CN107915936B - Composite particle and method for producing same - Google Patents
Composite particle and method for producing same Download PDFInfo
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- CN107915936B CN107915936B CN201710238219.9A CN201710238219A CN107915936B CN 107915936 B CN107915936 B CN 107915936B CN 201710238219 A CN201710238219 A CN 201710238219A CN 107915936 B CN107915936 B CN 107915936B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
Abstract
The invention provides a composite particle and a method for producing the same, which can improve the solubility of polyvinyl formal resin in epoxy resin. The present invention provides composite particles which are easily dissolved in an epoxy resin by kneading a polyvinyl formal resin having fine pores with a liquid epoxy resin without melting the polyvinyl formal resin, and filling the fine pores with the liquid epoxy resin, and a method for producing the composite particles. The liquid epoxy resin may be one liquid epoxy resin, a mixture of at least two liquid epoxy resins, or a solution of at least one solid epoxy resin in at least one liquid epoxy resin.
Description
Technical Field
The present invention relates to composite particles having improved solubility in epoxy resins and a method for producing the same. The composite particles are particles obtained by mixing a liquid epoxy resin into fine-pore polyvinyl formal particles, and filling the fine pores with the liquid epoxy resin.
Background
The composite particles of the present invention can be used as a toughening agent for epoxy resins. Epoxy resins are widely used in the fields of adhesives, paints, civil engineering and construction materials, electric and electronic insulating materials, sealing materials, matrix resins for composite materials, and the like because of their excellent adhesiveness, strength, heat resistance, mechanical properties, and electrical properties.
In particular, when an epoxy resin is used as a matrix resin of a composite material, molding is often performed using an intermediate material called a prepreg, and characteristics such as tack (tack) and drape (drape) are required. Further, a thermoplastic resin is often blended for the purpose of improving adhesion between the carbon fibers and the matrix resin. Polyvinyl acetals are frequently used as the thermoplastic resin, and polyvinyl formal resins are representative thereof.
In addition, for the purpose of maintaining the heat resistance (glass transition temperature) of the cured epoxy resin and improving the toughness, polyvinyl acetals having carboxyl groups introduced therein may be uniformly compatible with the epoxy resin. Polyvinyl acetals used as toughening agents for composite materials are represented by polyvinyl formal resins. In order to uniformly compatibilize the polyvinyl formal resin in the epoxy resin, it is necessary to heat the epoxy resin at 130 ℃ or higher, and there is a concern about the trouble of the dissolution step and the thermal history in the dissolution step.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent publication No. Hei 4-15253
[ patent document 2] Japanese patent publication No. Hei 4-80054
[ non-patent document ]
[ non-patent document 1] general description of epoxy resin volume 4 application part II page 187, compiled by the epoxy resin technical Association
Disclosure of Invention
[ problems to be solved by the invention ]
In order to obtain the toughening effect of the cured epoxy resin by the polyvinyl formal resin, it is necessary to uniformly dissolve the polyvinyl formal resin in the epoxy resin. However, the polyvinyl formal resin must be heated from 130 ℃ to 150 ℃ when dissolved in the epoxy resin. The present invention addresses the problem of providing composite particles having good solubility in epoxy resins even at temperatures of 120 ℃ or lower.
[ means for solving problems ]
In order to improve the solubility of a polyvinyl formal resin in an epoxy resin, the present inventors have obtained composite particles which are easily dissolved in an epoxy resin by mixing a liquid epoxy resin with a polyvinyl formal resin having fine pores without melting the polyvinyl formal resin, and filling the fine pores with the liquid epoxy resin.
Namely, the present invention is as follows.
[1] A composite particle comprising a component (B) filled in pores of particles of the component (A), wherein the content of the component (A) is 50 to 99 wt% and the content of the component (B) is 1 to 50 wt%,
component A: a polyvinyl formal resin;
component B: liquid epoxy resin.
[2] The composite particles according to [1], wherein the polyvinyl formal resin of component A is a compound comprising a constituent unit a, a constituent unit b, and a constituent unit c,
[3] The composite particles according to [1] or [2], wherein the polyvinyl formal resin of component A is a compound further comprising a constituent unit d,
In the formula of constituent unit d, R1Independently hydrogen or an alkyl group of carbon number 1 to 5.
