filler, 200-450 mass parts is more preferable, and 200-300 mass parts is more preferable. 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.

  Although there is no restriction | limiting in particular in the shape of an inorganic filler, The thing of a weight average particle diameter of 0.5 micrometer-50 micrometers is preferable, 0.5 micrometer-30 micrometers are more preferable, 1 micrometer-20 micrometers are more preferable. When the average particle size is less than 0.5 μm, the viscosity tends to be high, and there is a tendency that a molded product cannot be produced. When the average particle size is more than 50 μm, 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 damping material molding 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. . In the molding method, 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 bending elastic modulus in this case is measured based on JIS K6911. When 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 conditions of 23 ° C. and 130 ° C., 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, a 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. And a bending elastic modulus is computed using the following formula | equation (1).

  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 coefficient 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. using a φ120 mm disk molding die (fan gate) to obtain a molded product. A test piece having a length of 45 mm × width of 3 mm × thickness of 3 mm was cut out from the obtained molded product, and the cut-out test piece was sinusoidally with a frequency of 1 Hz using a tensile complex modulus measuring apparatus (manufactured by GABO, EPLEXOR100N). A loss factor (tan δ) 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. Moreover, in the measurement of a tensile complex elastic modulus, the range of 20-130 degreeC can be measured by 2 degreeC space | interval, and the master plot using a frequency-temperature conversion rule can be performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example.

<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.

<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, then maleic anhydride 20 moles, phthalic anhydride 30 moles. 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.

<Vinyl ester resin (Tg: 130 ° C.)>
A compound composition comprising 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 casting plate (manufacturing method is described below) prepared only with each unsaturated polyester resin or vinyl ester resin. The temperature at which the loss factor (tan δ) is maximum obtained by the measurement method specified in JIS K7244- (4) was adopted as Tg.

  More specifically, 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 φ120 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 δ) 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. In addition, the test piece was installed with the distance between clamps of 30 mm. Moreover, in the measurement of the tensile complex elastic modulus, the range of 20-300 degreeC was measured at 2 degreeC intervals, and the master plot using the frequency-temperature conversion rule was performed. The temperature at which the obtained loss coefficient (tan δ) was maximized was adopted as Tg.

<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 material for damping materials of Examples 1-11 and Comparative Examples 1-12 was 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.

  FIG. 1 is a view showing an appearance of a molded product obtained by transfer molding 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, and 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.

  Next, as shown in FIG. 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). About this obtained test piece 4a, 4b, loss factor (tan-delta) was measured based on JISK7244- (4), and the average value of the test piece of an orientation direction and a non-orientation direction was shown in Table 1 and Table 2. . 2A is a top view of the disk molding die, and FIG. 2B is a left side view of the disk molding die.

  More specifically, 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 δ) 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 conditions of 23 ° C. and 130 ° C., 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, a 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. And the bending elastic modulus was computed using the following formula | equation (1). The results are shown in Tables 1 and 2.

Moreover, about bending strength, bending strength was computed using the following formula | equation (2). When the broken part of the test piece was other than the central part obtained by dividing the test piece into three equal parts, this was not adopted as the test value, and the retest was performed. The results are shown in Tables 1 and 2.

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.

  INDUSTRIAL APPLICABILITY The present invention can be used as a molding material for obtaining a molded article for a structural member that requires vibration damping.

DESCRIPTION OF SYMBOLS 1 Molded product 2 Molded product main body 3 Gate part 4 Test piece

Claims (9)

Two or more kinds of unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different glass transition temperatures after curing alone, elastomer (B) which 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. It is comprised from at least 1 sort (s) of a certain segment (Y), and the molar ratio of the structural unit derived from the monomer in the said segment (X) and the structural unit derived from the monomer in the said segment (Y) is 5: 5 to 3: 7. Molding material for damping material. Two or more kinds of unsaturated polyester resins (A-1) or vinyl ester resins (A-2) having different glass transition temperatures after curing alone, elastomer (B) which 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; For a damping material comprising two or more types of segments, and 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. The damping amount 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. The addition amount of a fiber (C) is 3-300 mass parts with respect to 100 mass parts of unsaturated polyester resin (A-1) or vinyl ester resin (A-2), The any one of Claims 1-3 Molding material for damping material. The said unsaturated polyester resin (A-1) or vinyl ester resin (A-2) consists of 2 or more types of resin whose glass transition temperature after hardening each is 100 degreeC or more and less than 100 degreeC, respectively. The molding material for damping materials in any one of 1-4. The damping material obtained by shape | molding the molding material for damping materials in any one of Claims 1-5 . The vibration damping material according to claim 6, wherein the bending elastic modulus at 130 ° C is 6 GPa or more. The damping material according to claim 6 or 7 , wherein a loss coefficient at 80 ° C is 0.05 or more and a loss coefficient at 120 ° C is 0.06 or more. A molded article for a structural member obtained by molding the damping material molding material according to any one of claims 1 to 5 .

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