[4] The composite particle as described in any one of [1] to [3], wherein the polyvinyl formal resin of component A is in a granular form and has a pore volume of 0.1ml/g to 0.9ml/g in the interior of the particle, and the particle diameter is 10 μm to 2000 μm.
[5] The composite particle according to any one of [1] to [4], wherein the liquid epoxy resin of the component B is liquid at 100 ℃.
[6] The composite particle according to any one of [1] to [5], wherein the liquid epoxy resin of the component B is a compound having at least 1 oxirane group.
[7] The composite particle according to any one of [1] to [6], wherein the liquid epoxy resin of the component B is one liquid epoxy resin, is obtained by mixing at least two liquid epoxy resins, or is obtained by dissolving at least one solid epoxy resin in at least one liquid epoxy resin.
[8] A method for producing composite particles according to any one of [1] to [7], wherein the polyvinyl formal resin as the component A is kneaded with the liquid epoxy resin as the component B without melting.
[ Effect of the invention ]
The present invention can provide composite particles of a polyvinyl formal resin and an epoxy resin, which are easily soluble in the epoxy resin, and a method for producing the same.
Drawings
FIG. 1 is a photomicrograph of the polyvinyl formal resin particles of component A taken at 350 times.
Detailed Description
The form of the present invention is a composite particle. The composite particle is characterized in that: the polyvinyl formal resin having fine pores is kneaded with a liquid epoxy resin without melting, and the fine pores are filled with the liquid epoxy resin.
The composite particles of the present invention comprise a polyvinyl formal resin as a component A and a liquid epoxy resin as a component B. Component B may also contain a reactive diluent.
The content of the polyvinyl formal resin of component a in the composite particles is 50 to 99% by weight, preferably 70 to 90% by weight.
When the content of the polyvinyl formal resin as the component A is 50 wt% or more, the content of the liquid epoxy as the component B is reduced, and the resulting composite can be handled in the form of particles, thereby improving the handling properties. Further, since the liquid component is reduced, agglomeration of particles due to dissolution of the surface of the composite particles during storage is prevented, and the composite particles are not agglomerated, and thus the solubility in the epoxy resin is prevented from being lowered, which is preferable.
When the content of the polyvinyl formal resin as the component a is 99% by weight or less, composite particles which are easily dissolved in the epoxy resin and are the object of the present invention can be obtained, and therefore, the content is preferable.
The content of the liquid epoxy resin of component B in the composite particles is 1 to 50% by weight, preferably 10 to 30% by weight.
When the content of the epoxy resin in the component B is 50 wt% or less, the composite can be handled in a particulate form, and the handling property is improved. Further, when the amount of the liquid epoxy resin as the component B is more than 1% by weight, the surface dissolution of the composite particles is suppressed during storage, and the particles are prevented from being agglomerated with each other, and are not agglomerated, and the solubility in the epoxy resin is prevented from being lowered, which is preferable.
When the content of the epoxy resin in the component B is 1 wt% or more, composite particles which are easily dissolved in the epoxy resin and are the object of the present invention can be obtained, and therefore, the content is preferable.
The polyvinyl formal resin as the component a in the present invention preferably contains the following constituent unit a, constituent unit b, and constituent unit c. Further, the constituent unit d may be included.
The total content of the constituent units a to d in the polyvinyl formal resin of component a is preferably 80% to 100% based on the total constituent units. Examples of the other constituent units that may be contained in the polyvinyl formal resin of component A include intermolecular formal units and hemiformal units. The content of vinyl formal chain units other than the constituent units a is preferably less than 5 mol%.
The constituent unit a is a constituent unit having a formal site, and can be formed by the reaction of continuous polyvinyl alcohol chain units with formaldehyde (HCHO).
The constituent unit b is a constituent unit containing a vinyl acetate chain.
The constituent unit c is a constituent unit containing a vinyl alcohol chain.
Constituent unit d is a chain having a carboxyl group, R in the formula1Hydrogen or an alkyl group having 1 to 5 carbon atoms is preferable, and hydrogen or an alkyl group having 1 to 3 carbon atoms is more preferable.
In the polyvinyl formal resin of the component A, the constituent units a to d may be arranged regularly (block copolymer, alternating copolymer, etc.) or may be arranged randomly (random copolymer), but preferably are arranged randomly.
The respective constituent units in the polyvinyl formal resin of component a are preferably: the content of the constituent unit a is 49.9 to 80 mol%, the content of the constituent unit b is 0.1 to 49.9 mol%, the content of the constituent unit c is 0.1 to 49.9 mol%, and the content of the constituent unit d is 0 to 49.9 mol%. More preferably: the content of the constituent unit a is 49.9 to 80 mol%, the content of the constituent unit b is 1 to 30 mol%, the content of the constituent unit c is 1 to 30 mol%, and the content of the constituent unit d is 0 to 30 mol%.
In order to sufficiently obtain chemical resistance, flexibility, abrasion resistance and mechanical strength of the polyvinyl formal resin of the component A, the content of the constituent unit a is preferably 49.9 mol% or more. The constituent unit a in the polyvinyl formal resin of component A is formed by formalizing vinyl alcohol chains continuously present in the molecular chain. That is, it is difficult to formalize a discontinuous vinyl alcohol chain (for example, 1 vinyl alcohol chain sandwiched between 2 vinyl formal chains) in the molecular chain. Therefore, it is preferable that the content of the constituent unit a is 80.0 mol% or less in the synthesis.
When the content of the constituent unit a is 0.1 mol% or more, the solubility of the polyvinyl formal resin of component A in a solvent or the solubility in an epoxy resin becomes good. When the content of the constituent unit b is 49.9 mol%, the polyvinyl formal resin of the component a is preferably resistant to deterioration in chemical resistance, flexibility, abrasion resistance and mechanical strength.
In view of solubility in a solvent or solubility in an epoxy resin, the content of the constituent unit c is preferably set to 49.9 mol%. In the production of the polyvinyl formal resin as the component A, the constituent unit b and the constituent unit c are in equilibrium with each other when the polyvinyl alcohol chain is formalized, and therefore the content of the constituent unit c is preferably 0.1 mol% or more.
In view of good viscosity and solubility in an epoxy resin, the content of the constituent unit d is preferably 49.9 mol% or less. In order to obtain a cured epoxy resin having excellent toughness while maintaining heat resistance (glass transition temperature) by smoothly proceeding a crosslinking reaction between the side chain carboxyl group and the epoxy resin, the content of the constituent unit d is preferably 0.1 mol% or more.
The weight average molecular weight of the polyvinyl formal resin of the component A is preferably 5000 to 300000, more preferably 10000 to 150000.
When the weight average molecular weight of the polyvinyl formal resin of component A is 5000 or more, the polyvinyl formal resin is preferably because the solubility in the epoxy resin is improved and the toughening action of the polyvinyl formal resin is obtained. On the other hand, when the weight average molecular weight is 300000 or less, the viscosity at the time of dissolution does not excessively increase, and it is preferable in terms of workability at the time of molding.
The polyvinyl formal resin of component A was granular, and many voids were observed in the granules (FIG. 1). Preferably: the particles have a pore volume within the particle of 0.1m1/g to 0.9 ml/g.
The composite particles of the present invention are obtained by containing a liquid epoxy resin in the pores. By filling the pores with a liquid epoxy resin in advance, the solubility when added to the epoxy resin is improved.
In addition, when the pore volume is 0.1ml/g or more, the composite particles of the present invention which are easily dissolved in the epoxy resin can be easily obtained. The upper limit of the pore volume is not particularly limited, but is preferably about 0.9 ml/g.
The polyvinyl formal resin of component A is in the form of pellets. The particle diameter thereof is preferably 10 μm to 2000. mu.m, more preferably 100 μm to 1500. mu.m.
When the particle diameter is 10 μm or more, the surface area per unit mass of the polyvinyl formal resin particles of component a is insufficient, and therefore the liquid epoxy resin of component B is not attached to the particle surface but impregnated into the particle pores sufficiently, and further, the surface of the polyvinyl formal resin particles of component a is not dissolved by the liquid epoxy resin of component B to cause agglomeration of the composite particles, and therefore, the composite particles are preferably soluble in the epoxy resin.
When the particle diameter is 2000 μm or less, it takes time to prevent the composite particles from dissolving in the epoxy resin, and the composite particles are easily dissolved in the epoxy resin, which is a feature of the present invention, and therefore, the particle diameter is preferable.
The liquid epoxy resin of component B is preferably an epoxy resin that is liquid at least at 100 ℃, and more preferably an epoxy resin that is liquid at 25 ℃ in view of operation at room temperature.
When the temperature at which the epoxy resin of the component B becomes liquid is 100 ℃ or lower, it is preferable that the polyvinyl formal resin of the component A is mixed with the epoxy resin because the melting of a part of the polyvinyl formal resin in the epoxy resin is suppressed and the composite particles are held.
The type of the liquid epoxy resin of the component B is not particularly limited as long as it is liquid at 100 ℃, but is preferably an epoxy resin which can be easily mixed with a polyvinyl formal resin.
In addition, even a solid epoxy resin can be used in the present invention if it is mixed with a liquid epoxy resin and is liquid at 100 ℃.
The epoxy resin is a compound having 2 or more epoxy groups in the molecule, and: bisphenol epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, glycidyl amine epoxy resins, isocyanate-modified epoxy resins, urethane-modified epoxy resins, alicyclic epoxy resins, biphenyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, fluorene epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more.
As the bisphenol type epoxy resin, there are: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol a type epoxy resin, and the like.
As the bisphenol a type epoxy resin, a product of mitsubishi chemical corporation comprises: jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1004, jER1055, jER1007, jER1009, jER 1010. The product of Diegon (DIC) comprises: epiclon (Epiclon)840, Epiclon (Epiclon)850, Epiclon (Epiclon)860, Epiclon (Epiclon)1050, Epiclon (Epiclon)1055, Epiclon (Epiclon)2050, Epiclon (Epiclon)3050, all of which are included in the article by Yongchang York corporation: airbet (Epotohto) YD-127, Airbet (Epotohto) YD-128, and Airbet (Epotohto) YD-134.
As bisphenol F type epoxy resin, Mitsubishi chemical corporation products contain: jER806, jER807, jER4004P, jER4005P, jER4007P, jER4010P, and the like. The product of Diegon (DIC) contains Epiclon 830, and the product of Dondow chemical corporation contains: airbet (Epotohto) YD-170, Airbet (Epotohto) YD-2001, Airbet (Epotohto) YD-2004, and Airbet (Epotohto) YD-2005 RL.
The bisphenol S type epoxy resin comprises: epiclon (Epiclon) EXA-1514, Epiclon (Epiclon) EXA-1515, manufactured by Dielsen (DIC) Ltd.
The brominated bisphenol A epoxy resin comprises: jER5046B80, jER 5047B75, jER 5050T60, jER 5050, jER 5051, manufactured by Mitsubishi chemical corporation, or Aipison clone (Epiclon)152, Aipison clone (Epiclon)153, manufactured by Nippon ink chemical industries, Ltd.
The phenol novolac type epoxy resin contains: jER152, jER154 of Mitsubishi chemical corporation, or Epiclon (Epiclon) N-740, Epiclon (Epiclon) N-770, Epiclon (Epiclon) N-775 of Dietson chemical corporation; products of eastern chemical company Limited include Aibert (Epotohto) YDPN-638 and the like.
The cresol novolac type epoxy resin contains: epiclon (Epiclon) N-660, Epiclon (Epiclon) N-665, Epiclon (Epiclon) N-670, Epiclon (Epiclon) N-673, Epiclon (Epiclon) N-695, made by Diegon (DIC) Co., Ltd, or EOCN-1020, EOCN-102S, EOCN-104S, made by Nippon chemical Co., Ltd.
The glycidyl amine type epoxy resin comprises: the products ELM-120, ELM-434HV, Epiclon 430-L, or Epiclon 430, or Eibert (Epotohto) YH-434L, or Jer604, or those of Mitsubishi chemical corporation, or GAN, GOT, of the products of Nippon chemical corporation, respectively, of Sumitomo chemical corporation, of Diegon chemical corporation, of Diego corporation, of Toyobo, of Japan.
The isocyanate-modified epoxy resin or urethane-modified epoxy resin comprises: AER4152 available from Asahi Kasei Chemicals Ltd, and ACR1348 available from Aidicke (ADEKA) Ltd.
The alicyclic epoxy resin includes: cyrocide (Celloxide)2021, and Cyrocide (Celloxide)2080, which are products of Daicel Chemical Industries, Inc., and the like.
The biphenyl type epoxy resin comprises: JeR XY4000, JeR YL6121H, and JeR YL6640, which are products of Mitsubishi chemical corporation, or NC-3000, which is a product of Nippon chemical corporation, and the like.
The naphthalene type epoxy resin comprises: epiclon HP4032 available from Diegon (DIC) or NC-7000 and NC-7300 available from Nippon Chemicals.
The dicyclopentadiene type epoxy resin contains: epiclon (Epiclon) HP7200, Epiclon (Epiclon) HP7200L, Epiclon (Epiclon) HP7200H, made by Diegon chemical Co., Ltd, XD-1000-1L, XD-1000-2L, and the like.
The liquid epoxy resin of component B is a compound having at least 1 oxirane group, and may contain a reactive diluent. The reactive diluent is preferably lower in molecular weight than a general epoxy resin and has a viscosity of 2 to 100 mPas at 25 ℃.
By adding a reactive diluent, composite particles that are more readily soluble in the epoxy resin can be obtained. Further, by not excessively adding a large amount, the melting of the surface of the polyvinyl formal particles of the component A is suppressed, and the agglomeration of the particles by fusion is prevented.
The reactive diluent includes the following compounds as monoepoxides.
There are alcohol-based allyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and higher alcohol glycidyl ether.
The phenol series has: phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, tolyl glycidyl ether, phenol (EO)5Glycidyl ether, sec-butyl phenyl glycidyl ether, cardanol diglycidyl ether and dibromophenyl glycidyl ether.
Other compounds are: glycidyl methacrylate, styrene oxide, tertiary carboxylic acid glycidyl ester.
Reactive diluents as diepoxides are: n, N' -diglycidylaniline, N-diglycidyl-O-toluidine, hexahydrophthalic anhydride diglycidyl ester, polyethylene glycol diglycidyl ether (N ═ 2 to 13), ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether (N ═ 3 to 11), neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl-O-phthalate, dibromoneopentyl glycol diglycidyl ether.
Reactive diluents as the triepoxides are: glycerol polyglycidyl ether and trimethylolpropane polyglycidyl ether.
The liquid epoxy resin of component B may be one liquid epoxy resin or a mixture of at least two epoxy resins. In addition, at least one solid epoxy resin may be dissolved in at least one liquid epoxy resin.
The method for kneading the polyvinyl formal resin of the component a and the epoxy resin of the component B is not particularly limited as long as each component can be kneaded uniformly, and a high-speed mixer, a belt blender, a planetary mixer, a kneader, and the like are preferable.
The temperature for kneading the polyvinyl formal resin of the component A and the epoxy resin of the component B is preferably 0 ℃ to 100 ℃. More preferably from 20 ℃ to 50 ℃. The mixing at room temperature is most suitable in terms of workability.
[ examples ]
The embodiments of the present invention will be described below with reference to examples, which are illustrative of the embodiments, but the present invention is not limited to the examples.
The polyvinyl formal resins used in examples 1 to 4 and comparative examples 1 to 2 were PVF-K type (weight average molecular weight 50,000) of binilac (Vinylec) (trademark) manufactured by JNC corporation, and the polyvinyl formal resins used in example 5 and comparative examples 3 to 4 were PVF-E type (weight average molecular weight 100,000) of binilac (Vinylec) (trademark) manufactured by JNC corporation. As for the average particle diameter of the lot used in this evaluation, PVF-K was 342 μm and PVF-E was 717 μm. The porosity of the fine pores was 0.71ml/g, which was determined from a photograph of a cross section of a representative particle having an average particle diameter of approximately 342 μm.
[ example 1]
< production of composite particles Using high-speed Mixer >
2000g of a polyvinyl formal resin (binicarb (trade mark) manufactured by JNC Co., Ltd., grade: PVF-K) was charged into a high-speed mixer, 500g of a bisphenol A type epoxy resin (jER 828 (trade mark) manufactured by Mitsubishi chemical Co., Ltd.) was added from the top of the high-speed mixer while stirring at 1000rpm, and then stirring was continued at room temperature for 15 minutes to produce composite particles.
< test for dissolution of composite particles in epoxy resin >
The prepared composite particles were weighed out to 12.5g, and added to a 200mL beaker in which 87.5g of jER828 (trademark) was weighed in advance, and the solubility was confirmed at 90 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the composite particles was confirmed 90 minutes after the dissolution initiation.
[ example 2]
< production of composite particles Using high-speed Mixer >
2000g of a polyvinyl formal resin (binicare (trade mark) manufactured by JNC Co., Ltd., grade: PVF-K) was charged into a high-speed mixer, and a mixed solution of 475g of a bisphenol A type epoxy resin (jER 828 (trade mark) manufactured by Mitsubishi chemical Co., Ltd.) and 25g of 1, 6-hexanediol diglycidyl ether (Denacol EX212 (trade mark) manufactured by Nagase ChemteX Co., Ltd.) as a reactive diluent was added from the upper part of the high-speed mixer while stirring at 1000rpm, and then stirring was continued at room temperature for 15 minutes to produce composite particles.
< test for dissolution of composite particles in epoxy resin >
The prepared composite particles were weighed out to 12.5g, and added to a 200mL beaker in which 87.5g of jER828 (trademark) was weighed in advance, and the solubility was confirmed at 90 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the composite particles was confirmed 80 minutes after the start of the autolysis.
[ example 3]
< production of composite particles Using high-speed Mixer >
2000g of a polyvinyl formal resin (binicare (trade mark) manufactured by JNC Co., Ltd., grade: PVF-K) was charged into a high-speed mixer, and a mixed solution of 450g of a bisphenol A type epoxy resin (jER 828 (trade mark) manufactured by Mitsubishi chemical Co., Ltd.) and 50g of 1, 6-hexanediol diglycidyl ether (Denacol EX212 (trade mark) manufactured by Nagase ChemteX Co., Ltd.) as a reactive diluent was added from the upper part of the high-speed mixer while stirring at 1000rpm, and then stirring was continued at room temperature for 15 minutes to produce composite particles.
< test for dissolution of composite particles in epoxy resin >
The prepared composite particles were weighed out to 12.5g, and added to a 200mL beaker in which 87.5g of jER828 (trademark) was weighed in advance, and the solubility was confirmed at 90 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the composite particles was confirmed 70 minutes after the start of the autolysis.
[ example 4]
< production of composite particles Using high-speed Mixer >
2000g of a polyvinyl formal resin (binicare (trade mark) manufactured by JNC Co., Ltd., grade: PVF-K) was charged into a high-speed mixer, and a mixed solution of 375g of a bisphenol A type epoxy resin (jER 828 (trade mark) manufactured by Mitsubishi chemical Co., Ltd.) and 125g of 1, 6-hexanediol diglycidyl ether (Denacol EX212 (trade mark) manufactured by Nagase ChemteX Co., Ltd.) as a reactive diluent was added from the upper part of the high-speed mixer while stirring at 1000rpm, and then stirring was continued at room temperature for 15 minutes to produce composite particles.
< test for dissolution of composite particles in epoxy resin >
The prepared composite particles were weighed out to 12.5g, and added to a 200mL beaker in which 87.5g of jER828 (trademark) was weighed in advance, and the solubility was confirmed at 90 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the composite particles was confirmed 45 minutes after the start of the autolysis.
[ example 5]
< production of composite particles Using high-speed Mixer >
2000g of a polyvinyl formal resin (binicarb (Vinylec) (trademark) manufactured by JNC Co., Ltd., grade: PVF-E) was charged into a high-speed mixer, 500g of a bisphenol A type epoxy resin (jER 828 (trademark) manufactured by Mitsubishi chemical Co., Ltd.) was added from the top of the high-speed mixer while stirring at 1000rpm, and then stirring was continued at room temperature for 15 minutes to produce composite particles.
< test for dissolution of composite particles in epoxy resin >
12.5g of the produced composite particles were weighed and added to a 200mL beaker in which 87.5g of jER828 (trademark) was previously weighed, and the solubility was confirmed at 120 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the composite particles was confirmed 180 minutes after the start of the autolysis.
Comparative example 1
< comparative particle >
A polyvinyl formal resin (Binilay (Vinylec) (trademark) manufactured by JNC Co., Ltd., grade: PVF-K) was weighed in an amount of 10g, without blending with a liquid epoxy resin by a high-speed mixer.
< comparative particle dissolution test in epoxy resin >
A weighed amount of 10g of a polyvinyl formal resin was added to a 200mL beaker containing 90g of jER828 (trademark) weighed in advance, and the solubility was confirmed at 90 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
After 6 hours, it was also confirmed that the undissolved polyvinyl formal resin remained.
Comparative example 2
< comparative particle >
A polyvinyl formal resin (Binilay (Vinylec) (trademark) manufactured by JNC Co., Ltd., grade: PVF-K) was weighed in an amount of 10g, without blending with a liquid epoxy resin by a high-speed mixer.
< comparative particle dissolution test in epoxy resin >
A weighed amount of 10g of a polyvinyl formal resin was added to a 200mL beaker containing 90g of jER828 (trademark) weighed in advance, and the solubility was confirmed at 130 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the polyvinyl formal resin was confirmed 90 minutes after the onset of the autolysis at 130 ℃.
Comparative example 3
< comparative particle >
A polyvinyl formal resin (Binilay (Vinylec) (trademark) manufactured by JNC Co., Ltd., grade: PVF-E) was weighed in an amount of 10g, without blending with a liquid epoxy resin by a high-speed mixer.
< comparative particle dissolution test in epoxy resin >
A weighed amount of 10g of a polyvinyl formal resin was added to a 200mL beaker containing 90g of jER828 (trademark) weighed in advance, and the solubility was confirmed at 120 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
After 6 hours, it was also confirmed that the undissolved polyvinyl formal resin remained.
Comparative example 4
< comparative particle >
A polyvinyl formal resin (Binilay (Vinylec) (trademark) manufactured by JNC Co., Ltd., grade: PVF-E) was weighed in an amount of 10g, without blending with a liquid epoxy resin by a high-speed mixer.
< comparative particle dissolution test in epoxy resin >
A weighed amount of 10g of a polyvinyl formal resin was added to a 200mL beaker containing 90g of jER828 (trademark) weighed in advance, and the solubility was confirmed at 150 ℃ while stirring at 120rpm using a laboratory stirrer. The content of the polyvinyl formal resin in the dissolved solution was 10% by weight.
< results of dissolution >
The dissolution of the polyvinyl formal resin was confirmed 180 minutes after the autolysis at 150 ℃.
The experimental results are summarized in tables 1 to 4.
TABLE 1. composition of each particle of examples 1 to 4 and polyvinyl formal resin of comparative examples 1 to 2
TABLE 2. composite particle composition of example 5 and polyvinyl formal resins of comparative examples 3 to 4
TABLE 3 evaluation results of solubility of the composite particles of examples 1 to 4 and the polyvinyl formal resins of comparative examples 1 to 2 in epoxy resins
Solubility: o is dissolution. X: dissolution was insufficient.
*: even after 360 minutes, it was not dissolved.
TABLE 4 evaluation results of solubility of the composite particle composition of example 5 in the epoxy resin with the polyvinyl formal resins of comparative examples 3 to 4
Solubility: o is dissolution. X: dissolution was insufficient.
*: even after 360 minutes, it was not dissolved.
As can be seen from tables 1 and 3, the composite particles of examples (weight average molecular weight: 50,000) had better solubility in epoxy resins at 90 ℃ than the polyvinyl formal resin particles of comparative example 1. It was also confirmed that the dissolution time can be shortened by increasing the content of the reactive diluent.
As can be seen from tables 2 and 4, the composite particles of examples (weight average molecular weight: 100,000) had better solubility in epoxy resins at 120 ℃ than the polyvinyl formal resin particles of comparative example 3.
In the case of the polyvinyl formal resin having a weight average molecular weight of 50,000, it is understood that the composite particles of the present invention require a dissolution temperature of 130 ℃ as in comparative example 2, but are also dissolved at a temperature of 100 ℃ or lower.
In addition, in the case of the polyvinyl formal resin with the weight average molecular weight of 100,000, the dissolution temperature of 150 ℃ is required as in comparative example 4, but the composite particles of the present invention are dissolved at a temperature as low as 120 ℃.
[ industrial applicability ]
The composite particle of the invention can be used as a toughening agent of a carbon fiber composite material.
Claims (8)
1. A composite particle, characterized by: the fine pores of the particles in the component A are filled with the component B, the content of the component A is 50 to 80 wt%, the content of the component B is 20 to 50 wt%,
the component A is as follows: a polyvinyl formal resin;
the component B: liquid epoxy resin.
2. The composite particle according to claim 1, wherein: the polyvinyl formal resin of component A is a compound comprising a constituent unit a, a constituent unit b and a constituent unit c,
3. the composite particle according to claim 1 or 2, wherein: the polyvinyl formal resin of component A is a compound further comprising a constituent unit d,
in the formula of constituent unit d, R1Independently hydrogen or an alkyl group of carbon number 1 to 5.
4. The composite particle according to claim 1 or 2, wherein: the polyvinyl formal resin of the component A is in the form of particles, and has a pore volume of 0.1 to 0.9ml/g in the interior of the particles, and a particle diameter of 10 to 2000. mu.m.
5. The composite particle according to claim 1 or 2, wherein: the liquid epoxy resin of the component B is liquid at least at 100 ℃.
6. The composite particle according to claim 1 or 2, wherein: the liquid epoxy resin of the component B is a compound having at least 1 oxirane group.
7. The composite particle according to claim 1 or 2, wherein: the liquid epoxy resin of the component B is one kind of liquid epoxy resin, one obtained by mixing at least two kinds of liquid epoxy resins, or one obtained by dissolving at least one kind of solid epoxy resin in at least one kind of liquid epoxy resin.
8. A method for producing the composite particle according to any one of claims 1 to 7, characterized in that: the polyvinyl formal resin as the component A is kneaded with the liquid epoxy resin as the component B without melting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-198920 | 2016-10-07 | ||
| JP2016198920 | 2016-10-07 |
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| CN107915936A CN107915936A (en) | 2018-04-17 |
| CN107915936B true CN107915936B (en) | 2021-02-19 |
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| CN201710238219.9A Active CN107915936B (en) | 2016-10-07 | 2017-04-12 | Composite particle and method for producing same |
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| JP (1) | JP2018062643A (en) |
| CN (1) | CN107915936B (en) |
| TW (1) | TW201813999A (en) |
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| WO2019202762A1 (en) * | 2018-04-20 | 2019-10-24 | Jnc株式会社 | Prepreg and fiber-reinforced composite material using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076626A (en) * | 1976-01-19 | 1978-02-28 | Union Carbide Corporation | High strength cast modules for supporting reverse osmosis membranes |
| JPS58108247A (en) * | 1981-12-21 | 1983-06-28 | Shikoku Chem Corp | Epoxy resin composition containing polyvinyl butyral resin |
| JP2002265621A (en) * | 2001-03-09 | 2002-09-18 | Japan U-Pica Co Ltd | Porous cured material and method for producing the same |
| JP2004244607A (en) * | 2002-12-20 | 2004-09-02 | Sk Kaken Co Ltd | Porous material |
| CN103467912A (en) * | 2013-08-08 | 2013-12-25 | 天津市凯华绝缘材料有限公司 | High flexibility epoxy resin composition |
-
2017
- 2017-04-12 CN CN201710238219.9A patent/CN107915936B/en active Active
- 2017-08-10 TW TW106127160A patent/TW201813999A/en unknown
- 2017-08-21 JP JP2017158773A patent/JP2018062643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076626A (en) * | 1976-01-19 | 1978-02-28 | Union Carbide Corporation | High strength cast modules for supporting reverse osmosis membranes |
| JPS58108247A (en) * | 1981-12-21 | 1983-06-28 | Shikoku Chem Corp | Epoxy resin composition containing polyvinyl butyral resin |
| JP2002265621A (en) * | 2001-03-09 | 2002-09-18 | Japan U-Pica Co Ltd | Porous cured material and method for producing the same |
| JP2004244607A (en) * | 2002-12-20 | 2004-09-02 | Sk Kaken Co Ltd | Porous material |
| CN103467912A (en) * | 2013-08-08 | 2013-12-25 | 天津市凯华绝缘材料有限公司 | High flexibility epoxy resin composition |
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| Publication number | Publication date |
|---|---|
| JP2018062643A (en) | 2018-04-19 |
| CN107915936A (en) | 2018-04-17 |
| TW201813999A (en) | 2018-04-16 |
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